Electrochemically debonded adhesive compositions

Abstract

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

Description

Technical Field

[0001] This invention relates to curable adhesive compositions that can be detached from a specific substrate to which they are applied. More specifically, this invention relates to curable and electrochemically detachable adhesive compositions comprising a polymerizable electrolyte. Background Technology

[0002] Adhesive bonding and polymer coatings are commonly used in the assembly and finishing of finished products. They are used in place of mechanical fasteners such as screws, bolts, and rivets to provide adhesion with reduced machine costs and greater applicability in the manufacturing process. Adhesive bonding distributes stress evenly, reduces the likelihood of fatigue, and seals joints against corrosive substances.

[0003] While adhesive bonding offers many advantages over mechanical fasteners, in practical applications (e.g., in the recycling of the primary adhesive material), adhesive-bonded items tend to be difficult to remove when necessary. Removal of the adhesive by mechanical methods (such as sandblasting or wire brushing) is often ruled out, partly because the adhesive is embedded between the substrates and is therefore difficult to access or grind without damaging the substrate surfaces. Removal by applying chemicals and / or high temperatures (as disclosed in U.S. Patent Nos. 4,171,240 (Wong) and 4,729,797 (Linde et al.) may be effective, but it is time-consuming and complex; furthermore, the required corrosive chemicals and / or harsh conditions can damage the separated substrates, rendering them unsuitable for subsequent applications.

[0004] Noting these issues, some authors have attempted to develop adhesive compositions that can be electrochemically debonded, in which an electric current acts through the cured composition to disrupt the bond at the interface between the adhesive and the substrate.

[0005] US 2007 / 0269659 (Gilbert) describes an adhesive composition that is debonded at two interfaces, the composition: (i) comprises a polymer and an electrolyte; (ii) promotes the bonding of two surfaces; and (iii) debonds from both the anode and cathode surfaces in response to a voltage applied to the two surfaces to form an anodic interface and a cathode interface.

[0006] US 2008 / 0196828 (Gilbert) describes a hot melt adhesive composition comprising: a thermoplastic component; and an electrolyte, wherein the electrolyte provides sufficient ionic conductivity to enable a Faraday reaction at the adhesive joint formed between the composition and a conductive surface, and allows the composition to detach from the surface.

[0007] WO2007 / 142600 (Stora Enso AB) describes an electrochemically weakenable adhesive composition that provides adhesive adhesion to conductive surfaces and sufficient ionic conductivity to weaken the adhesive adhesion when a voltage is applied to the adhesive composition, wherein the composition contains an effective amount of at least one ionic compound to impart the ionic conductivity, and wherein the melting point of the ionic compound is not higher than 120°C.

[0008] EP 3363875 A (Nitto Denko Corporation) provides an electrically peelable adhesive composition that forms an adhesive layer having high adhesion and being easily peeled off upon application of voltage for a short time. The electrically peelable adhesive composition of this invention comprises a polymer and 0.5-30% by weight of an ionic liquid based on the polymer, wherein the anion of the ionic liquid is a bis(fluorosulfonyl)imide anion.

[0009] WO2013 / 135677 (Henkel AG&Co. KGaA) describes a hot melt adhesive containing: 20 to 90 wt% of at least one polyamide with 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 additional additives, wherein the adhesive has a softening point of 100°C to 220°C.

[0010] WO2016 / 135341 (Henkel AG&Co. KGaA) describes a reactive hot melt adhesive composition that at least partially loses its adhesive strength when a voltage is applied, thus allowing detachment of substrates already bonded with the adhesive. More specifically, the reactive hot melt adhesive composition comprises: a) at least one isocyanate-functionalized polyurethane polymer; and b) at least one organic or inorganic salt.

[0011] WO2017 / 133864 (Henkel AG&Co. KGaA) describes 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 the surface of one or more non-conductive substrates with conductive ink; b) applying an electrically debonded hot melt adhesive composition to the conductive ink-coated surface of the first substrate and / or the second substrate; c) contacting the first substrate with the second substrate such that the electrically debonded hot melt adhesive composition is sandwiched between the two substrates; d) forming an adhesive bond between the two substrates to provide a bonded substrate; and e) applying a voltage to the bonded substrate, thereby significantly reducing the adhesive force at at least one interface between the electrically debonded hot melt adhesive composition and the substrate surface.

[0012] When the adhesive composition already contains ionic liquids or electrolytes, achieving compatibility between the electrolyte and the polymer matrix can be challenging. In the known art, leakage and phase separation of the electrolyte from the cured polymer matrix have been considered drawbacks in the application of electrically debonded adhesives.

[0013] There remains a need in the art for an adhesive composition that can be readily applied to the surface of substrates to be bonded, provides effective adhesion within a composite structure containing the substrates after curing, but can be effectively detached from those substrates by readily applying a potential to the cured adhesive. Furthermore, the cured adhesive should provide a stable polymer matrix from which leakage of components is minimized and where phase separation does not occur. Summary of the Invention

[0014] According to a first aspect of the invention, a curable and electrochemically detangleable adhesive composition is provided, wherein, based on the weight of the composition, the adhesive composition comprises:

[0015] 40 to 99 wt%, preferably 45 to 90 wt%, of at least one olefinic unsaturated nonionic monomer;

[0016] 0.9 to 50 wt%, preferably 5 to 30 wt%, of b) at least one polymerizable ionic compound, wherein the polymerizable ionic compound comprises:

[0017] b1) At least one compound according to general formula IV:

[0018]

[0019] and / or

[0020] b2) At least one compound according to general formula V:

[0021]

[0022] Where: R 7 Selected from: C1-C 30 Alkyl; C2-C8 alkenyl; C1-C 30 Heteroalkyl; C 3- C 30 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C6 alkylene group, and R b It is a C1-C6 alkyl group;

[0023] Each R 8 Independently selected from H, C1-C 18 Alkyl, C1-C 18 Heteroalkyl, C3-C 18 cycloalkyl, C6-C 18 Aryl, C1-C9 heteroaryl, C 7- C 18 Alkyl aryl, or C2-C5 heterocyclic alkyl;

[0024] R 9 It is an H or C1-C4 alkyl group;

[0025] Each R 10 Selected independently from: C1-C 30 Alkyl; C1-C 30 Heteroalkyl; C 3- C 30 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C6 alkylene group, and R b It is a C1-C6 alkyl group;

[0026] A is a non-polymerizable anion;

[0027] T is an olefinic unsaturated anion;

[0028] d and m are each an integer with a value of at least 1;

[0029] e and n have values ​​that make the compound electrically neutral; and

[0030] It is a covalent bond, C1-C2 alkylene, -CH2OC(=O)-, -CH2CH2OC(=O)-, p-benzyl or p-tolyl; and

[0031] c) at least one free radical initiator, 0.1 to 10% by weight, preferably 0.1 to 5% by weight.

[0032] The adhesive composition can be formulated as a one-component (1K) composition, a two-component (2K) composition, or a multi-component composition. Note the preference for part b) which consists of the compounds according to part b1) and / or part b2).

[0033] In embodiments of the composition, based on the weight of the composition, a portion a) comprises 40 to 95% by weight, preferably 45 to 90% by weight, of a1) at least one (meth)acrylate monomer represented by formula I:

[0034] H2C = CGCO2R 1 (I)

[0035] Wherein: G is hydrogen, halogen, or C1-C4 alkyl; and

[0036] R 1 Selected from C1-C 30 Alkyl, C2-C 30 Heteroalkyl, C3-C 30 Cycloalkyl, C2-C8 heterocycloalkyl, C2-C 20 alkenyl and C2-C 12 Alkyne group.

[0037] The composition a) may also be characterized by comprising, based on the weight of the composition, 0 to 30% by weight, for example 0 to 15% by weight, a2) at least one (meth)acrylate monomer represented by formula II:

[0038] H2C=CQCO2R 2 (II)

[0039] Wherein: Q can be hydrogen, halogen, or C1-C4 alkyl; and

[0040] R 2 Can be selected from C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 Alkyl and C7-C 18 Aryl group.

[0041] In another embodiment of the composition which is not intended to be mutually exclusive with the embodiments given above, based on the weight of the composition, a portion thereof a) comprises 0 to 50% by weight, preferably 5 to 25% by weight of a3) at least one (meth)acrylate-functionalized oligomer.

[0042] Regarding the electrolyte b) of the curable and electrochemically debinding composition, both the ionic compounds of formulas IV and V, as defined above and detailed below, contain functional groups reactive to free radical polymerization, preferably vinyl, allyl, or acrylic functional groups. Thus, the polymerizable electrolyte should polymerize with any of the aforementioned monomers a).

[0043] Regarding compound (b1) of formula IV, the cation is based on an imidazolium ring and becomes covalently bonded to the binder matrix upon completion of the selected curing curve: the counter anion (A) moves freely within the polymer matrix. Conversely, regarding compound (b2) of formula V, the polymerizable electrolyte anion becomes covalently bonded to the binder matrix upon curing, and the imidazolium ring-based cation moves freely within the matrix.

[0044] Preferred compounds b1) that may exist alone or in combination include, but are not limited to: 3-vinyl-1-methyl-1H-imidazolium iodide; 3-vinyl-1-methyl-1H-imidazolium chloride; 3-vinyl-1-methyl-1H-imidazolium bromide; 3-vinyl-1-methyl-1H-imidazolium methane sulfonate; 3-vinyl-1-methyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methane sulfonamide; 3-vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methane sulfonamide; 3-vinyl-1-methyl-1H-imidazolium hexafluorophosphate; 3-vinyl-1-methyl-1H-imidazolium 3-Vinyl-1-methyl-1H-imidazolium 4-methylbenzenesulfonate; 3-Vinyl-1-methyl-1H-imidazolium tetrafluoroborate; 3-Vinyl-1-ethyl-1H-imidazolium iodide; 3-Vinyl-1-ethyl-1H-imidazolium bromide; 3-Vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 3-Vinyl-1-ethyl-1H-imidazolium hexafluorophosphate; 3-Vinyl-1-ethyl-1H-imidazolium tetrafluoroborate; 3-Vinyl-1-(1-methylethyl)-1H-imidazolium bromide; 3-(1,1-dimethylethyl)-1-vinyl-1H-imidazolium Onyx bromide; 3-vinyl-1-propyl-1H-imidazolium bromide; 3-vinyl-1-(phenylmethyl)-1H-imidazolium bromide; 1-vinyl-3-(4-methylphenyl)-1H-imidazolium chloride; 3-vinyl-1-(1-methylpropyl)-1H-imidazolium chloride; 1-butyl-3-vinyl-1H-imidazolium bromide; 3-[(4-vinylphenyl)methyl]-1-methyl-iodide; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium chloride; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl] Methanesulfonamide; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium hexafluorophosphate; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium tetrafluoroborate; 3-[(4-vinylphenyl)methyl]-1-ethyl-1H-imidazolium chloride; salt of 1-[(4-vinylphenyl)methyl]-3-ethyl-1H-imidazolium and 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1-(3-aminopropyl)-3-[(4-vinylphenyl)methyl]-1H-imidazolium chloride; 1-butyl-3-[(4-vinylphenyl)methyl]-1H-imidazolium chloride.

[0045] Preferred compounds b2, which may exist alone or in combination, include, but are not limited to: 1-methyl-3-hexyl-1H-imidazolium 4-vinylbenzenesulfonate; 1-dodecyl-3-vinyl-1H-imidazolium 4-vinylbenzenesulfonate; 1-methyl-3-propyl-1H-imidazolium 4-vinylbenzenesulfonate; and 3-ethyl-1-methyl-1H-imidazolium 4-(1-methylvinyl)benzenesulfonate.

[0046] In particular, favorable results have been obtained when part b) of the composition contains at least one compound selected from the following or consists of at least one compound selected from the following: 3-methyl-1-hexyl-1H-imidazolium 4-vinylbenzenesulfonate; 3-vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; and 3-methyl-1-butyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide.

[0047] According to a second aspect of the invention, an adhesive structure is provided, the adhesive structure comprising:

[0048] A first material layer having a conductive surface; and

[0049] A second material layer having a conductive surface.

[0050] The cured, electrochemically debonded adhesive composition as defined above and in the appended claims is disposed between the first material layer and the second material layer.

[0051] According to a third aspect of the invention, a method is provided for detaching an adhesive structure as defined above and in the appended claims, the method comprising the steps of:

[0052] i) Applying a voltage to both surfaces to form an anode interface and a cathode interface; and

[0053] ii) Debond the surface.

[0054] Preferably, step i) of the method is characterized by at least one of the following:

[0055] a) An applied voltage of 1 to 100V; and

[0056] b) The voltage is applied for a duration of 1 second to 180 minutes.

[0057] By applying a potential to the adhesive layer between the composition and the conductive surface, the adhesive properties of the composition are disrupted. Unintentionally, it is assumed that a Faraday reaction occurring at the interface between the adhesive composition and the conductive surface disrupts the interaction between the adhesive and the substrate, thereby weakening the adhesion. This interface disruption can result from one or more processes, such as chemical degradation of the debonded material, gas escape at the interface, and / or material embrittlement due to changes in the crosslinking density of the adhesive composition.

[0058] definition

[0059] As used herein, unless the context clearly indicates otherwise, the singular forms “a / an” and “the” include plural referents.

[0060] As used herein, the term “comprising / comprises / comprised of” is synonymous with “including / includes” or “containing / contains”, and is inclusive or open-ended, and does not exclude additional undescribed members, elements or method steps.

[0061] As used herein, the term “composed of” excludes any element, component, member or method step not specified.

[0062] When quantities, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper limits, lower limits, or preferred upper and lower limits, it should be understood that any range that can be obtained by combining any upper or preferred value with any lower or preferred value is also specifically disclosed, whether or not the obtained range is explicitly mentioned in the context.

[0063] Furthermore, according to the standard understanding, the weight range expressed as "0 to x" specifically includes 0% by weight: the component defined by the range may not be present in the composition or may be present in the composition in an amount of up to x% by weight.

[0064] The terms “preferred,” “preferred,” “desired,” and “particularly” are generally used herein to refer to embodiments of the present disclosure that may provide particular benefits in certain circumstances. However, the description of one or more preferred, preferred, desired, or particularly embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude those other embodiments from the scope of the present disclosure.

[0065] As used throughout this application, the word "may" is used in a permissive sense (i.e., meaning possible) rather than in a mandatory sense.

[0066] As used herein, room temperature is 23°C ± 2°C. As used herein, “ambient conditions” means the temperature and pressure of the environment in which the composition is situated or the coating or the substrate of the coating is situated.

[0067] In the context of this invention, 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 shortly before application and then react, typically without additional activation, accompanied by bond formation and thus the formation of a polymer network. Higher temperatures may be applied herein to accelerate the crosslinking reaction.

[0068] As used herein, the term "electrochemically debonded" means that after the adhesive has cured, the bond strength can decrease by at least 50% after a period of time of applying a potential of 50V for up to 60 minutes. The cured adhesive is applied between two substrates bonded by the adhesive, such that an electric current flows through the adhesive layer. Bond strength is measured by a tensile lap shear (TLS) test performed at room temperature and based on ASTM D3163-01, the Standard Test Method for Determining Strength of Adhesively Bonded Rigid Plastic Lap-Shear Joints in Shear by Tension Loading. The bonded overlap area is 2.5 cm × 1.0 cm (1” × 0.4”), with a bond thickness of 0.1 cm (40 mil).

[0069] The term "electrolyte," according to its standard meaning in the art, is used herein as a substance containing free ions that can conduct electricity through the displacement of charged carriers. This term is intended to cover molten electrolytes, liquid electrolytes, semi-solid electrolytes, and solid electrolytes, wherein at least one of the cationic or anionic components of its electrolyte structure is substantially free to displace, thereby acting as charge carriers.

[0070] The curable adhesive compositions of the present invention and the cured adhesives obtained therefrom have an “electrolyte function” because the adhesive materials allow the conduction of ions (anions, cations, or both anions and cations).

[0071] Electrolyte function is understood to be derived from the ability of the composition and cured adhesive to solubilize at least one polarity of ions.

[0072] The term "Faraday reaction" refers to an electrochemical reaction in which materials are oxidized or reduced.

[0073] As used herein, the term "monomer" refers to a substance that can undergo polymerization to provide structural units for the chemical structure of a polymer. As used herein, the term "monofunctional" refers to a substance having one polymerizable moiety. As used herein, the term "multifunctional" refers to a substance having more than one polymerizable moiety.

[0074] As used herein, the term "olefinic unsaturated monomer" refers to any monomer containing terminal double bonds that can be polymerized under normal conditions of free radical addition polymerization.

[0075] As used herein, the term “equivalent (eq.)” refers to the relative amount of reactive groups present in a reaction, as is usually the case in chemical notation.

[0076] As used herein, “(meth)acryloyl” is an abbreviation for “acryloyl” and / or “methacryloyl”. Therefore, the term “(meth)acrylate” refers to both acrylates and methacrylates.

[0077] As used in this article, "C1-C" n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms; it is a group of alkanes and includes both straight-chain and branched organic groups. Therefore, "C1-C..." 30 An "alkyl" group refers to a monovalent group containing 1 to 30 carbon atoms, which is an alkane group and includes straight-chain 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 this invention, such alkyl groups may be unsubstituted or may be substituted by one or more substituents selected from halogens, hydroxyl groups, nitrile groups (-CN), amide groups, and amino groups (-NH2). Where applicable, preferences for a given substituent will be indicated in the specification. However, generally, attention should be paid to alkyl groups containing 1-18 carbon atoms (C1-C4). 18 Alkyl groups (e.g., alkyl groups containing 1-12 carbon atoms, C1-C64) 12 Alkyl groups or alkyl groups containing 1-6 carbon atoms (C1-C6 alkyl groups) are preferred.

[0078] As used in this article, the term "C1-C" 18 "Hydroxyalkyl" refers to a HO-(alkyl) group having 1 to 18 carbon atoms, wherein the substituents are connected by oxygen atoms, and the alkyl group is as defined above.

[0079] "Alkoxy" refers to a monovalent group represented by -OA, where A is an alkyl group: non-limiting examples are methoxy, ethoxy and isopropoxy.

[0080] As used herein, the term “C1-C6 alkylene” is defined as a saturated divalent hydrocarbon group having a straight-chain, branched, or cyclic moiety or a combination thereof and having 1 to 6 carbon atoms.

[0081] The term "C3-C" 30 "Cycloalkyl" should be understood to mean an optionally substituted, saturated, monocyclic, bicyclic, or tricyclic hydrocarbon group having 3 to 30 carbon atoms. Generally, attention should be paid to cycloalkyl groups containing 3-18 carbon atoms (C3-C4). 18 The preferred cycloalkyl group is cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornene. In this invention, such cycloalkyl groups may be unsubstituted or may be substituted by one or more substituents selected from halogens, C1-C6 alkyl groups, and C1-C6 alkoxy groups.

[0082] As used herein, "C6-C" is used alone or as a significant part of (e.g., in "araneyl") 18 The term "aryl" refers to an optionally substituted monocyclic, bicyclic, or tricyclic cyclic system, wherein the monocyclic system is aromatic, or at least one ring in the bicyclic or tricyclic system is aromatic. Bicyclic and tricyclic systems comprise benzofused 2- or 3-membered carbon rings. In this invention, such aryl groups may be unsubstituted or may be substituted with one or more substituents selected from halogens, C1-C6 alkyl groups, and C1-C6 alkoxy groups. Exemplary aryl groups include: phenyl; (C1-C4)alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthrayl; and anthracel. Note also that phenyl is preferred.

[0083] As used in this article, "C2-C" 20 "Alkenyl" refers to a hydrocarbon group having 2 to 20 carbon atoms and at least one olefinic unsaturated unit. Alkenyl groups can be linear, branched, or cyclic and can optionally be substituted. As will be understood by those skilled in the art, the term "alkenyl" also includes groups having "cis" and "trans" configurations, or alternatively "E" and "Z" configurations. However, generally, care should be taken regarding groups containing 2 to 10 carbon atoms (C... 2-10 ) or contains 2 to 8 carbon atoms (C 2-8 The preferred form is the unsubstituted alkenyl group of the C2-C group. 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 ═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-cyclohexyl-1-enyl; 1-cyclohexyl-2-enyl; and 1-cyclohexyl-3-enyl.

[0084] As used herein, “alkylaryl” means an aryl group substituted with an alkyl group, and “substituted alkylaryl” means an alkylaryl group further having one or more of the above-described substituents. Furthermore, as used herein, “aralkyl” means an alkyl group substituted with an aryl group as defined above.

[0085] As used herein, the term "hetero" refers to a group or part containing one or more heteroatoms selected from N, O, Si, P, and S. Thus, for example, "heterocyclic" refers to a cyclic group having N, O, Si, P, or S as part of its ring structure. The moiety "heteroalkyl," "heterocycloalkyl," and "heteroaryl" are alkyl, cycloalkyl, and aryl groups as defined above, respectively, containing N, O, Si, P, or S as part of their structure.

[0086] For completeness, the term "C2-C" is used. 30 "Heteroalkyl" refers to an "alkyl" group in which at least one carbon atom has been replaced by a heteroatom, and the group has a total of 2 to 30 carbon atoms. A specific example of such a heteroalkyl group is "C2-C". 18 "Alkoxyalkyl" refers herein to an alkyl group having an alkoxy substituent as defined above, wherein the (alkyl-O-alkyl) moiety comprises a total of 1 to 18 carbon atoms: such groups include methoxymethyl (-CH2OCH3), 2-methoxyethyl (-CH2CH2OCH3), and 2-ethoxyethyl (-CH2CH2OCH2CH3). Further examples of heteroalkyl groups are "C2-C..." 30 "Aminoalkyl" refers to an aminoalkyl group selected from at least one of -NH(R'), -N(R')(R”) or N+ (R')(R”)(R”') is a group substituted with an alkyl group, wherein R', R” and R”' are C1-C6 alkyl groups provided that the group contains a total of 2 to 30 carbon atoms: such groups include 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl and 2-(trimethylamino)ethyl.

[0087] The term "C1-C9 heteroaryl" refers to an aromatic group having 1-9 carbon atoms and 1-4 heteroatoms, which may be linked via heteroatoms (if feasible) or carbon atoms. The heteroaryl ring may be fused or otherwise connected to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocyclic alkyl rings. Examples of heteroaryl groups include, but are not limited to: pyridine; furan; thiophene; 5,6,7,8-tetrahydroisoquinoline; pyrimidine; thiophene; benzothiophene; pyridinyl; quinolinyl; pyrazinyl; pyrimidinyl; imidazolyl; benzimidazolyl; furanyl; benzofuranyl; thiazolyl; benzothiazolyl; isoxazolyl; oxadiazolyl; isothiazolyl; benzoisothiazolyl; triazolyl; tetrazolyl; pyrroleyl; indolyl; pyrazolyl; and benzopyrazolyl.

[0088] The term "C2-C8 heterocyclic alkyl" refers to a saturated cyclic hydrocarbon group having 2-8 carbon atoms and 1-4 heteroatoms, said group being linked via heteroatoms (if feasible) or carbon atoms. The heterocyclic alkyl ring may optionally be fused or otherwise linked to other heterocyclic alkyl and / or non-aromatic hydrocarbon rings. Preferred heterocyclic alkyl groups have 3 to 7 members. Examples of heterocyclic alkyl groups include, but are not limited to: piperazine; morpholine; piperidine; tetrahydrofuran; pyrrolidine; pyrazole; piperidinyl; piperazinyl; morpholinyl; and pyrrolidinyl.

[0089] As used herein, the term "aliphatic" includes saturated and unsaturated, non-aromatic, straight-chain, branched, acyclic, or cyclic hydrocarbons, which are optionally substituted with one or more functional groups, provided that the substitution results in the formation of a stable moiety. As those skilled in the art will understand, "aliphatic" is intended to include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties.

[0090] As used herein, "aromatic" refers to the principal group of an unsaturated cyclic hydrocarbon containing one or more rings, said group may contain carbon (C), nitrogen (N), oxygen (O), sulfur (S), boron (B), or any combination thereof. At least some carbons are included. Aromatics includes both aryl rings and heteroaryl rings. Aryl rings or heteroaryl rings may also be substituted with additional aliphatic groups, aromatic groups, or other groups, provided that the substitution results in the formation of a stable moiety.

[0091] As used herein, the term "free radical initiator" refers to any chemical substance that, upon exposure to sufficient energy (in the form of radiation, heat, etc.), decomposes into two uncharged parts, each having at least one unpaired electron. For completeness, the term "free radical initiator" includes thermal free radical initiators and free radical photoinitiators, which can be activated by an energetically activated beam upon irradiation with an energetically activated beam (such as electromagnetic radiation): thermal free radical initiators are preferred herein.

[0092] The molecular weights of the macromolecular, oligomeric, and polymeric components used to describe the curable composition mentioned in this specification can be measured using gel permeation chromatography (GPC) with polystyrene calibration standards, as per ASTM 3536.

[0093] Unless otherwise specified, the viscosity of the coating compositions described herein was measured using a Brinell viscometer under standard conditions of 20°C and 50% relative humidity (RH). The calibration method, rotor type, and rotation speed of the Brinell viscometer were selected according to the manufacturer's instructions to suit the composition being measured. Detailed Implementation

[0094] a) Nonionic matrix monomers

[0095] The compositions of the present invention comprise at least one olefinically unsaturated nonionic monomer, which is (co)polymerized to produce a matrix of a desiccant adhesive. Monomer a) can in principle be any olefinically unsaturated nonionic monomer. However, the present invention is particularly applicable to compositions in which (meth)acrylic acid monomers constitute at least 50 mol%, preferably at least 75 mol%, of the total molar amount of the olefinically unsaturated nonionic monomers present.

[0096] a1) Aliphatic and alicyclic (meth)acrylate monomers

[0097] In a key embodiment of the invention, based on the weight of the composition, the composition of the invention comprises 40 to 95% by weight, preferably 45 to 90% by weight, of a1) at least one (meth)acrylate monomer represented by formula I:

[0098] H2C = CGCO2R 1 (I)

[0099] Wherein: G is hydrogen, halogen, or C1-C4 alkyl; and

[0100] R 1 Selected from: C1-C 30 Alkyl; C2-C 30 Heteroalkyl; C3-C 30 Cycloalkyl; C2-C8 heterocycloalkyl; C2-C 20 alkenyl groups; and C2-C 12Alkyne group.

[0101] For example, R 1 Can be selected from C1-C 18 Alkyl, C2-C 18 Heteroalkyl, C3-C 18 Cycloalkyl, C2-C8 heterocycloalkyl, C2-C8 alkenyl and C2-C8 ynyl.

[0102] Desiredly, the one or more monomers a1) are characterized by: R 1 Selected from C1-C 18 Alkyl and C3-C 18 Cycloalkyl. This preferred statement is explicitly intended to include R therein. 1 This embodiment is a C1-C6 hydroxyalkyl group.

[0103] Examples of (meth)acrylate monomers according to 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.

[0104] a2) Aromatic (meth)acrylate monomers

[0105] Based on the weight of the composition, the compositions of the present invention may further comprise 0 to 30% by weight, for example 0.1 to 30% by weight, 0.1 to 25% by weight, or 0.1 to 15% by weight of a2) at least one (meth)acrylate monomer represented by formula II:

[0106] H2C=CQCO2R 2 (ii)

[0107] Wherein: Q can be hydrogen, halogen, or C1-C4 alkyl; and

[0108] R 2 Can be selected from C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 Alkyl and C7-C 18 Aryl group.

[0109] Exemplary (meth)acrylate monomers according to formula (II) a2) that can be used alone or in combination include, but are not limited to: benzyl (meth)acrylate; phenoxyethyl (meth)acrylate; phenoxydiethylene glycol (meth)acrylate; phenoxypropyl (meth)acrylate; and phenoxydipropylene glycol (meth)acrylate.

[0110] a3)(meth)acrylate functionalized oligomers

[0111] In a key embodiment of the invention, where there is no intention to exclude aliphatic and alicyclic monomers (a1) and aromatic monomers (a2), the composition of the invention shall, based on the weight of the composition, contain 0 to 50 wt%, preferably 5 to 25 wt%, of at least one (meth)acrylate-functionalized oligomer (a3). The oligomer may have one or more acrylate groups and / or methacrylate groups attached to the oligomer backbone, the (meth)acrylate functional groups being located at the ends of the oligomer and / or distributed along the oligomer backbone.

[0112] Preferably, the at least one (meth)acrylate-functionalized oligomer has: i) two or more (meth)acrylate functional groups per molecule; and / or ii) a weight-average molecular weight (Mw) of 300 to 1000 Daltons.

[0113] Examples of such oligomers that can be used alone or in combination include, but are not limited to: (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 polybutadiene; (meth)acrylate 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 particularly disclosed in: U.S. Patent 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. Specific examples of the above polyether (meth)acrylate oligomers include, but are not limited to: PEG 200DMA (n≈4); PEG 400DMA (n≈9); PEG 600DMA (n≈14); and PEG 800DMA (n≈19), wherein the specified number (e.g., 400) represents the weight-average molecular weight of the diol portion of the molecule.

[0114] This invention does not exclude the presence of other olefinically unsaturated nonionic monomers that do not conform to the definitions of a1), a2), and a3). However, the addition of such additional monomers should be limited to the following condition: the total amount of olefinically unsaturated nonionic monomers should not exceed 95% by weight based on the total weight of the composition. Desiredly, the total amount of olefinically unsaturated nonionic monomers should not exceed 90% by weight based on the total weight of the composition.

[0115] This invention is not intended to limit the scope of the invention. Other such olefinically unsaturated nonionic monomers may include: organosilicon (meth)acrylate monomers, such as those taught and claimed in U.S. Patent No. 5,605,999 (Chu); α,β-olefinically unsaturated monocarboxylic acids containing 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, and crotonic acid; C1-C of crotonic acid. 18 Alkyl esters; α,β-ene unsaturated dicarboxylic acids containing 4 to 6 carbon atoms, and their anhydrides, monoesters, and diesters; vinyl esters, such as vinyl acetate, vinyl propionate, and VEOVA available from Shell Chemical Company.TM Monomers of the series; vinyl halides and vinylidene halides; vinyl ethers, such as vinyl ethyl ether; vinyl ketones, including alkyl vinyl ketones, cycloalkyl vinyl ketones, aryl vinyl ketones, arylalkyl vinyl ketones, and arylcycloalkyl 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, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate. Esters, glycerol tri(meth)acrylates and pentaerythritol tetra(meth)acrylates; 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, dibutyl glycol di(meth)acrylate, di(1,5-pentanediol) dimethacrylate; polyethylene glycol di(meth)acrylates; and bisphenol A di(meth)acrylates, such as ethoxylated bisphenol A (meth)acrylates (“EBIPMA”).

[0116] Representative examples of other olefinically unsaturated polymerizable nonionic monomers include, but are not limited to: ethylene glycol dimethacrylate (EGDMA); monoesters and diesters of fumaric anhydride, maleic anhydride, and itaconic anhydride with C1-C4 alcohols (such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol). Representative examples of vinyl monomers include, but are not limited to, compounds such as: vinyl acetate; vinyl propionate; vinyl ethers, such as vinyl ethyl ether; and vinyl ethyl ketone. Representative 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-vinylcyclohexene, 3-vinylcyclohexene, and 4-vinylcyclohexene.

[0117] b) Electrolytes

[0118] The compositions of the present invention comprise 0.9 to 50 wt%,, for example 5 to 50 wt%, or 10 to 45 wt%, of b) at least one polymerizable ionic compound, wherein said polymerizable ionic compound comprises:

[0119] b1) At least one compound according to general formula IV:

[0120]

[0121] and / or

[0122] b2) At least one compound according to general formula V:

[0123]

[0124] Where: R 7 Selected from: C1-C 30 Alkyl; C2-C8 alkenyl; C1-C 30 Heteroalkyl; C 3- C 30 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C6 alkylene group, and R b It is a C1-C6 alkyl group;

[0125] Each R 8 Independently selected from H, C1-C 18 Alkyl, C1-C 18 Heteroalkyl, C3-C 18 cycloalkyl, C6-C 18 Aryl, C1-C9 heteroaryl, C 7- C 18 Alkyl aryl, or C2-C5 heterocyclic alkyl;

[0126] R 9 It is an H or C1-C4 alkyl group;

[0127] Each R 10 Selected independently from: C1-C 30 Alkyl; C1-C 30 Heteroalkyl; C 3- C 30 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C6 alkylene group, and R b It is a C1-C6 alkyl group;

[0128] A is a non-polymerizable anion;

[0129] T is an olefinic unsaturated anion;

[0130] d and m are each an integer with a value of at least 1;

[0131] e and n have values ​​that make the compound electrically neutral; and

[0132] It is a covalent bond, C1-C2 alkylene, -CH2OC(=O)-, -CH2CH2OC(=O)-, p-benzyl or p-tolyl.

[0133] In the above formula, preferably, R 7 Selected from C1-C 12 Alkyl; C2-C6 alkenyl; C1-C 12 Heteroalkyl; C 3- C 18 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C6 alkylene group, and R b It is a C1-C6 alkyl group. More specifically, R 7 Selected from C1-C8 alkyl; C2-C4 alkenyl; C1-C8 heteroalkyl; C 3- C 12 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C4 alkylene group, and R b It is a C1-C4 alkyl group. Considering R... 7 It can be alkenyl, and it should be noted that the imidazolium moiety can have more than one olefinic unsaturated group: in this regard, exemplary moieties include: 1-3-divinyl-1-H-imidazolium; and 3-vinyl-1-(2-propenyl-1-yl)-1-H-imidazolium.

[0134] Each R 8 Preferably selected independently from H or C1-C6 alkyl groups, and more particularly independently from H or C1-C2 alkyl groups. It may be mentioned that at least one R is preferred. 8 It's H.R. 9 Preferably, it is an H or C1-C2 alkyl group, and more particularly an H or methyl group.

[0135] Preferably, each R 10 Independently selected from C1-C 12 Alkyl; C1-C12 Heteroalkyl; C 3- C 18 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C6 alkylene group, and R b It is a C1-C6 alkyl group. More specifically, R 10 Selected from: C1-C8 alkyl; C1-C8 heteroalkyl; C 3- C 12 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C4 alkylene group, and R b It is a C1-C4 alkyl group.

[0136] For compounds of formula IV, anion A is usually selected from: fluoride ion; chloride ion; bromide ion; iodide ion; perchlorate ion; nitrate ion; nitrite ion; phosphate ion; sulfate ion; sulfite ion; carbonate ion; bicarbonate ion; hydrogen phosphate ion; hydrogen sulfate ion; bisulfite ion; dihydrogen phosphate ion; trifluorophosphate ion; hexafluorophosphate ion; methyl sulfate ion; ethyl sulfate ion; methyl carbonate ion; methanesulfonate ion; ethylsulfonate ion; 4-methylbenzenesulfonate ion; diethyl phosphate ion; formate ion; acetate ion; propionate ion; tartrate ion; octanoate ion; bis(2,4,4-trimethylpentyl)phosphine ion; bis(malonato)borate ion; bis(oxalato)borate ion; bis(pentafluoroethyl)phosphine ion; tetracyanoborate ion; tetrafluoroborate ion; Bis(phthalato)borate; bis(salicylato)borate; bis(trifluoromethylsulfonate)imide; bis(trifluoromethanesulfonyl)methane; bis(trifluoromethyl)imine; tetra(hydrosulfonate)borate; tetra(methylsulfonate)borate; trifluoromethylsulfonate; tri(heptafluoropropyl)trifluorophosphate; tri(nonafluorobutyl)trifluorophosphate; tri(pentafluoroethyl)trifluorophosphate; tri(pentafluoroethylsulfonyl)trifluorophosphate; trichlorozincate; trifluoroacetate; bromoaluminate; chloroaluminate; dichlorocopperate; thiocyanate; toluenesulfonate; and dicyanamide.

[0137] Preferably, anion A is selected from: fluoride ion; chloride ion; bromide ion; iodide ion; perchlorate ion; nitrate ion; formate ion; acetate ion; octanoate ion; tetrafluoroborate ion; trifluorophosphate ion; hexafluorophosphate ion; methyl sulfate ion; ethyl sulfate ion; methyl carbonate ion; methanesulfonate ion; 4-methylbenzenesulfonate ion; trifluoromethanesulfonate ion; bis(trifluoromethanesulfonate)imide, trifluorophosphate ion and trifluoroacetate ion; and tri(perfluoroethyl)trifluorophosphate ion.

[0138] More specifically, anion A is selected from: fluoride ion; chloride ion; bromide ion; iodide ion; tetrafluoroborate ion; hexafluorophosphate ion; methyl sulfate ion; ethyl sulfate ion; methanesulfonate ion; 4-methylbenzenesulfonate ion; and bis(trifluoromethanesulfonate)imide.

[0139] Anion T can be selected from: olefinic unsaturated carboxylate anion (R-COO-); olefinic unsaturated sulfonate anion (R-SO3-). - ); olefinic unsaturated phosphonate anion (R-PO3) 2- ); olefinic unsaturated phosphonate anion (RP(H)O2) -); and olefinic unsaturated phosphate anions (RO-PO3). 2- ), wherein R is an organic group containing ethylenic unsaturation, said group being polymerized under normal conditions and preferably derived from (meth)acrylic acid, ethylene acid or allyl acid.

[0140] Representative anions T include: (meth)acrylate; itaconic acid; maleate; crotonate; isocrotonate; vinylbenzoate; 2-acrylamido-2-methylpropanesulfonate; sulfoethyl(meth)acrylate; sulfopropyl(meth)acrylate; sulfonated acrylamide; allyl sulfonate; vinyl sulfonate; 4-vinylbenzenesulfonate (4-styrenesulfonate); 4-isopropenylbenzenesulfonate (4-methylstyrenesulfonate); allylphosphonate; and monoacryloyloxyethyl phosphate.

[0141] Exemplary compounds according to formula IV (b1) include, but are not limited to: 3-vinyl-1-methyl-1H-imidazolium iodide; 3-vinyl-1-methyl-1H-imidazolium chloride; 3-vinyl-1-methyl-1H-imidazolium bromide; 3-vinyl-1-methyl-1H-imidazolium methanesulfonate; 3-vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 3-vinyl-1-methyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 3-vinyl-1-methyl-1H-imidazolium hexafluorophosphate; 3-vinyl-1-methyl-1H-imidazolium 4-methylbenzenesulfonate. ; 3-Vinyl-1-methyl-1H-imidazolium tetrafluoroborate; 3-Vinyl-1-ethyl-1H-imidazolium iodide; 3-Vinyl-1-ethyl-1H-imidazolium bromide; 3-Vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 3-Vinyl-1-ethyl-1H-imidazolium hexafluorophosphate; 3-Vinyl-1-ethyl-1H-imidazolium tetrafluoroborate; 1,3-Divinyl-1H-imidazolium chloride; 1,3-Divinyl-1H-imidazolium tetrafluoroborate; 1,3-Divinyl-1H-imidazolium hexafluorophosphate; 3-Vinyl-1-ethyl-2-methyl-1H-imidazolium iodide; 3-Vinyl-1-ethyl-1H-imidazolium tetrafluoroborate; 3-Vinyl-1-ethyl-1H-imidazolium tetrafluorophosphate; 3-Vinyl-1-ethyl-2-methyl-1H-imidazolium iodide; 3-Vinyl-1-ethyl-1H-imidazolium tetrafluorophosphate ... Alkenyl-1,2-dimethyl-1H-imidazolium iodide; 3-vinyl-1,2-dimethyl-1H-imidazolium chloride; 3-vinyl-2-ethyl-1-methyl-1H-imidazolium iodide; 3-(aminomethyl)-1-vinyl-1H-imidazolium bromide; 3-vinyl-1-(1-methylethyl)-1H-imidazolium bromide; 3-(1,1-dimethylethyl)-1-vinyl-1H-imidazolium bromide; 3-vinyl-1-propyl-1H-imidazolium bromide; 1-(2-aminoethyl)-3-vinyl-1H-imidazolium chloride; 1-(cyanomethyl)-3-vinyl-1H-imidazolium bromide; 1-[2-(diethylamino)ethyl]-3-vinyl -1H-imidazolium chloride; 3-vinyl-1-(2-propen-1-yl)-1H-imidazolium chloride; 3-vinyl-1-(2-propen-1-yl)-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 3-vinyl-1-(2-propen-1-yl)-1H-imidazolium bromide; 3-vinyl-1-(phenylmethyl)-1H-imidazolium bromide; 1-vinyl-3-(4-methylphenyl)-1H-imidazolium chloride; 3-vinyl-1-(2-hydroxyethyl)-1H-imidazolium chloride; 3-vinyl-1-(1-methylpropyl)-1H-imidazolium chloride; 1-butyl-3-vinyl-1H-imidazolium bromide;3-Vinyl-1-(2-ethoxyethyl)-1H-imidazolium bromide; 1-Methyl-3-(2-propen-1-yl)-1H-imidazolium iodide; 1-Methyl-3-(2-propen-1-yl)-1H-imidazolium chloride; 1-Methyl-3-(2-propen-1-yl)-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1-Methyl-3-(2-propen-1-yl)-1H-imidazolium hexafluorophosphate; 1-Methyl-3-(2-propen-1-yl)-1H-imidazolium tetrafluoroborate; 1-Ethyl-3-(2-propen-1-yl)-1H-imidazolium iodide; 2-Methyl-3-(2-propen-1-yl) -1-propyl-1H-imidazolium bromide; 3-(2-propen-1-yl)-1-propyl-1H-imidazolium bromide; 3-(2-hydroxyethyl)-1-(2-propen-1-yl)-1H-imidazolium bromide; 1-butyl-3-(2-propen-1-yl)-1H-imidazolium bromide; 1,3-di-2-propen-1-yl-1H-imidazolium bromide; 1,3-di-2-propen-1-yl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1,3-di-2-propen-1-yl-1H-imidazolium tetrafluoroborate; 3-(2-hydroxyethyl)-1-(2-propen-1-yl)-1H-imidazolium bromide; 1- (2-Cyanoethyl)-3-(2-Propylene-1-yl)-1H-Imidazolium bromide; 1-Methyl-3-(2-oxopropyl)-1H-Imidazolium tetrafluoroborate; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium iodide; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium chloride; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium hexafluorophosphate; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium tetrafluoroborate Salts; 3-[(4-vinylphenyl)methyl]-1-ethyl-1H-imidazolium chloride; salts of 1-[(4-vinylphenyl)methyl]-3-ethyl-1H-imidazolium and 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1-(3-aminopropyl)-3-[(4-vinylphenyl)methyl]-1H-imidazolium chloride; 1-butyl-3-[(4-vinylphenyl)methyl]-1H-imidazolium chloride; 1-methyl-3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-1H-imidazolium bromide; 1-ethyl-3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-1H-imidazolium iodide;And 1-butyl-3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-1H-imidazolium iodide. For completeness, such compounds may be present alone or in combination of two or more in the compositions of the present invention.

[0142] This invention is not intended to be limiting; representative compounds according to formula IV include:

[0143]

[0144] For completeness, in the above description, NTf2- represents the bis(trifluoromethanesulfonyl)imide anion.

[0145] Exemplary compounds according to formula V (b2) include, but are not limited to: 3-(3-cyanopropyl)-1-methyl-1H-imidazolium 2-acrylate; 3-hexyl-1-methyl-1H-imidazolium 2-acrylate; 3-hexadecyl-1-methyl-1H-imidazolium 2-acrylate; 3-ethyl-1-methyl-1H-imidazolium 2-methyl-2-acrylate; 1-methyl-3-(phenylmethyl)-1H-imidazolium 2-methyl-2-acrylate; 3-ethyl-1-methyl-1H-imidazolium 1-[2-[(1-oxo-2-propen-1-yl)oxy]ethyl]1,2-phthalate; 3-ethyl-1-methyl-1H-imidazolium 2-methyl-2-[(1-oxo-2-propen-1-yl)oxy]ethyl]1,2-phthalate; [-2-propen-1-yl)amino]-1-propane sulfonate; 3-butyl-1-methyl-1H-imidazolium 3-sulfopropyl 2-methyl-2-acrylate; salts of 3-ethyl-1-methyl-1H-imidazolium and 2-(phosphonoyloxy)ethyl 2-methyl-2-acrylate; 1-methyl-3-hexyl-1H-imidazolium 4-vinylbenzene sulfonate; 1-dodecyl-3-vinyl-1H-imidazolium 4-vinylbenzene sulfonate; 3-vinyl-1-hexadecyl-1H-imidazolium 4-vinylbenzene sulfonate; 1-methyl-3-propyl-1H-imidazolium 4-vinylbenzene sulfonate; and 3-ethyl-1-methyl-1H-imidazolium 4-(1-methylvinyl)benzene sulfonate. For completeness, such compounds may be present alone or in combinations of two or more in the compositions of the present invention.

[0146] This invention is not intended to be limiting; representative compounds according to formula V include:

[0147]

[0148] It should be noted that, in some embodiments, the electrically desiccant adhesive formulation may contain both of the following: b1) one or more compounds according to formula IV; and b2) one or more compounds according to 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.

[0149] c) Free radical initiators

[0150] The compositions of the present invention include c) at least one free radical initiator. Based on the total weight of the composition, the composition should generally 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 free radical initiator described in c).

[0151] This invention is not intended to limit the scope of the invention. One exemplary class of free radical initiators applicable herein is organic peroxides selected from, for example: cyclic peroxides; diacyl peroxides; dialkyl peroxides; hydroperoxides; peroxycarbonates; peroxydicarbonates; peroxyesters; and peroxyketals.

[0152] While certain peroxides (such as dialkyl peroxides) have been disclosed, particularly in U.S. Patent Nos. 3,419,512 (Lees) and 3,479,246 (Stapleton), as useful initiators and may indeed be useful herein, hydroperoxides represent a preferred class of initiators for use in this invention. Furthermore, while hydrogen peroxide itself can be used, organic hydroperoxides are the most desirable polymerization initiators. For completeness, the definition of hydroperoxides 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 peroxide and hydroxycyclohexyl peroxide, and tert-butyl perbenzoate, respectively.

[0153] In embodiments of the present invention, the free radical initiator comprises at least one hydroperoxide compound represented by the following formula or consists of at least one hydroperoxide compound represented by the following formula:

[0154] R p OOH

[0155] Where: R p It is an aliphatic or aromatic group containing up to 18 carbon atoms, and

[0156] Preferably, R p It is C1-C 12 Alkyl, C6-C 18 Aryl or C7-C 18Aryl group.

[0157] As an exemplary peroxide initiator that can be used alone or in combination, cumene hydroperoxide (CHP) may be mentioned; Alkyl hydroperoxide; tert-butyl hydroperoxide (TBH); tert-butyl perbenzoate; tert-butyl peroxyvalerate; di-tert-butyl peroxide; tert-butyl peroxyacetate; tert-butyl peroxy-2-hexanoate; tert-pentyl hydroperoxide; 1,2,3,4-tetramethylbutyl hydroperoxide; benzoyl peroxide; dibenzoyl peroxide; 1,3-bis(tert-butylperoxyisopropyl)benzene; diacetyl peroxide; 4,4-bis(tert-butylperoxy)valerate butyl ester; p-chlorobenzoyl peroxide; tert-butyl isopropylbenzene peroxide; di-tert-butyl peroxide; diisopropylbenzene peroxide; 2,5-dimethyl-2,5-di-tert-butylperoxyhexane; 2,5-dimethyl-2,5-di-tert-butyl-peroxyhex-3-yne; and 4-methyl-2,2-di-tert-butylperoxypentane.

[0158] In no way is this invention limited. Another exemplary class of free radical initiators applicable herein is azo polymerization initiators selected, for example, from: azo nitriles; azo esters; azo amides; azomididines; azo imidazoline; and macromolecular azo initiators.

[0159] 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-carboxylonitrile); 4,4'-azobis(4-cyanovaleric acid); dimethyl 2,2'-azobis(2-methylpropionic acid); 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]; 2 2,2'-Azobis(N-butyl-2-methylpropionamide); 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride; 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]; 2,2'-Azobis(2-methylpropanediamine) dihydrochloride; 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropanediamine] tetrahydrate; a polymer of 4,4-azobis(4-cyanovaleric acid) and α,ω-bis(3-aminopropyl)polydimethylsiloxane (VPS-1001, available from Wako Pure Chemical Industries, Ltd.); and a 4,4'-azobis(4-cyanovaleric acid) polyethylene glycol polymer (VPE-0201, available from Wako Pure Chemical Industries, Ltd.).

[0160] It is not excluded that the composition of the present invention may contain at least one free radical photoinitiator compound, which initiates the polymerization or hardening of the composition when irradiated with photochemical radiation.

[0161] Generally, radical photoinitiators are classified into those that form radicals through cleavage (referred to as "Norrish Type I") and those that form radicals through hydrogen abstraction (referred to as "Norrish Type II"). Norrish Type II photoinitiators require a hydrogen donor to act as the radical source: because initiation is based on a bimolecular reaction, Norrish Type II photoinitiators are typically slower than Norrish Type I photoinitiators, which form radicals on a monomolecular basis. On the other hand, Norrish Type II photoinitiators exhibit better optical absorption properties in the near-ultraviolet spectral region. Those skilled in the art should be able to select an appropriate radical photoinitiator based on the photochemical radiation used in curing and the sensitivity of one or more photoinitiators at that wavelength.

[0162] Preferred free radical photoinitiators are selected from the following: benzoylphosphine oxide; aryl ketones; benzophenone; hydroxylated ketones; 1-hydroxyphenyl ketones; ketals; and metallocenes. For completeness, combinations of two or more of these photoinitiators are not excluded in this invention.

[0163] Particularly preferred free radical photoinitiators are selected from the following: benzoin dimethyl ether; 1-hydroxycyclohexylphenyl ketone; benzophenone; 4-chlorobenzophenone; 4-methylbenzophenone; 4-phenylbenzophenone; 4,4'-bis(diethylamino)benzophenone; 4,4'-bis(N,N'-dimethylamino)benzophenone (milchone); isopropylthioxanthone; 2-hydroxy-2-methylphenylpropanone (Daracur) 1173); 2-methyl-4-(methylthio)-2-morpholinophenylacetone; methyl benzoylcarboxylate; methyl 2-benzoylbenzoate; 2-ethylhexyl 4-(dimethylamino)benzoate; ethyl 4-(N,N-dimethylamino)benzoate; phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; and ethyl phenyl(2,4,6-trimethylbenzoyl)phosphine sulfate. Similarly, for safety reasons, combinations of two or more of these photoinitiators are not excluded in this invention.

[0164] When the compositions of the present invention contain free radical photoinitiators, irradiation of the curable composition generates an active substance from one or more photoinitiators that initiate the curing reaction. Once this substance is generated, the curing chemistry follows the same thermodynamic rules as any chemical reaction: the reaction rate can be accelerated by heat. The use of heat treatment to enhance the implementation of photochemical radiation curing of monomers is well known in the art.

[0165] As those skilled in the art will recognize, photosensitizers can be incorporated into the composition to improve the efficiency of the photoinitiator (c) in utilizing the transferred energy. The term "photosensitizer," according to its standard meaning, is used to denote any substance that increases the rate of photoinitiated polymerization or causes a wavelength shift in which polymerization occurs. Based on the weight of the free radical photoinitiator, the photosensitizer should be used in an amount of 0 to 25% by weight.

[0166] The use of free radical (photo)initiators can generate residual compounds in the final cured product through (photo)chemical reactions. These residues can be detected using conventional analytical techniques such as infrared spectroscopy, ultraviolet spectroscopy, and NMR spectroscopy; gas chromatography or liquid chromatography; and mass spectrometry. Therefore, the present invention can comprise a cured matrix (co)polymer and detectable amounts of residues from the free radical (photo)initiator. The residues are present in small amounts and generally do not interfere with the desired physicochemical properties of the final cured product.

[0167] d) Solubilizer

[0168] The compositions of the present invention may optionally contain a solubilizer. Based on the weight of the composition, the composition may, for example, contain 0.1 to 10 wt% or 0.1 to 5 wt% of a solubilizer. The solubilizer has the function of promoting the miscibility of electrolyte b) within the adhesive composition: the solubilizer may or may not form part of the polymer matrix formed during the curing of the adhesive composition, but it does help to promote ion transfer therein. Therefore, the solubilizer is preferably a polar compound and should ideally be a liquid at room temperature.

[0169] Suitable categories of solubilizers include: polyphosphazenes; polymethylene sulfides; polyalkylene glycols; polyethyleneimine; silicone surfactants, such as polyalkylsiloxanes and polyalkylene-modified polydimethylsiloxanes, including but not limited to poly(C2-C3)alkylene-modified polydimethylsiloxanes; copolymers of functionalized polyalkylsiloxanes with epoxy resins, such as copolymers of polydimethylsiloxane (PDMS) with epoxy resins; polyols; and sugars. For completeness, fluorinated silicone surfactants (such as fluorinated polysilanes) are intended to be included within the term silicone surfactant.

[0170] Polyols and sugars, such as ethylene glycol, 1,3-propanediol, cyclohexanediol, hydroquinone, catechol, resorcinol, phloroglucinol, hydroxyhydroquinone, tris(hydroxymethyl)benzene, tris(hydroxymethyl)benzene having 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, hexane-1,3,5-triol, erythritol, 1,2,4,5-tetrahydroxybenzene, threitol, arabinitol, 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.

[0171] In polyoxyalkylene glycols, it is particularly preferred to use polyoxyalkylene glycols with a weight average molecular weight of 200 to 10,000 g / mol, for example 200 to 2,000 g / mol.

[0172] Additives and auxiliary ingredients

[0173] The compositions obtained in this invention will generally also contain adjuvants and additives that can impart improved properties to these compositions. For example, adjuvants and additives may impart one or more of the following: improved elasticity; improved elastic recovery; longer permissible processing time; faster curing time; and lower residual tack. Such adjuvants and additives include: nonpolymerizable electrolytes; toughening agents; conductive particles; nonconductive fillers; catalysts; plasticizers; stabilizers, including UV stabilizers; antioxidants; reactive diluents; desiccants; adhesion promoters; fungicides; flame retardants; rheology adjuvants; colored pigments or pastes; and / or additional optional nonreactive diluents within a small range.

[0174] Such adjuvants and additives may be used as needed in such combinations and proportions, provided that they do not adversely affect the characteristics and fundamental properties of the composition. While there may be exceptions in some cases, these adjuvants and additives should not total more than 20% by weight of the total composition, and preferably should not exceed 10% by weight.

[0175] The presence of a non-polymerizable electrolyte in the compositions of the present invention is not excluded. Exemplary electrolytes include non-polymerizable salts of cations selected from: ammonium; pyridinium; phosphonium; imidazolium; oxazolium; guadinium; and thiazolium. While there are no particular limitations on the anions of such non-polymerizable salts, preferred anions are selected from: halides; PF6. - CF3SO3 - (CF3SO3)2N - CF3CO2 - and CCl3CO2 - pseudohalides and halogenated compounds; carboxylic acid anions, especially formate, acetate, propionate, butyrate and lactate; hydroxycarboxylic acid anions; pyridinate and pyrimidinate; carboxylic acid imides, bis(sulfonyl)imides and sulfonylimides; sulfate, especially methyl sulfate and ethyl sulfate; sulfite; sulfonate, especially methanesulfonate; and phosphate, especially dimethyl phosphate, diethyl phosphate and (2-ethylhexyl) phosphate.

[0176] When included in the composition, the nonpolymerizable electrolyte should be present in an amount of less than 10% by weight of the total weight of the polymerizable ionic compound (part b).

[0177] The presence of a toughening agent in the compositions of the present invention can facilitate debonding of the cured adhesive. Unintentionally, the toughening agent promotes phase separation within the cured adhesive under an applied potential. In particular, good debonding results have been obtained when the compositions of the present invention contain at least one toughening agent selected from: epoxy resin-elastomer adducts; and toughened rubber in the form of core-shell particles dispersed in a matrix polymer.

[0178] Elastomer-containing adducts can be used alone, or combinations of two or more specific adducts can be used. Furthermore, each adduct can be independently selected from solid or liquid adducts at a temperature of 23°C. Typically, useful adducts will be characterized by a weight ratio of epoxy resin to elastomer of 1:5 to 5:1, for example, 1:3 to 3:1. Additionally, a guiding reference for suitable epoxy resin / elastomer adducts is U.S. Patent Publication 2004 / 0204551. Furthermore, exemplary commercially available epoxy resin / elastomer adducts used herein include, but are not limited to: HYPDX RK8-4, commercially available from CVC Chemical; and B-Tough A3, commercially available from Croda Europe Limited.

[0179] The term "core-shell rubber" or CSR, according to its standard meaning in the art, refers to a rubber particle core formed of a polymer comprising an elastomeric polymer or a rubber-like polymer as the main component, and a shell formed of a polymer grafted onto said core. The shell partially or completely covers the surface of the rubber particle core during the graft polymerization process. The core should constitute at least 50% by weight of the core-shell rubber particle.

[0180] The polymer material of the core should have a glass transition temperature not exceeding 0°C (T0). g Preferably, the glass transition temperature is -20°C or lower, more preferably -40°C or lower, and even more preferably -60°C or lower. g The polymer of the shell is the glass transition temperature (T). g Non-elastic, thermoplastic, or thermosetting polymers with temperatures above room temperature, preferably above 30°C, and more preferably above 50°C.

[0181] Without limiting the invention, the core may consist of: diene homopolymers, such as butadiene or isoprene homopolymers; diene copolymers, such as butadiene or isoprene copolymers with one or more olefinically unsaturated monomers (such as vinyl aromatic monomers, (meth)acrylonitrile, or (meth)acrylate); polymers based on (meth)acrylate monomers, such as polybutyl acrylate; and polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0182] Similarly, without limiting the invention, the shell can be composed 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 can have acid groups that are ionicly crosslinked by forming metal carboxylates, particularly by forming salts of divalent metal cations. The shell polymer or copolymer can also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0183] Preferably, the average particle size (d50) of any included core-shell rubber particles is from 10 nm to 300 nm, for example, from 50 nm to 250 nm: the particle size refers to the diameter or maximum size 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 types of core-shell rubber (CSR) particles with different particle size distributions in the composition to provide a balance of key properties of the resulting cured product, including shear strength, peel strength, and resin fracture toughness.

[0184] The core-shell rubber can be selected from commercially available products, examples of which include: Paraaloid EXL 2650A, EXL 2655, and EXL2691 A, available from The Dow Chemical Company; and [other products], available from Arkema Inc. XT100; available from Kaneka Corporation. The MX series, especially the MX 120, MX 125, MX 130, MX 136, MX 551, and MX553; as well as the METABLEN SX-006 available from Mitsubishi Rayon.

[0185] The compositions of the present invention may contain conductive particles. Depending on the weight of the composition, the composition may contain, for example, 0 to 10% by weight or 0.1 to 5% by weight of conductive particles.

[0186] In general, there is no particular intention to limit the shape of the particles used as conductive fillers: needle-like, spherical, elliptical, cylindrical, bead-like, cubic, or plate-like particles can be used alone or in combination. Furthermore, it is envisioned that aggregates of more than one particle type can be used. Similarly, there is no particular intention to limit the size of the particles used as conductive fillers. However, such conductive fillers will typically have an average volumetric particle size of 0.1 to 1500 μm, for example, 1 to 1250 μm, as measured by laser diffraction / scattering.

[0187] Exemplary conductive particulate fillers include, but are not limited to: silver; copper; gold; palladium; platinum; nickel; nickel coated with gold or silver; 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; antimony-doped tin oxide; conductive nanospheres; nano-silver; nano-aluminum; nano-copper; nano-nickel; carbon nanotubes; and mixtures thereof. Granular silver and / or carbon black are preferably used as conductive fillers.

[0188] The compositions of the present invention may optionally contain non-conductive fillers. Depending on the weight of the composition, the composition may, for example, contain 0 to 10% by weight or 0.1 to 5% by weight of non-conductive particles.

[0189] In general, there is no particular intention to limit the shape of the particles used as non-conductive fillers: needle-shaped, spherical, elliptical, cylindrical, bead-shaped, cubic, or plate-shaped particles can be used alone or in combination. Furthermore, it is envisioned that aggregates of more than one particle type can be used. Similarly, there is no particular intention to limit the size of the particles used as non-conductive fillers. However, such non-conductive fillers will typically have an average volumetric particle size of 0.1 to 1500 μm, for example, 1 to 1250 μm, as measured by laser diffraction / scattering methods.

[0190] Exemplary non-conductive fillers include, but are not limited to: calcium carbonate, calcium oxide, calcium hydroxide (lime powder), precipitated silica and / or pyrolytic silica, zeolite, bentonite, wollastonite, magnesium carbonate, diatomaceous earth, barium sulfate, alumina, clay, talc, titanium dioxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass beads, glass powder, and other ground minerals. Organic fillers may also be used, particularly wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, rice husks, ground walnut shells, and other chopped fibers. Short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber may also be added.

[0191] Pyrolytic silicic acid and / or precipitated silicic acid advantageously have 10 to 90 m 2 / g BET surface area. When used, they do not cause any additional increase in viscosity of the compositions according to the invention, but do help to enhance the cured composition.

[0192] Similarly, it is conceivable to use materials with a high BET surface area, advantageously 100 to 250 m². 2 / g of pyrolytic silica and / or precipitated silica as fillers: Due to the large BET surface area, the effect of reinforcing the curing composition is achieved with a smaller weight proportion of silica.

[0193] Hollow spheres with mineral or plastic shells are also suitable as non-conductive fillers. For example, these can be marketed under the trade name Glass. Commercially purchased hollow glass spheres. Hollow spheres based on plastic (such as...) or It can be used and is described in EP 0 520 426 B1: it is made of inorganic or organic matter and each has a diameter of 1 mm or less, preferably 500 μm or less.

[0194] Non-conductive fillers that impart thixotropic properties to the composition may be preferred for many applications: such fillers are also described as rheology adjuvants, such as hydrogenated castor oil, fatty acid amides, or expandable plastics (such as PVC).

[0195] The desired viscosity of the resulting curable composition determines the amount of filler used. Regarding this latter consideration, the total amount of both conductive and non-conductive fillers present in the composition should not prevent the composition from being readily applicable to a substrate by a chosen method. For example, a curable composition intended to be extruded from a suitable dispensing device (such as a tube) should have a viscosity of 1,000 to 150,000, preferably 10,000 to 100,000 mPas.

[0196] The "plasticizer" used for the purposes of this invention is a substance that reduces the viscosity of a composition and thereby promotes its processability. In this document, based on the total weight of the composition, the plasticizer may comprise up to 10% by weight or up to 5% by weight, and is preferably selected from: dicarboxylic acid esters; ethers of monofunctional, linear, or branched C4-C16 alcohols, such as Cetiol OE (available from Cognis Deutschland GmbH, Düsseldorf); esters of rosin 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 with OH groups or epoxidized fatty acids; glycolates; benzoates; phosphate esters; sulfonates; trimellitates; polyether plasticizers, such as terminally capped polyethylene glycol or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. It should be noted that phthalates can be used as plasticizers in principle, but these are not preferred due to their toxicological potential.

[0197] The term "stabilizer" used for the purposes of this invention should be understood as an antioxidant, UV stabilizer, heat stabilizer, or hydrolytic stabilizer. In this document, the stabilizer may comprise up to 10% by weight or up to 5% by weight, based on the total weight of the composition. Standard commercially available examples of stabilizers suitable for use herein include: hindered phenols; thioethers; benzotriazoles; benzophenone; benzoate esters; cyanoacrylates; acrylates; hindered amine light stabilizer (HALS) type amines; phosphorus; sulfur; and mixtures thereof.

[0198] It should be noted that compounds with metal chelating properties can be used in the compositions of the present invention to help enhance the adhesion of the cured adhesive to the substrate surface. Furthermore, acetoacetate-functionalized modified resins sold by King Industries under the trade name K-FLEX XM-B301 are also suitable as adhesion promoters.

[0199] To further extend shelf life, it is generally recommended to further stabilize the compositions of the invention against moisture penetration by using a desiccant. Sometimes it is also necessary to reduce the viscosity of the adhesive compositions according to the invention for a particular application by using one or more reactive diluents. The total amount of reactive diluent present, based on the total weight of the composition, will typically be 0 to 10% by weight, for example, 0.1 to 5% by weight.

[0200] The presence of solvents and non-reactive diluents in the compositions of the present invention is not excluded if they can usefully adjust the viscosity of the composition. For example, but only for illustrative purposes, the 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 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, such as Products (available from Exxon); alkylphenols, such as tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecantrienylphenol; styryl phenols; bisphenols; aromatic hydrocarbon resins, especially those containing phenolic groups, such as ethoxylated or propoxylated phenols; adipates; sebacic acid esters; phthalates; benzoates; organophosphates or sulfonates; and sulfonamides.

[0201] In addition to the above, preferably, the total amount of the non-reactive diluent is less than 10% by weight, particularly less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0202] Methods and Applications

[0203] To form the composition, the above components are brought together and mixed. Importantly, the mixing ensures that the polymerizable electrolyte (compound b1) and / or compound b2) are uniformly distributed within the adhesive composition: such thorough and effective mixing determines the uniform distribution of charged substances within the polymer matrix obtained after curing, thereby providing sufficient ionic conductivity to support electrochemical reactions at the interface with the conductive substrate.

[0204] As is known in the art, in order to form a one-component (1K) curable composition, the components of the composition are brought together and uniformly mixed under conditions that inhibit or prevent the reaction of reactive components: such conditions are readily understood by those skilled in the art. Therefore, it is generally preferred not to mix the curable components manually, but rather to mix them in predetermined amounts under anhydrous conditions without intentional light irradiation by a machine (e.g., a static or dynamic mixer).

[0205] For two-component (2K) compositions, the reactive components are brought together and mixed in a manner that causes them to harden. For both one-component (1K) and two-component (2K) compositions, the reactive compounds should be mixed under sufficient shear force to produce a homogeneous mixture. This is considered to be achievable without special conditions or equipment. That is, suitable mixing devices may include: static mixing devices; magnetic stirring rod devices; wire whisk devices; augers; batch mixers; planetary mixers; CW Brabenders or... Type-type mixers; and high-shear mixers, such as blade mixers and rotary high-speed mixers.

[0206] For small-scale liner applications that typically use volumes less than 2 liters, the preferred packaging for a two-component (2K) composition is a side-by-side twin-canister or coaxial canister, in which two tubular chambers are arranged side-by-side or built into each other and sealed with pistons: the actuation of these pistons allows the components to be advantageously extruded from the canisters via a tightly fitted 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, the two components are extruded via a hydraulic press, particularly via a follower plate, and supplied via piping to a mixing device that ensures a fine and highly uniform mixing of the hardener and binder components. In any case, for any packaging, it is important that the binder component is housed in an airtight and moisture-proof seal so that both components can be stored for extended periods (ideally 12 months or longer).

[0207] Non-limiting examples of the two-component dispensing apparatus and method that may be suitable for use with the present invention include those described in U.S. Patent Nos. 6,129,244 and 8,313,006.

[0208] Where applicable, the two-component (2K) composition should be broadly formulated to exhibit an initial viscosity (measured immediately after mixing, e.g., at most two minutes after mixing) that does not impede the application of the composition to a substrate. Furthermore, the two-component (2K) composition should also be formulated to exhibit a pot life of at least 30 minutes, and typically at least 60 or 120 minutes, whereby the "pot life" is the time required for the viscosity of the curable composition to reach twice the viscosity of a freshly mixed curable composition at 20°C and 50% relative humidity.

[0209] According to the broadest aspect of the invention, the above-described composition is applied to a substrate and then cured in situ. Pretreatment of the relevant surface to remove foreign matter is generally recommended before application of the composition; this step (if applicable) can promote subsequent adhesion of the composition to it. Such treatments are known in the art and can be carried out in a single-stage or multi-stage manner, for example, using one or more of the following: etching treatment with an acid suitable for the substrate and optionally an oxidizing agent; acoustic treatment; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric pressure 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 with water, preferably with deionized water or demineralized water. In those cases using an aqueous alkaline degreasing bath, any degreasing agent remaining on the surface should be expected to be removed by rinsing the substrate surface with deionized water or demineralized water.

[0210] In some embodiments, adhesion of the coating composition of the present invention to a preferably pretreated substrate can be promoted by applying a primer thereto. While those skilled in the art will be able to select a suitable primer, guiding references for selecting a primer include, but are not limited to, U.S. Patent Nos. 3,671,483; 4,681,636; 4,749,741; 4,147,685; and 6,231,990.

[0211] The composition is then applied to a preferably pretreated, optionally primer-coated surface of a substrate by conventional application methods such as: brushing; roller coating, for example using a 4-application roller device in the case of a solvent-free composition or a 2-application roller device for a solvent-containing composition; doctor blade application; printing; and spraying, including but not limited to air atomization spraying, air-assisted spraying, airless spraying, and high-volume low-pressure spraying.

[0212] 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 a cured, electrochemically debonded adhesive composition as defined above and in the appended claims is disposed between the first material layer and the second material layer. To produce such a structure, an adhesive composition may be applied to at least one inner surface of the first material layer and / or the second material layer, and the two layers may then optionally be brought into contact under applied pressure such that the electrochemically debonded adhesive composition is disposed between the two layers.

[0213] It is recommended to apply the composition to the surface with a wet film thickness of 10 to 5000 μm, for example 50 to 2500 μm. Applying thinner layers within this range is more cost-effective and provides a reduction in the possibility of harmful thick cured areas. However, strict control must be exercised when applying thinner coatings or layers to avoid both the formation of discontinuous cured films and short contact areas.

[0214] The curing of the compositions of the present invention typically occurs at temperatures between 40°C and 200°C, preferably between 50°C and 190°C, and particularly between 60°C and 180°C. A suitable temperature depends on the specific compounds present and the desired curing rate, 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 aforementioned range is advantageous because it eliminates the need for significant heating or cooling of the mixture from the generally dominant ambient temperature. However, where applicable, the temperature of the mixture formed by the components of the composition can be raised above the mixing temperature and / or the application temperature using conventional means, including microwave induction.

[0215] The invention will be described with reference to the accompanying drawings, in which:

[0216] Figure 1a An adhesive structure according to a first embodiment of the invention is depicted.

[0217] Figure 1b An adhesive structure according to a second embodiment of the invention is depicted.

[0218] Figure 2a The initial debonding of the structure of the first embodiment when a voltage is applied to the structure is depicted.

[0219] Figure 2b The initial debonding of the structure of the second embodiment when a voltage is applied to the structure is depicted.

[0220] As attached Figure 1a As shown, an bonded structure is provided, wherein a cured adhesive layer (10) is disposed between two conductive substrates (11). A non-conductive material layer (12) may be disposed on the conductive substrates (11) to form a structure as shown. Figure 1b The more complex bonded structure is depicted in the diagram. Each layer of the conductive substrate (11) is in electrical contact with a power source (13), which can be a battery or an AC-driven DC power source. The positive and negative terminals of the power source (13) are shown in a fixed position, but those skilled in the art will certainly recognize that the polarity of the system can be reversed.

[0221] Two conductive substrates (11) are shown in the form of layers, which may be composed, in particular, of: a metal film; a metal mesh or grid; deposited metal particles; a resin material that is conductive by means of conductive elements disposed therein; or a conductive oxide layer. Examples of exemplary conductive elements include silver wires, single-walled carbon nanotubes, and multi-walled carbon nanotubes. Examples of exemplary conductive oxides include: doped indium oxide, such as indium tin oxide (ITO); doped zinc oxide; antimony tin oxide; cadmium stannate; and zinc stannate. In addition to the choice of conductive materials, those skilled in the art will recognize that the effectiveness of the debonding operation may be reduced when the conductive substrate (11) is in the form of a grid or mesh (which provides limited contact with the cured adhesive layer (10)).

[0222] When a voltage is applied between each conductive substrate (11), current is supplied to the adhesive composition (10) disposed therebetween. This initiates an electrochemical reaction at the interface between the substrate (11) and the adhesive composition, which should be understood as oxidation at positively charged interfaces or anodic interfaces and reduction at negatively charged interfaces or cathodic interfaces. This reaction is believed to weaken the adhesive bond between the substrates, thereby allowing easy removal of the removable composition from the substrates.

[0223] For illustrative purposes only Figure 2a and Figure 2b As shown, debonding occurs at the positive electrode interface, i.e., the interface between the adhesive composition (10) and the conductive surface (11) that is in electrical contact with the positive electrode. By reversing the current direction before separating the substrates, the adhesive adhesion at the interface between the two substrates can be weakened.

[0224] However, it should be noted that the composition of the adhesive layer (10) can be adjusted so that debonding occurs at the positive or negative interface, or simultaneously from both. In some embodiments, the voltage applied to both surfaces to form the anodic and cathode interfaces will cause debonding to occur simultaneously at the anodic and cathode adhesive / substrate interfaces. In alternative embodiments, if the composition is not responsive to direct current at either interface, reversed polarity can be used to cause simultaneous debonding of the two substrate / adhesive interfaces. The current can be applied in any suitable waveform, provided that sufficient total time is allowed for debonding under each polarity. Sine, rectangular, and triangular waveforms may be suitable in this regard, and can be applied by a controlled voltage source or a controlled current source.

[0225] This invention is not intended to limit the scope of the invention. It is believed that the debonding operation can be effectively performed under at least two of the following conditions: a) an applied voltage of 1 to 100 V, for example 20 to 50 V; and b) a duration of voltage application of 1 second to 180 minutes, for example 1 second to 30 minutes. In cases where the release of the conductive substrate from the cured adhesive is facilitated by applying force (e.g., via a weight or spring), the potential may only need to be applied for about a few seconds.

[0226] The following examples illustrate the present invention, but are not intended to limit the scope of the invention in any way.

[0227] Example

[0228] The following materials and their abbreviations are used in the embodiments:

[0229] MMA: Methyl methacrylate

[0230] MAA: Methacrylic acid

[0231] EGDMA: Ethylene glycol dimethacrylate

[0232] PEG-MEA: Polyethylene glycol methyl ether acrylate

[0233] BENZYL MA: Benzyl methacrylate

[0234] HEMA: (hydroxyethyl) methacrylate

[0235] IBOA: Isoborneol Acrylate

[0236] AIBN: Azobisisobutyronitrile, available from Sigma Aldrich

[0237] BPO: Benzoyl peroxide, available from PanReac Applied Chemie

[0238] HEXMIM StSO3: 3-Methyl-1-hexyl-1H-imidazolium 4-vinylbenzenesulfonate

[0239] EMIM acrylate: 1-Ethyl-3-methyl-1H-imidazolium acrylate

[0240] ViEIM NTf2: 3-Vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide

[0241] BMIM NTf2: 3-Methyl-1-butyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide

[0242] PEG400: Polyethylene glycol, available from Sigma Aldrich

[0243] CN966H90: An aliphatic polyester-based urethane diacrylate oligomer blended with 10% 2-(2-ethoxyethoxy)ethyl acrylate, available from Sartomer.

[0244] SR9054: Acrylic acrylate adhesive accelerator, available from Sartomer

[0245] Preparation of the first group of formulations: formulations EDA1 to EDA14, as well as controls 1, 2 and 3, were prepared by mixing and forming the formulations described in Tables 1a and 1b below.

[0246] Table 1a

[0247]

[0248] Table 1b

[0249]

[0250] The quantities in parentheses for polymerizable electrolytes given in Tables 1a and 1b are in millimoles (mmol).

[0251] Controls 1, 2, and 3 consist of nonionic matrix monomers that form a binder in the absence of any ionic substances. Formulations EDA1 to EDA7, EDA9 to EDA11, and EDA13 to EDA14 are based on copolymerization of nonionic matrix monomers with polymerizable ionic compounds.

[0252] EDA8 is a mixture of a nonionic matrix monomer and a cured polymerizable electrolyte (PE) copolymer, obtained as follows: First, ViEIM NTf2 (0.359 g) and HexMIM StSO3 (0.104 g) are mixed with azobisisobutyronitrile (0.008 g) at a high speed of 3600 rpm for one minute; then the mixture is cured at 80°C for 15 minutes, followed by curing at 120°C for 2 hours; finally, the cured material is mixed with the nonionic matrix monomer and azobisisobutyronitrile.

[0253] EDA12 is a reference and is based on a mixture of nonionic matrix monomers and nonpolymerizable ionic compounds (BMIM NTf2).

[0254] The substrates for application of formulations EDA1 to EDA14 and the control were 1.25 mm thick aluminum (AA6016), and the coating compositions were applied using glass beads with a diameter of 100 to 200 micrometers as spacers. The substrates were cut into 2.5 cm × 10 cm samples for tensile testing. The tensile lap shear (TLS) test was performed at room temperature based on ISO 4587 Adhesives—Determination of tensile lap-shear strength of rigid-to-rigid bonded assemblies (ISO, 2003). The bonded overlap area for each substrate was 2.5 cm × 1.0 cm, and the bond thickness was 0.1 cm (40 mil). INSTRON 3366 with a 10 kN cell was used.

[0255] The applied adhesive composition was cured in the overlapping area by applying a temperature of 80°C for 15 minutes and then a temperature of 120°C for 120 minutes. The bonded structure was then stored at room temperature for 24 hours prior to the initial tensile test.

[0256] Example 1

[0257] Tensile lap shear strength was studied before and after a constant potential of 50V was applied to the adhesive layer for 30 minutes following the 24-hour storage period. The results are recorded in Table 2 below.

[0258] Table 2

[0259] adhesives Initial bond strength (MPa) Adhesive strength (MPa) after 50V and 30 minutes Comparison 1 2.03(±0.59) 2.11(±0.28) EDA1 3.67(±0.56) 3.15(±0.06) EDA2 2.18(±0.36) 1.48(±0.20) EDA3 3.44(±0.31) 0 EDA4 3.07(±0.58) 0.71(±0.62) EDA5 2.63(±0.51) 1.10(±0.23) EDA6 2.66(±0.34) 1.71(±0.12) EDA7 3.85(±0.71) 2.80(±0.63) EDA8 2.09(±0.13) 2.08(±0.33) EDA9 2.61(±0.09) 0.97(±0.09) EDA10 1.98(±0.41) 0 EDA11 2.35(±0.11) 0 EDA12 (reference) 1.60(±0.60) 0 Comparison 2 1.76(±0.77) 1.17(±0.61) EDA13 2.60(±0.54) 1.54(±0.12) Comparison 3 1.53(±0.63) 2.32(±0.45) EDA14 2.67(±0.86) 0

[0260] Formulations containing polymerizable ionic compounds increase initial adhesive strength. After voltage is applied, the adhesive strength of formulations based on copolymerization of polymerizable ionic compounds and nonionic matrix monomers decreases.

[0261] Example 2

[0262] This embodiment investigates the electrodelamination behavior of the adhesive formulation EDA5 by measuring the tensile lap shear strength before and after applying different constant potentials to the adhesive layer for a duration of 30 minutes following the 24-hour storage period. The results are recorded in Table 3 below.

[0263] Table 3

[0264]

[0265] Example 3

[0266] This embodiment investigates the electrodelamination behavior of certain of the aforementioned adhesives by measuring the tensile lap shear strength before and after applying a constant potential of 50V to the adhesive layer for 30 minutes, following both the 24-hour storage period and the 2-month storage period. The results are recorded in Table 4 below.

[0267] Table 4

[0268]

[0269] Formulations based on copolymerization of nonionic matrix monomers and polymerizable ionic compounds maintained their initial adhesive strength after two months and still showed a decrease in adhesive strength after voltage was applied.

[0270] Preparation of the second group of formulations: formulations EDA15 to EDA19 and control 4 were prepared by mixing and described in Table 5 below.

[0271] Table 5

[0272]

[0273] Control 4 is composed of nonionic matrix monomers that form a binder in the absence of any ionic substances. Formulations EDA15 to EDA18 are based on copolymerization of nonionic matrix monomers with polymerizable ionic compounds.

[0274] EDA19 is a reference and is based on a mixture of nonionic matrix monomers and nonpolymerizable ionic compounds (BMIM NTf2).

[0275] The substrates for application of formulations EDA15 to EDA19 and Control 4 were 1.25 mm thick aluminum (AA6016) and 1.5 mm thick stainless steel (1.4301), and the coating compositions were applied using glass beads with a diameter of 100 to 200 micrometers as spacers. The substrates were cut into samples measuring 2.5 cm × 10 cm (1” × 4”) for tensile testing. The tensile lap shear (TLS) test was performed at room temperature based on ISO 4587 Adhesives—Determination of tensile lap shear strength of rigid-to-rigid bonded components (International Organization for Standardization, 2003). The bonded overlap area for each substrate was 2.5 cm × 1.0 cm, and the bond thickness was 0.1 cm (40 mil). A Zwick Z020 with a 20 kN element was used.

[0276] The applied adhesive composition was cured in the overlapping area by applying a temperature of 80°C for 15 minutes and then a temperature of 120°C for 30 minutes. The bonded structure was then stored at room temperature for 24 hours prior to the initial tensile test.

[0277] Example 4

[0278] Tensile lap shear strength was studied before and after a constant potential of 50V was applied to the adhesive layer for 30 minutes following the 24-hour storage period. The results are recorded in Table 6 below.

[0279] Table 6

[0280]

[0281] Formulations EDA15 and EDA18, containing polymerizable ionic compounds, maintained their initial adhesive strength, while formulation EDA17 showed a decrease in initial strength. Formulation EDA19, containing nonpolymerizable ionic liquids, showed a 50% decrease in initial strength. After applying voltage, the adhesive strength of formulations based on the copolymerization of polymerizable ionic compounds with nonionic matrix monomers decreased.

[0282] Example 5

[0283] This embodiment investigates the electrodelamination behavior of certain of the aforementioned adhesives (EDA15, compared to EDA19) by measuring the tensile lap shear strength before and after applying a constant potential of 50V to the adhesive layer for a duration of 30 minutes, following the 24-hour storage period and after storage periods of 1 week, 1 month, 2 months, and 3 months. A climatized chamber set to 23°C and 50% relative humidity was used. The results are recorded in Tables 7 and 8 below.

[0284] Table 7

[0285]

[0286] Table 8

[0287]

[0288] Formulation EDA15, based on the copolymerization of a nonionic matrix monomer and a polymerizable ionic compound, showed a slight decrease in adhesive strength (12%) after three months. Formulations based on a mixture of a nonpolymerizable ionic liquid and a nonionic matrix monomer showed a greater decrease in adhesive strength (30%) for both aluminum and stainless steel after two months. All formulations showed a decrease in adhesive strength after the application of voltage.

[0289] In view of the foregoing description and embodiments, it will be apparent to those skilled in the art that equivalent modifications may be made thereto without departing from the scope of the claims.

Claims

1. A curable and electrochemically detangleable adhesive composition, wherein, based on the weight of the composition, the adhesive composition comprises: 40 to 99% by weight of a) at least one olefinically unsaturated nonionic monomer, said olefinically unsaturated nonionic monomer being a combination of the following components: • At least one (meth)acrylate monomer represented by Formula I, and / or at least one (meth)acrylate monomer represented by Formula II: H2C=CGCO2R 1 (I) in: -G is hydrogen, halogen, or C1-C4 alkyl; and -R 1 Selected from C1-C 30 Alkyl, C1-C6 hydroxyalkyl, C2-C 30 Heteroalkyl, C3-C 30 Cycloalkyl, C2-C8 heterocycloalkyl, C2-C 20 alkenyl and C2-C 12 alkynyl group, H2C=CQCO2R 2 (II) in: -Q is hydrogen, halogen, or C1-C4 alkyl; and -R 2 Selected from C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 Alkyl and C7-C 18 Aryl group, at least one (meth)acrylate-functionalized oligomer, •Optionally available olefinic unsaturated nonionic monomers selected from the following: α,β-olefinic unsaturated monocarboxylic acids containing 3 to 5 carbon atoms, poly(meth)acrylates of alkane polyols, and mixtures thereof; 0.9 to 50% by weight of b) at least one polymerizable ionic compound, wherein said polymerizable ionic compound comprises: b1) At least one compound according to general formula IV: and / or b2) At least one compound according to general formula V: Where: R 7 Selected from: C1-C 30 Alkyl; C2-C8 alkenyl; C1-C 30 Heteroalkyl; C 3- C 30 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b ,in R a It is a C1-C6 alkylene group, and R b It is a C1-C6 alkyl group; Each R in the compound according to general formula IV 8 Independently selected from H, C1-C 18 Alkyl, C1-C 18 Heteroalkyl, C3-C 18 cycloalkyl, C6-C 18 Aryl, C1-C9 heteroaryl, C 7- C 18 Alkyl aryl, or C2-C5 heterocyclic alkyl; Each R in the compound according to general formula V 8 Independently selected from H or C1-C6 alkyl groups; R 9 It is an H or C1-C4 alkyl group; Each R 10 Independently selected from C1-C8 alkyl, C1-C8 heteroalkyl, C 3- C 12 cycloalkyl, or C 2- C5 heterocyclic alkyl groups; A is a non-polymerizable anion selected from: fluoride ion; chloride ion; bromide ion; iodide ion; tetrafluoroborate; trifluorophosphate; hexafluorophosphate; methyl sulfate; ethyl sulfate; methanesulfonate; 4-methylbenzenesulfonate; trifluoromethanesulfonate; bis(trifluoromethanesulfonate)imide; trifluoroacetate; and tri(perfluoroethyl)trifluorophosphate; T is an olefinically unsaturated anion selected from: (meth)acrylate; itaconic acid; maleate; crotonate; isocrotonate; vinylbenzoate; 2-acrylamido-2-methylpropanesulfonate; sulfoethyl(meth)acrylate; sulfopropyl(meth)acrylate; sulfonated acrylamide; allylsulfonate; vinylsulfonate; 4-vinylbenzenesulfonate; 4-isopropenylbenzenesulfonate; allylphosphonate; and monoacryloyloxyethyl phosphate. d and m are each an integer with a value of at least 1; e and n have values ​​that make the compound electrically neutral; and It is a covalent bond, or a C1-C2 alkylene bond; and c) at least one free radical initiator, ranging from 0.1 to 10% by weight.

2. The adhesive composition according to claim 1, wherein the adhesive composition comprises: 45 to 95% by weight of at least one olefinic unsaturated nonionic monomer of a); 5 to 30% by weight of at least one polymerizable ionic compound described in b); 0.1 to 5% by weight of c) at least one free radical initiator; and 0 to 10% by weight of d) solubilizer.

3. The adhesive composition according to claim 1 or claim 2, wherein, Based on the weight of the composition, part a) comprises 40 to 95% by weight of at least one (meth)acrylate monomer represented by Formula I.

4. The adhesive composition according to claim 1 or claim 2, wherein, Based on the weight of the composition, portion a) comprises up to 50% by weight of the at least one (meth)acrylate-functionalized oligomer.

5. The adhesive composition according to claim 4, wherein, Based on the weight of the composition, part a) comprises 5 to 25% by weight of the at least one (meth)acrylate-functionalized oligomer.

6. The adhesive composition according to claim 1 or claim 2, wherein part a) comprises at least one α,β-olefinic unsaturated monocarboxylic acid having 3 to 5 carbon atoms.

7. The adhesive composition according to claim 1 or claim 2, wherein in part b): R 7 Selected from C1-C8 alkyl; C2-C4 alkenyl; C1-C8 heteroalkyl; C 3- C 12 cycloalkyl; C6-C 18 Aryl; C1-C9 heteroaryl; C 7- C 18 alkylaryl; C 2- C5 heterocyclic alkyl; or -R a -C(=O)-R b , where R a It is a C1-C4 alkylene group, and R b It is a C1-C4 alkyl group; Each R 8 Independently selected from H or C1-C2 alkyl groups; R 9 It is H or methyl; and Each R 10 Independently selected from C1-C8 alkyl; C1-C8 heteroalkyl; C3-C 12 Cycloalkyl; or C2-C5 heterocycloalkyl.

8. The adhesive composition according to claim 1 or claim 2, wherein portion b) comprises: b1) At least one compound selected from the group consisting of: 3-vinyl-1-methyl-1H-imidazolium iodide; 3-vinyl-1-methyl-1H-imidazolium chloride; 3-vinyl-1-methyl-1H-imidazolium bromide; 3-vinyl-1-methyl-1H-imidazolium methane sulfonate; 3-vinyl-1-methyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methane sulfonamide; 3-vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methane sulfonamide; 3-vinyl-1-methyl-1H-imidazolium hexafluorophosphate; 3-vinyl-1-methyl-1H- Imidazolium 4-methylbenzenesulfonate; 3-vinyl-1-methyl-1H-imidazolium tetrafluoroborate; 3-vinyl-1-ethyl-1H-imidazolium iodide; 3-vinyl-1-ethyl-1H-imidazolium bromide; 3-vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 3-vinyl-1-ethyl-1H-imidazolium hexafluorophosphate; 3-vinyl-1-ethyl-1H-imidazolium tetrafluoroborate; 3-vinyl-1-(1-methylethyl)-1H-imidazolium bromide; 3-(1,1-dimethylethyl)-1-vinyl-1H-imidazolium bromide; 3-vinyl -1-propyl-1H-imidazolium bromide; 3-vinyl-1-(phenylmethyl)-1H-imidazolium bromide; 1-vinyl-3-(4-methylphenyl)-1H-imidazolium chloride; 3-vinyl-1-(1-methylpropyl)-1H-imidazolium chloride; 1-butyl-3-vinyl-1H-imidazolium bromide; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium iodide; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium chloride; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methane sulfonamides; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium hexafluorophosphate; 3-[(4-vinylphenyl)methyl]-1-methyl-1H-imidazolium tetrafluoroborate; 3-[(4-vinylphenyl)methyl]-1-ethyl-1H-imidazolium chloride; salts of 1-[(4-vinylphenyl)methyl]-3-ethyl-1H-imidazolium and 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1-(3-aminopropyl)-3-[(4-vinylphenyl)methyl]-1H-imidazolium chloride; 1-butyl-3-[(4-vinylphenyl)methyl]-1H-imidazolium chloride; and / or b2) At least one compound selected from the following: 1-methyl-3-hexyl-1H-imidazolium 4-vinylbenzenesulfonate; 1-methyl-3-propyl-1H-imidazolium 4-vinylbenzenesulfonate; and 3-ethyl-1-methyl-1H-imidazolium 4-(1-methylvinyl)benzenesulfonate.

9. The adhesive composition according to claim 1 or claim 2, wherein part b) comprises at least one compound selected from: 3-methyl-1-hexyl-1H-imidazolium 4-vinylbenzenesulfonate; 3-vinyl-1-ethyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; and 3-methyl-1-butyl-1H-imidazolium 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide.

10. The adhesive composition according to claim 1 or claim 2, wherein portion c) comprises at least one azo radical initiator selected from: azonitrs; azo esters; azo amides; azomides; azoimidazolines; and macromolecular azo initiators.

11. The adhesive composition according to claim 1 or claim 2, wherein, Based on the weight of the composition, the composition contains up to 10% by weight of d) a solubilizer, and the solubilizer is selected from: polyoxyalkylene glycols; Organosilicon surfactants; polyols; and sugars.

12. The adhesive composition according to claim 1 or claim 2, wherein, Based on the weight of the composition, the composition contains at most 10% by weight of conductive particles.

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

14. An adhesive structure, said adhesive structure comprising: A first material layer having a conductive surface; as well as A second material layer having a conductive surface; The curable and electrochemically debonded adhesive composition according to any one of claims 1 to 13 is disposed between the first material layer and the second material layer.

15. A method for detaching an adhesive structure according to claim 14, the method comprising the following steps: 1) Apply voltage to the two surfaces to form an anode interface and a cathode interface; as well as 2) De-adhere the surface.

16. The method of claim 15, wherein the voltage applied in step 1 is from 0.5 to 200 V.

17. The method of claim 16, wherein the voltage applied in step 1 is applied for a duration of 1 second to 30 minutes.

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