JP2023530767A - Electrochemically strippable adhesive composition - Google Patents

Abstract

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

Description

The present invention is directed to curable adhesive compositions that are releasable from certain substrates to which they are applied. More specifically, the present invention is directed to a curable, electrochemically releasable adhesive composition comprising a polymerizable electrolyte.

Adhesive bonding and polymer coatings are commonly used in product assembly and finishing. They are used to replace mechanical fasteners such as screws, bolts and rivets to provide joints with reduced machining costs and improved compatibility with manufacturing processes. Adhesive bonds evenly distribute stress, reduce the potential for fatigue, and seal the joint from corrosive species.

Although adhesive bonding offers many advantages over mechanical fasteners, it tends to be difficult to disassemble adhesively bonded objects required in practical applications, such as recycling of the primary material that is bonded. Adhesive removal by mechanical processes such as sandblasting or wire brushing cannot be polished without damaging the surface of the substrates, in part due to the adhesive being placed between the substrates. or because it is difficult to polish, it is often excluded. Decomposition by the application of chemicals and/or high temperatures, as disclosed in US Pat. No. 4,171,240 (Wong) and US Pat. No. 4,729,797 (Linde et al.), may be effective but is slow to perform. can be complicated. Also, the aggressive chemicals and/or the harsh conditions required can damage the substrate being separated and render it unsuitable for subsequent use.

Some authors have focused on these problems and proposed an electrochemically strippable adhesive composition in which passage of an electric current through the curing composition acts to break the bond at the adhesive-substrate interface. I am considering developing a product.

US 2007/0269659 (Gilbert) describes (i) containing a polymer and an electrolyte, (ii) facilitating bonding of the two surfaces, and (iii) applying to both surfaces such that anodic and cathodic interfaces are formed. A dual interface peelable adhesive composition is disclosed that releases from both the anode and cathode surfaces in response to an applied voltage.

US 2008/0196828 (Gilbert) describes a hot melt adhesive composition comprising a thermoplastic component and an electrolyte, wherein the electrolyte undergoes a Faraday reaction at the bond formed between the composition and an electrically conductive surface. Hot-melt adhesive compositions are disclosed that provide the composition with sufficient ionic conductivity to allow the release of the composition from a surface.

WO 2007/142600 (Stora Enso AB) describes providing an adhesive bond to a conductive surface and sufficient ionic conducting properties to allow weakening of said adhesive bond when a voltage is applied to the adhesive composition. wherein said composition comprises at least one ionic compound in an amount sufficient to impart said ionic conduction properties, said ionic compound having a temperature of 120° C. or less An adhesive composition is disclosed having a melting point of .

EP 3363875 A (Nitto Denko Corporation) discloses an electrically detachable adhesive composition that forms an adhesive layer with high adhesion that can be easily detached with the application of a voltage for a short period of time. The electrically releasable adhesive composition of the same reference comprises a polymer and 0.5 to 30% by weight of an ionic liquid based on the weight of the polymer, wherein the anion of the ionic liquid is bis(fluorosulfonyl)imide. is an anion.

WO 2013/135677 (Henkel AG & Co. KGaA) describes 20-90% by weight of at least one polyamide with a molecular weight (Mw) of 10,000-250,000 g/mol; A hot melt adhesive is disclosed comprising an organic or inorganic salt of 1;

WO 2016/135341 (Henkel AG & Co. KGaA) describes a reaction in which the adhesion is at least partially lost when an electric voltage is applied, thus allowing the release of adhesively bonded substrates. A flexible hot melt adhesive composition is disclosed. More specifically, the reactive hot melt adhesive composition comprises a) at least one isocyanate-functional polyurethane polymer; and b) at least one organic or inorganic salt.

WO 2017/133864 (Henkel AG & Co. KGaA) describes a method for reversibly joining a first substrate and a second substrate, wherein at least the first substrate is a non-conductive substrate, the method a) coating the surface of a non-conductive substrate with a conductive ink; c) contacting the first and second substrates such that the electrically releasable hot melt adhesive composition is interposed between the two substrates; d) ) enabling the formation of an adhesive bond between two substrates to provide a bonded substrate; e) at least one adhesive between the electrically removable hot melt adhesive composition and the substrate surface; A method is disclosed that includes applying a voltage to the joined substrates such that the bond at the two interfaces is substantially weakened.

U.S. Patent No. 4,171,240 U.S. Patent No. 4,729,797 US 2007/0269659 US 2008/0196828 WO 2007/142600 EP 3363875A WO 2013/135677 WO 2016/135341 WO 2017/133864

When ionic liquids or electrolytes are included in the adhesive composition, it can be difficult to achieve compatibility between the electrolyte and the polymer matrix. Electrolyte leakage and phase separation from the cured polymer matrix have been recognized in the known art as drawbacks in the application of electrically strippable adhesives.

It is known in the art that adhesives that can be conveniently applied to the surfaces of the substrates to be bonded and provide effective bonding within composite structures containing said substrates when cured, but that readily apply an electrical potential to the cured adhesive. Thus, there is still a need to provide adhesive compositions that can be effectively released from these substrates. The cured adhesive should also provide a stable polymer matrix with minimal component leakage and no phase separation.

で示される化合物、および／または
ｂ２）少なくとも１の、一般式Ｖ：

［式中、Ｒ^７は、C₁-C₃₀アルキル；C₂-C₈アルケニル；C₁-C₃₀ヘテロアルキル；C₃-C₃₀シクロアルキル；C₆-C₁₈アリール；C₁-C₉ヘテロアリール；C₇-C₁₈アルキルアリール；C₂-C₅ヘテロシクロアルキル；または-R^a-C(=O)-R^b〔ここで、Ｒ^ａはC₁-C₆アルキレン基であり、Ｒ^ｂはC₁-C₆アルキル基である〕から選択され；
各Ｒ^８は独立して、H、C₁-C₁₈アルキル、C₁-C₁₈ヘテロアルキル、C₃-C₁₈シクロアルキル、C₆-C₁₈アリール、C₁-C₉ヘテロアリール、C₇-C₁₈アルキルアリールまたはC₂-C₅ヘテロシクロアルキルから選択され；
Ｒ^９は、HまたはC₁-C₄アルキルであり；
各Ｒ^１０は独立して、C₁-C₃₀アルキル；C₁-C₃₀ヘテロアルキル；C₃-C₃₀シクロアルキル；C₆-C₁₈アリール；C₁-C₉ヘテロアリール；C₇-C₁₈アルキルアリール；C₂-C₅ヘテロシクロアルキル；または-R^a-C(=O)-R^b〔ここで、Ｒ^ａはC₁-C₆アルキレン基であり、Ｒ^ｂはC₁-C₆アルキル基である〕から選択され；
Ａは、非重合性アニオンであり；
Ｔは、エチレン性不飽和アニオンであり；
ｄおよびｍはそれぞれ、少なくとも１の整数であり；
ｅおよびｎは、化合物が電気的に中性になるような数値であり；

は、共有結合、C₁-C₂アルキレン、-CH₂OC(=O)-、-CH₂CH₂OC(=O)-、p-ベンジルまたはp-トリルである］
で示される化合物を含んでなる、接着剤組成物が提供される。 According to a first embodiment of the present invention, a curable, electrochemically releasable adhesive composition comprising, based on the weight of the composition,
40-99% by weight, preferably 45-90% by weight of a) at least one ethylenically unsaturated nonionic monomer;
0.9-50% by weight, preferably 5-30% by weight b) at least one polymerizable ionic compound; and 0.1-10% by weight, preferably 0.1-5% by weight c) at least one wherein the polymerizable ionic compound comprises a free radical initiator of
b1) at least one of general formula IV:

and/or b2) at least one of general formula V:

_{C2 -} ^C8 alkenyl; _C1 - _{C30 heteroalkyl} ; _C3 - _C30 cycloalkyl _{; C6 - C18} aryl _{; C7} - _C18 alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a _C1 - _C6 alkylene group; R ^b is a _C1 - _C6 alkyl group];
Each ^R8 is independently H, _C1 - _C18 alkyl, _C1 - _C18 heteroalkyl, _C3 - _C18 cycloalkyl, _C6 - _C18 aryl, _C1 - _C9 heteroaryl, _{C7 -C18} alkylaryl or _C2 - _C5 heterocycloalkyl;
^R9 is H or _C1 - _C4 alkyl;
_C1 - _C30 ^heteroalkyl _{; C3} - _C30 cycloalkyl; _{C6 - C18} aryl; _C1 - _{C9 heteroaryl} ; ₁₈ alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a C ₁ -C ₆ alkylene group and R ^b is a C ₁ -C ₆ alkyl groups];
A is a non-polymerizable anion;
T is an ethylenically unsaturated anion;
d and m are each an integer of at least 1;
e and n are such that the compound is electrically neutral;

is a covalent bond, _C1 - _C2 alkylene, _{-CH2OC (} =O)-, _-CH2CH2OC (=O)-, p-benzyl or p-tolyl]
An adhesive composition is provided comprising a compound represented by

FIG. 1a shows a bonded structure according to a first embodiment of the invention. FIG. 1b shows a bonded structure according to a second embodiment of the invention. Figure 2a shows the initial delamination of the structure of the first embodiment upon application of a voltage to the structure of the first embodiment. Figure 2b shows the initial debonding of the second embodiment structure upon application of a voltage to the second embodiment structure.

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

In one embodiment of the composition, part a) thereof comprises from 40 to 95%, preferably from 45 to 90%, by weight of the composition, of a1) formula (I):
_H2C = _CGCO2R1 ( ^I )
[wherein G is hydrogen, halogen or a _C1 - _C4 alkyl group;
R ¹ is from _C1 - _C30 alkyl, _C2 - _C30 heteroalkyl, _C3 - _C30 cycloalkyl; _C2 - _C8 heterocycloalkyl; _C2 - _C20 alkenyl and _C2 - _C12 alkynyl selected]
at least one (meth)acrylate monomer represented by

Part a) of the composition further comprises 0 to 30%, for example 0 to 15% by weight based on the weight of the composition, of a2) formula (II):
_H2C = _CQCO2R2 ( ^II )
[wherein Q can be hydrogen, halogen or a _C1 - _C4 alkyl group; ^R2 is _C6 - _C18 aryl, _C1 - _C9 heteroaryl, _C7 - _C18 alkaryl and C ₇ - _C18aralkyl ]
may be characterized by containing at least one (meth)acrylate monomer represented by

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

Considering the electrolyte b) of the curable, electrochemically strippable composition, both the ionic compounds of formulas IV and V described above and described below are functionalized reactive to radical polymerization. groups, preferably vinyl, allyl or acrylic functionalities. Thereby, the polymerizable electrolyte should polymerize with any of the above monomers a).

For compounds of formula IV(b1), the cation is based on the imidazolium ring and covalently bonds to the adhesive matrix upon completion of the selected curing profile: the counteranion (A) is free to move within the polymer matrix. . Conversely, for compounds of formula V(b2), the anions of the polymerizable electrolyte are covalently bound to the adhesive matrix upon curing, while the imidazolium ring-based cations are free to move within the matrix.

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

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

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

According to a second embodiment of the present invention, comprising a first material layer with an electrically conductive surface and a second material layer with an electrically conductive surface, as described above and in the appended claims. A bonded structure is provided wherein an electrochemically releasable curable adhesive composition is disposed between a first material layer and a second material layer.

According to a third embodiment of the invention,
i) applying a voltage to both surfaces to form an anodic and cathodic interface; and
ii) There is provided a method of debonding a bonded structure as described above and in the appended claims, comprising the step of debonding these surfaces.

Step i) of the method preferably comprises
characterized by at least one of a) an applied voltage of 1-100 V; and b) a voltage application of between 1 second and 180 minutes.

The adhesive properties of the composition are destroyed by applying an electrical potential to the bond line between the composition and the conductive surface. While not intending to be bound by the following theory, the Faraday reaction that occurs at the interface between the adhesive composition and the conductive surface disrupts the interaction between the adhesive and the substrate, thereby It is believed that the bond between them is weakened. This interfacial failure can be the result of one or more processes such as chemical degradation of the peelable material, gassing at the interface, and/or material embrittlement due to changes in the crosslink density of the adhesive composition, for example.

DEFINITIONS As used herein, the singular forms "a,""an," and "the" include plural referents unless the context clearly dictates otherwise.
As used herein, the terms “comprising,” “including,” and “included” are synonymous with “comprising,” “included,” “contains,” or “contains.” open-ended and does not exclude additional components, elements, or method steps not described.
As used herein, the term “consisting of” excludes any unspecified element, component, member, or method step.
When amounts, concentrations, dimensions and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values, upper preferred values and lower preferred values, upper or preferred values and lower or preferred values are interchangeable. It should be understood that ranges obtained by combining are also specifically disclosed regardless of whether the context explicitly mentions them.
Also, in accordance with standard understanding, a weight range designated "0-x" specifically includes 0 weight percent: the component defined by said range may be absent or absent in the composition. , may be present in the composition in an amount up to x weight percent.
The terms "preferred,""preferably,""preferably," and "particularly" are frequently used herein to refer to embodiments of the disclosure that may provide certain benefits under certain circumstances. . However, the recitation of one or more preferred, preferred, or particular embodiments does not imply that other embodiments are not useful or exclude those other embodiments from the scope of the disclosure. nor is it intended to
Throughout this specification, the term "may" is used in a permissive rather than mandatory sense, ie, in the sense of possibility.
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 exists or in which the coating layer or the substrate of said coating layer exists.

A "two-part (2K) composition" herein is a composition in which the first component (1) and the second component (2) must be stored in separate containers due to their (high) reactivity. understood to be a thing. The two parts are mixed only immediately before application and then typically react without additional activation to form bonds and thereby form a polymer network. Higher temperatures may be applied in the present invention to facilitate the cross-linking reaction.
As used herein, the term "electrochemically releasable" means that the bond strength can be weakened by at least 50% when a potential of 50 V is applied for 60 minutes after curing of the adhesive. A curing adhesive is applied between two substrates to be joined by said adhesive and an electric current is passed through the adhesive bond line. Bond strength is determined by a tensile lap shear (TLS) test performed at room temperature according to ASTM D3163-01, "Test Method for Standard Measurement of Strength of Adhesively Bonded Rigid Plastic Lap Shear Joints in Shear by Tensile Loads". measured by The bond overlap area was 2.5 cm by 1.0 cm (1 inch by 0.4 inch) and the adhesive thickness was 0.1 cm (40 mils).
The term "electrolyte" is used herein according to its standard meaning in the art as a substance containing free ions capable of conducting electricity by displacement of charge carrier species. The term is intended to encompass molten electrolytes, liquid electrolytes, semi-solid electrolytes and solid electrolytes in which at least one of the cationic or anionic components of the electrolyte structure is essentially freely substituted and functions as a charge carrier. ing.
The curable adhesive compositions of the present invention and the cured adhesives obtained therefrom have an "electrolyte function" in that the adhesive allows the conduction of ions, either anions, cations or both.
Electrolyte function is understood to derive from the ability of the composition and cured adhesive to solvate ions of at least one polarity.
The term "Faraday reaction" means an electrochemical reaction in which substances are oxidized or reduced.

As used herein, the term "monomer" refers to a substance that can undergo a polymerization reaction to contribute a building block to the chemical structure of the polymer. As used herein, the term "monofunctional" refers to having one polymerizable moiety. As used herein, the term "polyfunctional" refers to having two or more polymerizable moieties.
As used herein, the term "ethylenically unsaturated monomer" refers to any monomer containing a terminal double bond that is polymerizable under normal conditions for radical addition polymerization.
As used herein, the term "equivalent weight (eq.)" refers to the relative number of reactive groups present in a reaction, as is customary in chemical notation.
As used herein, "(meth)acrylic" is an abbreviation that refers to "acrylic" and/or "methacrylic". The term "(meth)acrylate" therefore refers collectively to acrylates and methacrylates.
As used herein, a "C ₁ -C _n alkyl" group refers to a monovalent or alkane group containing from 1 to n carbon atoms and includes straight and branched chain organic groups. do. A “C ₁ -C ₃₀ alkyl” group therefore refers to a monovalent radical, ie, an alkane group, containing from 1 to 30 carbon atoms, and includes straight and branched chain organic groups. Alkyl groups include, but are not limited to: methyl; ethyl; propyl; isopropyl; n-butyl; - Ethylhexyl. In the present invention such alkyl groups may be unsubstituted or substituted with one or more substituents selected from halogen, hydroxy, nitrile (-CN), amido and amino ( _-NH2 ). may Where applicable, preferences for named substituents are indicated in the specification. Generally, however, alkyl groups having 1 to 18 carbon atoms (C ₁ -C ₁₈ alkyl), such as alkyl groups having 1 to 12 carbon atoms (C ₁ -C ₁₂ alkyl) or 1 to 6 It should be noted that alkyl groups having carbon atoms ( _C1 - _C6 alkyl) are preferred.
As used herein, the term "C ₁ -C ₁₈ hydroxyalkyl" refers to HO-(alkyl) groups having 1 to 18 carbon atoms. wherein the point of attachment of the substituent is through the oxygen atom and the alkyl group is as defined above.
An "alkoxy group" refers to a monovalent group represented by -OA. Here, A is an alkyl group, non-limiting examples of which are methoxy, ethoxy and isopropyloxy groups.

The term "C ₁ -C ₆ alkylene" as used herein means a saturated divalent hydrocarbon having from 1 to 6 carbon atoms having linear, branched or cyclic moieties or combinations thereof. defined as the base.
The term " _C3 - _C30 cycloalkyl" is understood to mean an optionally substituted saturated monocyclic, bicyclic or tricyclic hydrocarbon radical having 3 to 30 carbon atoms. be done. It should be noted that, in general, cycloalkyl groups having 3 to 18 carbon atoms (C ₃ -C ₁₈ cycloalkyl groups) are preferred. Examples of cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; In the present invention such cycloalkyl groups may be unsubstituted or substituted with one or more substituents selected from halogen, _C1 - _C6 alkyl and _C1 - _C6 alkoxy. good.
As used herein, a " _C6 - _C18 aryl" group, used alone or as part of a larger group such as an "aralkyl group", refers to whether the monocyclic ring system is aromatic , or optionally substituted monocyclic, bicyclic and tricyclic ring systems wherein at least one of the rings of the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic ring systems include benzofused 2- to 3-membered carbocyclic rings. In the present invention such aryl groups may be unsubstituted or optionally substituted with one or more substituents selected from halogen, _C1 - _C6 alkyl and _C1 - _C6 alkoxy. . Exemplary aryl groups include: phenyl; ( _C1 - _C4 )alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; It may be noted that phenyl groups are preferred.
As used herein, " _C2 - _C20 alkenyl" refers to hydrocarbyl groups having from 2 to 20 carbon atoms and having at least one unit of ethylenic unsaturation. The alkenyl group may be straight, branched or cyclic and may be optionally substituted. The term "alkenyl" includes groups having "cis" and "trans" configurations, or alternatively "E" and "Z" configurations, as understood by those of ordinary skill in the art. It should be noted, however, that in general unsubstituted alkenyl groups having 2 to 10 (C _2-10 ) or 2 to 8 (C _2-8 ) carbon atoms are preferred. Examples of said _C2 - _C12 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 ; -CH _{2CH = 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 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohexyl-3-enyl.

As used herein, "alkylaryl" refers to alkyl-substituted aryl groups and "substituted alkylaryl" refers to alkylaryl groups further bearing one or more of the above substituents. Also, as used herein, "aralkyl" means an alkyl group substituted with an aryl group as described above.
The term "hetero" as used herein means a group or moiety containing one or more heteroatoms selected from N, O, Si, P and S. For example, "heterocycle" refers to a cyclic group having N, O, Si, P or S as part of the ring structure. As used herein, "heteroalkyl,""heterocycloalkyl," and "heteroaryl" groups each contain N, O, Si, P, or S as part of their structure. "Cycloalkyl" and "aryl" groups.
For completeness, the term " _C2 - _C30 heteroalkyl" refers to an "alkyl" group having a total of 2 to 30 carbon atoms, wherein at least one carbon atom is substituted with a heteroatom. point to A specific example of such a heteroalkyl group is a “C ₂ -C ₁₈ alkoxyalkyl”, which refers to an alkyl group having an alkoxy substituent as described above, wherein the (alkyl-O-alkyl) moieties total from 1 to 18 carbon atoms]: such groups are methoxymethyl _{( -CH2OCH3} ), 2 _- methoxyethyl ( _-CH2CH2OCH3 ) and ₂ - _ethoxyethyl ( _{-CH2CH2 OCH2CH3 )} . Another example of a heteroalkyl group is " _C2 - _C30 aminoalkyl" [which contains a total of 2 to 30 carbon atoms and includes -NH(R'), -N(R')(R" ) or N ⁺ (R')(R")(R"'), wherein R', R" and R"' are _C1 - _C6 alkyl is: such groups include 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl and 2-(trimethylamino)ethyl.
The term “C ₁ -C ₉ heteroaryl” refers to an aromatic group having 1 to 9 carbon atoms and 1 to 4 heteroatoms, where the group optionally contains heteroatoms, or carbon atoms. may be coupled via The heteroaryl ring can be fused or attached to one or more heteroaryl, aromatic or non-aromatic hydrocarbon rings or heterocycloalkyl rings. Examples of heteroaryl groups include, but are not limited to: pyridine; furan; thiophene; 5,6,7,8-tetrahydroisoquinoline; pyrimidine; benzothiazolyl; isoxazolyl; oxadiazolyl; isothiazolyl; benzisothiazolyl; triazolyl; tetrazolyl; pyrrolyl; indolyl;

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

a) Nonionic Matrix Monomer The composition of the present invention comprises at least one ethylenically unsaturated nonionic monomer, the (co)polymerization of which yields a peelable adhesive matrix. Monomer a) can in principle be any ethylenically unsaturated nonionic monomer. However, the invention is particularly applicable to compositions in which the (meth)acrylic monomers constitute at least 50 mol %, preferably at least 75 mol % of the total molar amount of ethylenically unsaturated nonionic monomers present. .

a1) Aliphatic and Cycloaliphatic (Meth)acrylate Monomers In an important embodiment of the invention, the composition of the invention comprises 40 to 95% by weight, preferably 45 to 90% by weight, based on the weight of the composition. a1) at least one of formula (I):
_H2C = _CGCO2R1 ( ^I )
[wherein G is hydrogen, halogen or a _C1 - _C4 alkyl group;
_C2 - _C30 heteroalkyl; _C3 ^- _C30 cycloalkyl; _{C2 - C8} heterocycloalkyl; _{C2 -C20 alkenyl} ; and _C2 - _C12 alkynyl selected from]
comprising a (meth)acrylate monomer represented by
For example, R ¹ is _C1 - _C18 alkyl, _C2 - _C18 heteroalkyl, _C3 - _C18 cycloalkyl; _C2 - _C8 heterocycloalkyl; _C2 - _C8 alkenyl and _C2 - _C8. may be selected from alkynyl;

Preferably, said monomer a1) is characterized in that R ¹ is selected from C ₁ -C ₁₈ alkyl and C ₃ -C ₁₈ cycloalkyl. This description of preferred embodiments is expressly intended to include embodiments in which R ¹ is C ₁ -C ₆ hydroxylalkyl.
Examples of (meth)acrylate monomers a1) of formula (I) include, but are not limited to: methyl (meth)acrylate; ethyl (meth)acrylate; butyl (meth)acrylate; hexyl (meth) Acrylates; 2-ethylhexyl (meth)acrylate; dodecyl (meth)acrylate; lauryl (meth)acrylate; cyclohexyl (meth)acrylate; isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate (HEMA); (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.

a2) Aromatic (meth)acrylate monomers The compositions of the present invention contain, based on the weight of the composition, 0 to 30% by weight, such as 0.1 to 30% by weight, 0.1 to 25% by weight or 0.1% by weight. ~15% by weight of a2) at least one of formula (II):
_H2C = _CQCO2R2 ( ^II )
[wherein Q may be hydrogen, halogen or a _C1 - _C4 alkyl group;
^R2 may be selected from _C6 - _C18 aryl, _C1 - _C9 heteroaryl, _C7 - _C18 alkaryl and _C7 - _C18 aralkyl]
may further contain a (meth)acrylate monomer represented by
Examples of (meth)acrylate monomers a2) of formula (II) include, but are not limited to, the following, which may be used alone or in combination: benzyl (meth)acrylate; phenoxyethyl (meth)acrylate; ) acrylates; phenoxydiethylene glycol (meth)acrylate; phenoxypropyl (meth)acrylate; and phenoxydipropylene glycol (meth)acrylate.

a3) (meth)acrylate-functionalized oligomers In an important embodiment of the invention, this is intended to mutually exclude the inclusion of aliphatic and cycloaliphatic monomers (a1) and aromatic monomers (a2). no), the composition of the present invention should contain from 0 to 50%, preferably from 5 to 25% by weight of a3) at least one (meth)acrylate-functionalized oligomer, based on the weight of the composition. Said oligomers may have one or more acrylate and/or methacrylate groups attached to the oligomer backbone, and the (meth)acrylate functional groups may be located at the ends of the oligomer and/or may be attached to the oligomer backbone. may be distributed along

The at least one (meth)acrylate functionalized oligomer i) has two or more (meth)acrylate functional groups per molecule; and/or ii) has a weight average molecular weight (Mw) of 300 to 1000 Daltons. preferable.

Examples of such oligomers include, but are not limited to, the following, which may be used alone or in combination: (meth)acrylate functionalized urethane oligomers such as (meth)acrylate functionalized polyester urethanes and (meth) (meth)acrylate functionalized polyepoxide resins; (meth)acrylate functionalized polybutadienes; (meth)acrylic polyols (meth)acrylates; polyester (meth)acrylate oligomers; polyamide (meth)acrylate oligomers; Ether (meth)acrylate oligomers. Such (meth)acrylate functionalized oligomers and methods for their preparation are described, inter alia, in US Pat. No. 4,574,138; US Pat. No. 4,439,600; US Pat. U.S. Patent No. 4,018,851; U.S. Patent No. 3,676,398; U.S. Patent No. 3,770,602; U.S. Patent No. 4,072,529; 4,206,025; disclosed in U.S. Pat. No. 5,002,976. Among the polyether (meth)acrylate oligomers, specific examples include, but are not limited to: PEG 200 DMA (n≈4); PEG 400 DMA (n≈9); PEG 600 DMA (n ≈14); and PEG 800 DMA (n≈19). Here the assigned number (eg 400) represents the weight average molecular weight of the glycol portion of the molecule.

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

While not intending to limit the invention, such additional ethylenically unsaturated nonionic monomers may include: silicone (meth)acrylate monomers, such as U.S. Pat. No. 5,605,999 (Chu ); α,β-ethylenically unsaturated monocarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid; C ₁ -C ₁₈ of crotonic acid. Alkyl esters; α,β-ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms and their anhydrides, monoesters and diesters; Vinyl esters such as vinyl acetate, vinyl propionate, and Shell. VEOVA ^TM series monomers available from Chemical Company; vinyl and vinylidene halides; vinyl ethers such as vinyl ethyl ether; alkyl vinyl ketones, cycloalkyl vinyl ketones, aryl vinyl ketones, arylalkyl vinyl ketones, and aryl cycloalkyl vinyls. vinyl ketones, including ketones; aromatic or heteroaliphatic vinyl compounds; poly(meth)acrylates of alkane polyols, such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate. acrylates, neopentyl glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; polyols of oxyalkane polyols; (meth)acrylates such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dibutylene glycol di(meth)acrylate, di(pentamethylene glycol) dimethacrylate; polyethylene glycol di(meth)acrylate; and bisphenol A di(meth)acrylates, such as ethoxylated bisphenol A (meth)acrylate (EBIPMA).

Typical examples of other ethylenically unsaturated polymerizable nonionic monomers include, but are not limited to: ethylene glycol dimethacrylate (EGDMA); methanol, ethanol, propanol, isopropanol, butanol, isobutanol, Mono- and diesters of fumaric, maleic and itaconic anhydrides with _C1 - _C4 alcohols such as tert-butanol. Typical examples of vinyl monomers include, but are not limited to: vinyl acetate; vinyl propionate; vinyl ethers such as vinyl ethyl ether; and vinyl ethyl ketone. Typical examples of aromatic or heteroaliphatic vinyl compounds include, but are not limited to: styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene, 2-vinylpyrrolidone, 5-ethylidene. - compounds such as 2-norbornene and 1-, 3- and 4-vinylcyclohexene;

で示される化合物、および／または
ｂ２）少なくとも１の、一般式Ｖ：

［式中、Ｒ^７は、C₁-C₃₀アルキル；C₂-C₈アルケニル；C₁-C₃₀ヘテロアルキル；C₃-C₃₀シクロアルキル；C₆-C₁₈アリール；C₁-C₉ヘテロアリール；C₇-C₁₈アルキルアリール；C₂-C₅ヘテロシクロアルキル；または-R^a-C(=O)-R^b〔ここで、Ｒ^ａはC₁-C₆アルキレン基であり、Ｒ^ｂはC₁-C₆アルキル基である〕から選択され；
各Ｒ^８は独立して、H、C₁-C₁₈アルキル、C₁-C₁₈ヘテロアルキル、C₃-C₁₈シクロアルキル、C₆-C₁₈アリール、C₁-C₉ヘテロアリール、C₇-C₁₈アルキルアリールまたはC₂-C₅ヘテロシクロアルキルから選択され；
Ｒ^９は、HまたはC₁-C₄アルキルであり；
各Ｒ^１０は独立して、C₁-C₃₀アルキル；C₁-C₃₀ヘテロアルキル；C₃-C₃₀シクロアルキル；C₆-C₁₈アリール；C₁-C₉ヘテロアリール；C₇-C₁₈アルキルアリール；C₂-C₅ヘテロシクロアルキル；または-R^a-C(=O)-R^b〔ここで、Ｒ^ａはC₁-C₆アルキレン基であり、Ｒ^ｂはC₁-C₆アルキル基である〕から選択され；
Ａは、非重合性アニオンであり；
Ｔは、エチレン性不飽和アニオンであり；
ｄおよびｍはそれぞれ、少なくとも１の整数であり；
ｅおよびｎは、化合物が電気的に中性になるような数値であり；

は、共有結合、C₁-C₂アルキレン、-CH₂OC(=O)-、-CH₂CH₂OC(=O)-、p-ベンジルまたはp-トリルである］
で示される化合物を含んでなる。 b) Electrolyte The composition of the present invention comprises 0.9 to 50% by weight, such as 5 to 50% by weight or 10 to 45% by weight b) of at least one polymerizable ionic compound, the polymerizable ionic The compound is
b1) at least one of general formula IV:

and/or b2) at least one of general formula V:

_{C2 -} ^C8 alkenyl; _C1 - _{C30 heteroalkyl} ; _C3 - _C30 cycloalkyl _{; C6 - C18} aryl _{; C7} - _C18 alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a _C1 - _C6 alkylene group; R ^b is a _C1 - _C6 alkyl group];
Each ^R8 is independently H, _C1 - _C18 alkyl, _C1 - _C18 heteroalkyl, _C3 - _C18 cycloalkyl, _C6 - _C18 aryl, _C1 - _C9 heteroaryl, _{C7 -C18} alkylaryl or _C2 - _C5 heterocycloalkyl;
^R9 is H or _C1 - _C4 alkyl;
_{C1 - C30} ^heteroalkyl _{; C3} - _C30 cycloalkyl; _{C6 - C18} aryl; _C1 - _C9 heteroaryl; ₁₈ alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a C ₁ -C ₆ alkylene group and R ^b is a C ₁ -C ₆ alkyl groups];
A is a non-polymerizable anion;
T is an ethylenically unsaturated anion;
d and m are each an integer of at least 1;
e and n are such that the compound is electrically neutral;

is a covalent bond, _C1 - _C2 alkylene, _{-CH2OC (} =O)-, _-CH2CH2OC (=O)-, p-benzyl or p-tolyl]
comprising a compound represented by

_{C2 -} ^C6 alkenyl; _C1 - _C12 heteroalkyl; _{C3 - C18} cycloalkyl; _{C6 - C18} aryl _; C7 _{- C18} alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where _R ^a is _C1 - _C6 alkylene and R ^b is a C ₁ -C ₆ alkyl group. _C1 - _C8 alkyl; _C2 - _C4 alkenyl; _C1 - _C8 heteroalkyl; _C3 - _C12 cycloalkyl; _{C6 -C18} ^aryl _{; C7 - C18} alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a _C1 - _C4 alkylene group; , R ^b is a C ₁ -C ₄ alkyl group. When R ⁷ can be an alkenyl group, the imidazolium group can have one or more ethylenically unsaturated groups: exemplary groups in this regard are 1-H-imidazolium, 1-3-diethenyl; Note that it includes -H-imidazolium, 3-ethenyl-1-(2-propen-1-yl)-.

Each R ⁸ is preferably independently selected from H or C ₁ -C ₆ alkyl, more particularly independently H or C ₁ -C ₂ alkyl. Preferably, at least one ^R8 can be H. R ⁹ is preferably H or C ₁ -C ₂ alkyl, more particularly H or methyl.

_{C1 - C12} ^heteroalkyl ; _C3 - _C18 cycloalkyl; _{C6 - C18} aryl; _C1 - _C9 heteroaryl; _{C2 - C5} heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is _a C ₁ -C ₆ alkylene group and R ^b is C is a ₁ - _C6 alkyl group]. _C1 - _C8 heteroalkyl; _C3 - _C12 ^cycloalkyl ; _{C6 - C18 aryl} ; _{C1 - C9} heteroaryl; ₁₈ alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b [wherein R ^a is a _C1 - _C4 alkylene group and R ^b is _{a C1} -C ₄ is an alkyl group].

For compounds of formula (IV), anion A is typically selected from the group consisting of: fluoride; chloride; bromide; iodide; sulphate; sulphite; carbonate; hydrogen carbonate; hydrogen phosphate; hydrogen sulphate; hydrogen sulphite; 4-methylbenzenesulfonate; diethyl phosphate; formate; acetate; propionate; tartrate; octanoate; bis(2,4,4-trimethylpentyl bis(oxalate)borate; bis(pentafluoroethyl)phosphinate; tetracyanoborate; tetrafluoroborate; bis(phthalate)borate; bis(salicylate)borate; bis(trifluoromethylsulfonate) imide; bis(trifluoromethanesulfonyl)methane; bis(trifluoromethyl)imidate; tetrakis(hydrogensulfonate)borate; tetrakis(methylsulfonate)borate; trifluoromethylsulfonate; nonafluorobutyl)trifluorophosphate; tris(pentafluoroethyl)trifluorophosphate; tris(pentafluoroethylsulfonyl)trifluorophosphate; trichlorozincate; trifluoroacetate; bromoaluminate; chloroaluminate; thiocyanate; tosylate; and dicyanamide.

Anion A is preferably fluoride; chloride; bromide; iodide; perchlorate; nitrate; formate; 4-methylbenzenesulfonate; trifluoromethylsulfonate; bis(trifluoromethylsulfonate)imide, trifluorophosphate, trifluoroacetate; and tris(perfluoroethyl)trifluorophosphate. selected from the group.

Bromide; Iodide; Tetrafluoroborate; Hexafluorophosphate; Methylsulfate; Ethylsulfate; sulfonate) imides.

Anions T are ethylenically unsaturated carboxylate anions (R-COO-); ethylenically unsaturated sulfonate anions (R-SO ₃ ^- ); ethylenically unsaturated phosphonate anions (R-PO ₃ ^2- ); saturated phosphinate anion (RP(H)O ₂ ^- ); and ethylenically unsaturated phosphate anion (RO-PO ₃ ^2- ), where R is an organic compound with ethylenic unsaturation that polymerizes under normal conditions. a group, which group is preferably derived from (meth)acrylic acid, vinylic acid or allylic acid.

Typical anions T include: (meth)acrylate; itanconate; maleate; crotonate; (meth)acrylates; sulfomethylated acrylamides; allylsulfonates; vinylsulfonates; 4-vinylbenzenesulfonate (4-styrenesulfonate); 4-isopropenylbenzenesulfonate (4-methylstyrenesulfonate); .

Examples of compounds b1) of formula (IV) include, but are not limited to: 1H-imidazolium, 3-ethenyl-1-methyl-, iodide; 1H-imidazolium, 3- Ethenyl-1-methyl-, chloride; 1H-imidazolium, 3-ethenyl-1-methyl-, bromide; 1H-imidazolium, 3-ethenyl-1-methyl-, methanesulfonate; 1H-imidazolium, 3-ethenyl -1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-methyl-, 1,1,1-tri Fluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-methyl-, hexafluorophosphate; 1H-imidazolium, 3-ethenyl-1-methyl-, 4- Methylbenzenesulfonate; 1H-imidazolium, 3-ethenyl-1-methyl-, tetrafluoroborate; 1H-imidazolium, 3-ethenyl-1-ethyl-, iodide; 1H-imidazolium, 3-ethenyl-1-ethyl -, bromide; 1H-imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl- 1-ethyl-, hexafluorophosphate; 1H-imidazolium, 3-ethenyl-1-ethyl-, tetrafluoroborate; 1H-imidazolium, 1,3-diethenyl-, chloride; 1H-imidazolium, 1,3- Diethenyl-, tetrafluoroborate; 1H-imidazolium, 1,3-diethenyl-, hexafluorophosphate; 1H-imidazolium, 3-ethenyl-1-ethyl-2-methyl-, iodide; 1H-imidazolium, 3- Ethenyl-1,2-dimethyl-, iodide; 1H-imidazolium, 3-ethenyl-1,2-dimethyl-, chloride; 1H-imidazolium, 3-ethenyl-2-ethyl-1-methyl-, iodide; 1H -imidazolium, 3-(aminomethyl)-1-ethenyl-, bromide; 1H-imidazolium, 3-ethenyl-1-(1-methylethyl)-, bromide; 1H-imidazolium, 3-(1,1 -dimethylethyl)-1-ethenyl-, bromide; 1H-imidazolium, 3-ethenyl-1-propyl-, bromide; 1H-imidazolium, 1-(2-aminoethyl)-3-ethenyl-, chloride; 1H -imidazolium, 1-(cyanomethyl)-3-ethenyl-, bromide; 1H-imidazolium, 1-[2-(diethylamino)ethyl]-3-ethenyl-, chloride; 1H-imidazolium, 3-ethenyl-1 -(2-propen-1-yl)-, chloride; 1H-imidazolium, 3-ethenyl-1-(2-propen-1-yl)-, 1,1,1-trifluoro-N-[(tri Fluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-(2-propen-1-yl)-, bromide; 1H-imidazolium, 3-ethenyl-1-(phenylmethyl)-, Bromide; 1H-imidazolium, 1-ethenyl-3-(4-methylphenyl)-, chloride; 1H-imidazolium, 3-ethenyl-1-(2-hydroxyethyl)-, chloride; 1H-imidazolium, 3 -ethenyl-1-(1-methylpropyl)-, chloride; 1H-imidazolium, 1-butyl-3-ethenyl-, bromide; 1H-imidazolium, 3-ethenyl-1-(2-ethoxyethyl)-, Bromide; 1H-imidazolium, 1-methyl-3-(2-propen-1-yl)-, iodide; 1H-imidazolium, 1-methyl-3-(2-propen-1-yl)-, chloride; 1H-imidazolium, 1-methyl-3-(2-propen-1-yl)-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 1-methyl-3-(2-propen-1-yl)-, hexafluorophosphate; 1H-imidazolium, 1-methyl-3-(2-propen-1-yl)-, tetrafluoroborate; 1H-imidazo Lithium, 1-ethyl-3-(2-propen-1-yl)-, iodide; 1H-imidazolium, 2-methyl-3-(2-propen-1-yl)-1-propyl-, bromide; 1H -imidazolium, 3-(2-propen-1-yl)-1-propyl-, bromide; 1H-imidazolium, 3-(2-hydroxyethyl)-1-(2-propen-1-yl)-, Bromide; 1H-imidazolium, 1-butyl-3-(2-propen-1-yl)-, bromide; 1H-imidazolium, 1,3-di-2-propen-1-yl-, bromide; 1H- Imidazolium, 1,3-di-2-propen-1-yl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 1,3- Di-2-propen-1-yl-, tetrafluoroborate; 1H-imidazolium, 3-(2-hydroxyethyl)-1-(2-propen-1-yl)-, bromide; 1H-imidazolium, 1 -(2-cyanoethyl)-3-(2-propen-1-yl)-, bromide; 1H-imidazolium, 1-methyl-3-(2-oxopropyl)-, tetrafluoroborate; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, iodide; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, chloride; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-[( 4-ethenylphenyl)methyl]-1-methyl-, hexafluorophosphate; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, tetrafluoroborate; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1-ethyl-, chloride; 1H-imidazolium, 1-[(4-ethenylphenyl)methyl]-3-ethyl-, 1,1,1-tri Salt of fluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 1-(3-aminopropyl)-3-[(4-ethenylphenyl)methyl]-, chloride; 1H- Imidazolium, 1-butyl-3-[(4-ethenylphenyl)methyl]-, chloride; 1H-imidazolium, 1-methyl-3-[[(1-oxo-2-propen-1-yl)oxy ]methyl]-, bromide; 1H-imidazolium, 1-ethyl-3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-, iodide; and 1H-imidazolium, 1-butyl -3-[[(1-oxo-2-propen-1-yl)oxy]methyl]-, iodide. For the sake of completeness, such compounds may be present singly or in combination of two or more in the compositions of the present invention.

Although not intended to limit the invention, representative examples of compounds of formula (IV) include the following.

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

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

Although not intended to limit the invention, representative examples of compounds of formula (V) include the following.

In one embodiment, the electrically strippable adhesive composition can include both b1) one or more compounds of formula (IV); and b2) one or more compounds of formula (V). Please note that When both are present, it is preferred that the ratio of b1) and b2) is from 5:1 to 1:1, eg from 4:1 to 2:1.

c) Free Radical Initiator The compositions of the present invention comprise c) at least one free radical initiator. The composition typically comprises c) at least one free radical-initiating should contain drugs.

Although not intended to limit the invention, exemplary types of free radical initiators suitable for use herein include, for example, cyclic peroxides; diacyl peroxides; dialkyl peroxides; peroxycarbonates; peroxydicarbonates; peroxyesters; and peroxyketals.

Certain peroxides, such as dialkyl peroxides, have been disclosed as useful initiators, inter alia, in U.S. Pat. No. 3,419,512 (Lees) and U.S. Pat. While obtaining, hydroperoxides represent a preferred type of initiator for the present invention. Hydrogen peroxide itself may also be used, but the most preferred initiators are organic hydroperoxides. For the sake of completeness, the definition of hydroperoxide includes materials such as organic peroxides or organic peresters that decompose or hydrolyze in situ to form organic hydroperoxides: Examples of mono- and peresters are cyclohexyl and hydroxycyclohexyl peroxides, respectively, and t-butyl perbenzoate.

In one embodiment of the invention, the free radical initiator has the formula:
R ^p OOH
[wherein R ^P is an aliphatic or aromatic group having up to 18 carbon atoms, preferably: R ^P is C ₁ -C ₁₂ alkyl, C ₆ -C ₁₈ aryl or C ₇ -C ₁₈ is an aralkyl group]
comprising or consisting of at least one hydroperoxide compound of

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

Although not intended to limit the invention, other exemplary types of free radical initiators suitable for use herein include, for example, azonitrile; azoester; azoamide; azoamidine; azoimidazoline; is an azo polymerization initiator selected from agents.

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

It is not excluded that the compositions of the present invention may contain at least one free-radical photoinitiator compound that initiates polymerization or curing of the composition upon exposure to actinic radiation.

Typically, free-radical photoinitiators form radicals by cleavage, known as "Norrish type I" and by abstraction of hydrogen to form radicals, known as "Norrish type II". are classified as those that exist. Norrish type II photoinitiators require a hydrogen donor to act as a source of free radicals: Because initiation is based on a bimolecular reaction, Norrish type II photoinitiators are generally of the Norrish type based on unimolecular formation of radicals. Slower than the I photoinitiator. On the other hand, Norrish type II photoinitiators have better light absorption properties in the near UV spectral region. One skilled in the art should be able to select a suitable free radical photoinitiator based on the actinic radiation used for curing and the sensitivity of the photoinitiator at that wavelength.

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

1-hydroxycyclohexylphenyl ketone; benzophenone; 4-chlorobenzophenone; 4-methylbenzophenone; 4-phenylbenzophenone; 4,4'-bis(diethylamino)benzophenone; '-bis(N,N'-dimethylamino)benzophenone (Michler's ketone); isopropylthioxanthone; 2-hydroxy-2-methylpropiophenone (Daracur 1173); 2-methyl-4-(methylthio)-2-morpholino Propiophenone; methyl phenyl glyoxylate; methyl 2-benzoyl benzoate; 2-ethylhexyl 4-(dimethylamino) benzoate; ethyl 4-(N,N-dimethylamino) benzoate; phenylbis(2,4,6-trimethyl) benzoyl)phosphine oxide; diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide; and ethylphenyl (2,4,6-trimethylbenzoyl)phosphinate. Again certainly, combinations of two or more of these photoinitiators are not excluded in the present invention.

When the composition of the present invention comprises a free-radical photoinitiator, irradiation of said curable composition produces active species from the photoinitiator that initiate the curing reaction. Once the seeds are generated, curing chemistry follows the same thermodynamic rules as chemical reactions: reaction rates can be accelerated by heat. The use of heat treatment to accelerate actinic curing of monomers is generally known in the art.

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

The use of free radical (photo)initiators can result in residual compounds from (photo)chemical reactions in the final cured product. Residues can be detected by conventional analytical techniques such as infrared, ultraviolet and NMR spectroscopy; gas or liquid chromatography; and mass spectroscopy. Thus, the present invention can include a cured matrix (co)polymer and detectable amounts of residue from free radical (photo)initiators. Residues are present in small amounts and usually do not interfere with the desired physico-chemical properties of the final cured product.

d) Solubilizer The composition of the present invention may optionally contain a solubilizer. The composition may contain, for example, 0.1-10% or 0.1-5% by weight of the solubilizer based on the weight of the composition. Solubilizers have the function of promoting miscibility of the electrolyte b) in the adhesive composition: the solubilizer may or may not form part of the polymer matrix formed upon curing of the adhesive composition. may be used, but serve to facilitate ion movement therein. The solubilizer is preferably a compound that is itself polar and should preferably be liquid at room temperature.

Suitable types of solubilizers include: polyphosphazenes; polymethylene sulfides; polyoxyalkylene glycols; polyethyleneimine; functionalized polyalkylsiloxanes and epoxy resin copolymers, such as polydimethylsiloxane (PDMS) and epoxy resin copolymers; polyhydric alcohols; and sugars. For the sake of completeness, fluorinated silicone surfactants, such as fluorinated polysiloxanes, are intended to be included in the term "silicone surfactant."

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

It may be noted that, among polyoxyalkylene glycols, the use of polyoxy(C ₂ -C ₃ )alkylene glycols having a weight average molecular weight of 200 to 10000 g/mol, eg 200 to 2000 g/mol is particularly preferred.

Additives and Auxiliary Components The compositions obtained in the present invention may typically further comprise additives and auxiliary components that can impart improved properties to these compositions. For example, additives and adjunct ingredients can provide one or more of the following: improved elastic properties, improved elastic recovery, extended processing time, decreased cure time, and reduced residual tack. Such additives and auxiliary ingredients include: non-polymeric electrolytes; reinforcing agents; conductive particles; electrically non-conductive fillers; catalysts; anti-oxidants; reactive diluents; desiccants; adhesion promoters; fungicides;

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

The presence of non-polymeric electrolytes in the compositions of the invention is not excluded. Exemplary electrolytes include non-polymerizable salts of cations selected from the group consisting of ammonium; pyridinium; phosphonium; imidazolium; oxazolium; The anions ^of _such ^{non -} _{polymerizable salts are} ^not _particularly limited, _preferred anions _are the halides _{; 3} CO ₂ ⁻ halogen-containing compounds and pseudohalides; carboxylic acid anions, especially formate, acetate, propionate, butyrate and lactate; hydroxycarboxylic acid anions; pyridinates and pyrimidinates; carboxylic acid imides, bis(sulfonyl)imides and sulfonylimides; sulfates, especially methylsulfate and ethylsulfate; sulfites; sulfonates, especially methanesulfonate; and phosphates, especially dimethylphosphate, diethylphosphate and di-(2-ethylhexyl)-phosphate.

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

The presence of a toughening agent in the composition of the invention can be beneficial to the release of cured adhesives. While not intending to be bound by theory, the toughener promotes phase separation within the cured adhesive under application of an electrical potential. Good release results have been obtained especially when the composition according to the invention comprises at least one reinforcing agent selected from reinforcing rubber in the form of core-shell particles dispersed in a matrix polymer; and epoxy elastomer adducts.

Elastomer-containing adducts may be used individually, or a combination of two or more specific adducts may be used. Also, each adduct can be independently selected from a solid adduct or a liquid adduct at a temperature of 23°C. Typically, useful adducts may feature a weight ratio of epoxy to elastomer of 1:5 to 5:1, such as 1:3 to 3:1. Also a reference for suitable epoxy/elastomer adducts is US Patent Publication 2004/0204551. Further, exemplary commercially available epoxy/elastomer adducts for use in the present invention include HYPDX RK8-4 available from CVC Chemical and B-Tough A3 available from Croda Europe Limited. but not limited to:

The term "core-shell rubber" or "CSR" is used according to its standard meaning in the art, a rubber particle core formed by a polymer comprising an elastomer or rubbery polymer as the main component, and a and the shell layer formed by the graft polymerized polymer. The shell layer partially or entirely covers the surface of the rubber particle core in the graft polymerization process. By weight, the core should constitute at least 50% by weight of the core-shell rubber particles.

The polymeric material of the core has a glass transition temperature (Tg) of 0°C or lower, preferably -20°C or lower, more preferably -40°C or lower, even more preferably -60°C or lower should. The polymer of the shell is a non-elastomeric, thermoplastic or thermoset polymer having a glass transition temperature (Tg) above room temperature, preferably above 30°C, more preferably above 50°C.

Without limiting the invention, the core comprises a diene homopolymer, such as a homopolymer of butadiene or isoprene; a diene copolymer, such as butadiene or isoprene, and one or more ethylenically unsaturated monomers such as vinyl aromatic monomers, copolymers with (meth)acrylonitrile or (meth)acrylate); polymers based on (meth)acrylic acid ester monomers (eg polybutyl acrylate); and polysiloxane elastomers such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

Similarly, without limiting the invention, the shell may include (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; It may consist of a polymer or copolymer of one or more monomers selected from (meth)acrylamide. The polymer or copolymer used for the shell may have acid groups that ionically crosslink through metal carboxylate formation, particularly through formation of salts of divalent metal cations. The shell polymer or copolymer may be covalently crosslinked by monomers having two or more double bonds per molecule.

Any core-shell rubber particles included preferably have an average particle size (d50) of 10 nm to 300 nm, such as 50 nm to 250 nm; measured by For the sake of completeness, the present invention employs different particle size distributions in the composition to provide a balance of key properties (including shear strength, peel strength, resin fracture toughness, etc.) of the resulting cured product. The presence of more than one type of core-shell rubber (CSR) particles is not excluded.

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

The compositions of the invention may contain electrically conductive particles. The composition may contain, for example, 0-10% or 0.1-5% by weight of conductive particles, based on the weight of the composition.

Generally, there is no intention to specifically limit the shape of the particles used as conductive fillers: acicular, spherical, ellipsoidal, cylindrical, beaded, cubic or platelet-shaped particles, alone or in combination. may be used. It is also envisioned that more than one particle type aggregate may be used. Likewise, there is no specific intention to limit the size of the particles used as conductive fillers. However, such conductive fillers may typically have an average volume particle size measured by laser diffraction/scattering of 0.1 to 1500 μm, such as 1 to 1250 μm.

Examples of conductive particulate fillers include, but are not limited to: silver; copper; gold; palladium; platinum; silver-coated copper; silver-coated aluminum; metal-coated glass spheres; metal-coated fillers; metal-coated polymers; silver-coated fibers; silver-coated spheres; nanocopper; nanonickel; carbon nanotubes; and mixtures thereof. Particulate silver and/or carbon black are preferably used as conductive fillers.

The compositions of the present invention may optionally contain electrically non-conductive fillers. The composition may comprise, for example, 0-10% or 0.1-5% by weight of electrically non-conductive particles, based on the weight of the composition.

In general, there is no intention to specifically limit the shape of the particles used as non-conductive fillers: particles that are needle-shaped, spherical, ellipsoidal, cylindrical, bead-shaped, cubic or platelet-shaped, either singly or May be used in combination. It is also envisioned that more than one particle type aggregate may be used. Likewise, there is no intention to specifically limit the size of the particles used as non-conductive fillers. However, such non-conductive fillers may typically have an average volume particle size measured by laser diffraction-scattering techniques of 0.1-1500 μm, such as 1-1250 μm.

Exemplary non-conductive fillers include, but are not limited to: calcium carbonate, calcium oxide, calcium hydroxide (lime powder), precipitated and/or calcined silicic acids, zeolites, bentonites, wollastons. Nite, magnesium carbonate, diatomite, barium sulfate, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass beads, glass powder, and other crushed mineral substances. Organic fillers can also be used, especially wood fibres, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, rice husks, ground walnut husks, and other chopped fibers. Short fibers such as glass fibres, glass filaments, polyacrylonitrile, carbon fibres, Kevlar fibres, or polyethylene fibres, can also be added.

Precipitated and/or calcined silica preferably has a BET surface area of 10 to 90 m ² /g. When used, they do not further increase the viscosity of the composition of the invention, but contribute to strengthening the cured composition.

It is likewise conceivable to use as fillers precipitated and/or calcined silicic acids with a higher BET surface area, preferably between 100 and 250 m ² /g; A material-strengthening effect is achieved with a lower weight proportion of silicic acid.

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

Non-conductive fillers that impart thixotropy to the composition may be suitable for many applications: such fillers are also referred to as rheology aids, e.g. plastic.

The desired viscosity of the resulting curable composition can depend on the amount of filler used. Considering the latter consideration, the total amount of fillers (both conductive and non-conductive) present in the composition is such that the composition is readily applied by the selected method of application of the composition to a substrate. should not be hindered. For example, a curable composition intended to be extruded through a suitable dispensing device such as a tube should have a viscosity of 1000-150,000 mPas, preferably 10,000-100,000 mPas.

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

A "stabilizer" for the purposes of the present invention should be understood as an antioxidant, UV stabilizer, thermal stabilizer or hydrolytic stabilizer. In the present invention, the stabilizers may total up to 10% or up to 5% by weight based on the total weight of the composition. Standard commercial examples of stabilizers suitable for use in the present invention include: sterically hindered phenols; thioethers; benzotriazoles; benzophenones; HALS) type amines; phosphorus; sulfur; and mixtures thereof.

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

To further extend shelf life, it is often recommended to further stabilize the compositions of the present invention with respect to moisture penetration by using a desiccant. There is also often a need to reduce the viscosity of the adhesive compositions of the present invention for specific applications by using reactive diluents. The total amount of reactive diluent present may typically be 0-10% by weight, eg 0.1-5% by weight, based on the total weight of the composition.

The presence of solvents and non-reactive diluents in the composition of the invention is also not excluded, provided that this can effectively reduce its viscosity. For example, for purposes of illustration only, a composition may contain one or more of the following: xylene; 2-methoxyethanol; dimethoxyethanol; 2-ethoxyethanol; 2-propoxyethanol; Ethanol; 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; n-butyl ether; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; diethylene glycol di-n-butyryl ether; propylene glycol butyl ether; propylene glycol phenyl ether; diphenylmethane; diisopropylnaphthalene; petroleum fractions such as Solvesso® products (available from Exxon); alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-penta decatrienyl phenols; styrenated phenols; bisphenols; aromatic hydrocarbon resins, especially those with phenolic groups, such as ethoxylated or propoxylated phenols; adipates; and sulfonamides.

Apart from the above, it is preferred that said non-reactive diluents in total constitute less than 10% by weight, in particular less than 5% or less than 2% by weight, based on the total weight of the composition.

Methods and Uses The above parts are mixed together to form the composition. It is important that the mixing results in a uniform distribution of the polymerizable electrolyte (compounds b1) and/or b2)) in the adhesive composition: such thorough and effective mixing ensures that the polymer matrix obtained after curing A uniform distribution of charged species within may be determined thereby providing sufficient ionic conductivity to support electrochemical reactions at the interface with the conductive substrate.

As is known in the art, to form a one-part (1K) curable composition, the components of the composition are combined under conditions that inhibit or prevent reaction of the reactive components. Mix homogeneously: such conditions can be readily understood by those skilled in the art. As such, it is often preferred to mix the curable components in predetermined amounts, e.g. under anhydrous conditions, without intentional exposure to light, by mechanical means such as static or dynamic mixers, rather than by hand. could be.

For two-part (2K) compositions, the reactive ingredients are brought together and mixed in such a way as to induce their curing. For both one-part (1K) and two-part (2K) compositions, the reactive compounds should be mixed under sufficient shear to obtain a homogeneous mixture. It is believed that this can be achieved without special conditions or special equipment. However, suitable mixing equipment can include: static mixing devices; magnetic stir bar devices; wire whisk devices; Auger; batch mixers; W. Brabender or Banburry® style mixers; and high shear mixers such as blade style blenders and rotary impellers.

For small-scale liner applications, where volumes of generally less than 2 liters are used, a preferred package for a two-part (2K) composition consists of two tubular chambers arranged either side-by-side or nested within each other, with a piston. Closed, side-by-side double cartridges or coaxial cartridges: the drive of these pistons, preferably through closely mounted static or dynamic mixers, allows the components to be expelled from the cartridges. For high-volume applications, the two components of the composition may advantageously be stored in drums or buckets: in this case, the two components are extruded through a hydraulic press, particularly a follower plate, through a pipeline, to the hardener and the binder component are supplied to a mixing device which ensures thorough and highly uniform mixing. In any event, it is important that the binder components be placed in any package with an airtight and moisture-proof seal so that both components can be stored for long periods of time, ideally 12 months or more. is.

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

Where applicable, two-part (2K) compositions should generally be prepared to exhibit an initial viscosity measured immediately after mixing, e.g. The method of application to the substrate is not limited. Also, two-part (2K) compositions should be formulated to exhibit a pot life of at least 30 minutes, usually at least 60 or 120 minutes. The "pot life" is the time required for the viscosity of the curable composition to reach a value of twice that of the freshly mixed curable composition at 20°C and 50% relative humidity.

According to the broadest method embodiment of the present invention, the composition is applied to a substrate and then cured in situ. Prior to application of the composition, it is often advisable to pre-treat the surfaces involved to remove foreign matter therefrom; this step can facilitate subsequent adhesion of the composition, if applicable. Such treatments are known in the art and can be carried out, for example, in a single-step or multi-step process consisting of one or more of the following: an etching treatment with an acid suitable for the substrate and optionally an oxidizing agent; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric pressure plasma treatment and flame plasma treatment; immersion in aqueous alkaline degreasing baths; treatment with aqueous cleaning emulsions; cleaning solvents such as carbon tetrachloride or trichlorethylene. treatment; and water washing, preferably with deionized or demineralized water. When using an aqueous alkaline degreasing bath, any degreasing agent remaining on the surface is preferably removed by rinsing the substrate surface with deionized or demineralized water.

In some embodiments, adhesion of the coating composition of the present invention to a preferably pretreated substrate may be facilitated by applying a primer thereto. While one of ordinary skill in the art can select suitable primers, references for primer selection include U.S. Patent No. 3,671,483; U.S. Patent No. 4,681,636; U.S. Patent No. 4,749,741; including but not limited to.

The composition is then applied to the surface of the preferably pretreated and optionally primed substrate by conventional application methods such as: brushing; Roll coating using single-apply roll equipment, or double-apply roll equipment when the composition is a solvent-borne composition; doctor blade application; printing methods; Spray methods including but not limited to.

As noted above, the present invention comprises a first material layer having an electrically conductive surface and a second material layer having an electrically conductive surface to electrochemically perform the processes described above and in the appended claims. A bonded structure is provided wherein a cured releasable adhesive composition is disposed between a first material layer and a second material layer. To manufacture such structures, an adhesive composition is applied to the initial surface of at least one of the first material layer and/or the second material layer and then electrically debonded, optionally with the application of pressure. The two layers may be brought into contact such that a possible adhesive composition is disposed between the two layers.

The composition is recommended to be applied to the surface with a wet film thickness of 10-5000 μm, eg 50-2500 μm. Application of thinner layers within this range is more economical and reduces the likelihood of detrimentally thick hardened areas. However, good control must be exercised in applying thinner coatings or layers to avoid both the formation of discontinuous cured films and short contact.

Curing of the applied composition of the invention typically occurs at temperatures in the range from 40°C to 200°C, preferably from 50°C to 190°C, especially from 60°C to 180°C. Suitable temperatures will depend on the particular compounds present and the rate of cure desired, and can be determined in individual cases by those skilled in the art, if necessary using simple preliminary tests. Of course, curing at lower temperatures within the aforementioned range is advantageous as it eliminates the need to substantially heat or cool the mixture from normal ambient temperatures. However, where applicable, the temperature of the mixture produced from each component of the composition may be above the mixing and/or application temperature using conventional means, including microwave induction.

The present invention will now be described with reference to the accompanying drawings.
FIG. 1a shows a bonded structure according to a first embodiment of the invention.
FIG. 1b shows a bonded structure according to a second embodiment of the invention.
Figure 2a shows the initial delamination of the structure of the first embodiment upon application of a voltage to the structure of the first embodiment.
Figure 2b shows the initial debonding of the second embodiment structure upon application of a voltage to the second embodiment structure.

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

Two electrically conductive substrates (11) are shown in the form of layers which can be composed, inter alia, of: metal films; metal meshes or grids; deposited metal particles; resinous material; or a conductive oxide layer. Examples of conductive elements include silver filaments, single-walled carbon nanotubes, and multi-walled carbon nanotubes. Examples of conductive oxides include doped indium oxides such as indium tin oxide (ITO), doped zinc oxide, antimony tin oxide, cadmium stannate, and zinc stannate. Aside from the choice of conductive material, those skilled in the art are aware of the effectiveness of the stripping operation when the conductive substrate (11) is in the form of a grid or mesh with limited contact with the cured adhesive layer (10). can be reduced.

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

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

However, it should be noted that the composition of the adhesive layer (10) can be adjusted so that delamination occurs at either the positive or negative interface, or from both simultaneously. In some embodiments, a voltage applied to both surfaces to form an anodic and cathodic interface causes delamination at both the anodic and cathodic adhesive/substrate interfaces simultaneously. In another embodiment, if the composition does not respond to direct current at both interfaces, opposite polarities can be used to simultaneously strip both substrate/adhesive interfaces. The current can be applied in any suitable waveform, provided that sufficient total time is allowed at each pole for delamination to occur. In this regard, sinusoidal, rectangular and triangular waveforms may be suitable and may be applied from controlled voltage or controlled current sources.

While not intending to limit the invention, it is believed that the stripping operation can be effectively carried out if at least one, preferably both, of the following conditions are promoted: a) 1-100 V, e.g. application of a voltage of 20-50 V; and b) application of a voltage for a period of 1 second to 180 minutes, such as 1 second to 30 minutes. If the release of the conductive substrate from the cured adhesive is facilitated by the application of force (eg applied via a weight or spring), the potential may only need to be applied in seconds.

The following examples illustrate the invention and are not intended to limit the scope of the invention.

EXAMPLES The following materials and their abbreviations were used in the examples.
MMA: methyl methacrylate
MAA: methacrylic acid
EGDMA: ethylene glycol dimethyl acrylate
PEG-MEA: polyethylene glycol methyl ether acrylate
BENZYL MA: benzyl methacrylate
HEMA: (hydroxyethyl) methacrylate
IBOA: isobornyl acrylate
AIBN: Azobisisobutyronitrile, available from Sigma Aldrich
BPO: Benzoyl Peroxide, available from PanReac AppliChem
HEXMIM StSO3: 1H-imidazolium, 3-methyl-1-hexyl-4-ethenylbenzenesulfonate
EMIM Acrylate: 1H-imidazolium, 1-ethyl-3-methyl-acrylate
ViEIM NTf2: 1H-imidazolium, 3-ethenyl-1-ethyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide
BMIM NTf2: 1H-imidazolium, 3-methyl-1-butyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide
PEG400: polyethylene glycol, available from Sigma Aldrich
CN966H90: Aliphatic polyester-based urethane diacrylate oligomer mixed with 10% 2(2-ethoxyethoxy)ethyl acrylate, available from Sartomer
SR9054: Acid Acrylate Adhesion Promoter, available from Sartomer

Preparation of a first set of compositions: Compositions EDA1-EDA14 and Controls 1, 2 and 3 described in Tables 1a and 1b below were prepared by mixing.

The amounts in parenthesis of the polymerizable electrolyte shown in Tables 1a and 1b are in millimoles (mmol).
Controls 1, 2 and 3 contain no ionic species and are composed of non-ionic matrix monomers that form adhesives. Compositions EDA1-EDA7, EDA9-EDA11 and EDA13-EDA14 are based on the copolymerization of nonionic matrix monomers and polymerizable ionic compounds.

EDA8 is a mixture of a nonionic matrix monomer and a cured polymerizable electrolyte (PE) copolymer and was obtained by the following method: First, ViEIM NTf2 (0.359 g) and HexMIM StSO3 (0.104 g) were mixed with azobis Isobutyronitrile (0.008g) was high speed mixed at 3600 rpm for 1 minute; the mixture was then cured at 80°C for 15 minutes and then at 120°C for 2 hours; Mixed with monomer and azobisisobutyronitrile.

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

The application substrate for compositions EDA1-EDA14 and the control below was 1.25 mm thick aluminum (AA6016) and the application of the coating composition was done using glass beads 100-200 microns in diameter as spacers. rice field. Substrates were cut into 2.5 cm x 10 cm samples for tensile testing. A tensile lap shear (TLS) test was performed at room temperature based on "ISO 4587 Adhesives - Determination of Tensile Lap Shear Strength of Bonded Assemblies of Rigid Substrates (International Organization for Standardization, 2003)". The bond overlap area for each substrate described was 2.5 cm x 1.0 cm and the adhesive thickness was 0.1 cm (40 mils). An INSTRON 3366 with a 10 kN cell was used.

Application at 80° C. for 15 minutes and 120° C. for 120 minutes cured the applied adhesive composition in the overlap area. The bonded structures were then stored at room temperature for 24 hours before the first tensile test.

重合性イオン性化合物を含有する組成物は、初期接合強度が上昇する。重合性イオン性化合物と非イオン性マトリックスモノマーとの共重合に基づく組成物の接合強度は、電圧の印加後に低下する。 Example 1
After the 24 hour storage time, the tensile lap shear strength was examined before and after applying a constant potential of 50 V to the adhesive layer for 30 minutes. The results are shown in Table 2 below.

A composition containing a polymerizable ionic compound has an increased initial bonding strength. The bond strength of compositions based on copolymerization of polymerizable ionic compounds and nonionic matrix monomers decreases after application of voltage.

Example 2
In this example, after the 24 hour storage time, the electropeeling behavior of the adhesive composition EDA5 was investigated by measuring the tensile lap shear strength before and after applying different constant potentials to the adhesive layer for 30 minutes. investigate. The results are shown in Table 3 below.

重合性イオン性化合物と非イオン性マトリックスモノマーとの共重合に基づく組成物は、２ヶ月後に初期接合強度を維持しており、電圧の印加後の接合強度の低下をなお示す。 Example 3
In this example, the tensile lap shear strength of the adhesive was determined by measuring the tensile lap shear strength before and after applying a constant potential of 50 V to the adhesive layer for 30 minutes after the storage time of 24 hours and after the storage time of 2 months. Examine the electro-peeling behavior. The results are shown in Table 4 below.

Compositions based on copolymerization of polymerizable ionic compounds and nonionic matrix monomers maintain initial bond strength after 2 months and still show a decrease in bond strength after application of voltage.

対照４は、イオン種なしで、接着剤を形成する非イオン性マトリックスモノマーにより構成されている。組成物ＥＤＡ１５～ＥＤＡ１８は、重合性イオン性化合物と非イオン性マトリックスモノマーとの共重合に基づく。
ＥＤＡ１９は、参考例であり、非重合性イオン性化合物（BMIM NTf2）と非イオン性マトリックスモノマーとの混合物に基づく。 Preparation of a second set of compositions: Compositions EDA15-EDA19 and Control 4 shown in Table 5 below were prepared by mixing.

Control 4 is composed of non-ionic matrix monomers forming an adhesive without ionic species. Compositions EDA15-EDA18 are based on the copolymerization of polymerizable ionic compounds and nonionic matrix monomers.
EDA19 is a reference example and is based on a mixture of a non-polymerizable ionic compound (BMIM NTf2) and a non-ionic matrix monomer.

The application substrates for the following compositions EDA15-EDA19 and Control 4 were aluminum (AA6016) with a thickness of 1.25 mm and stainless steel (1.4301) with a thickness of 1.5 mm, with 100-100 as a spacer. Application of the coating composition was performed using glass beads with a diameter of 200 microns. For tensile testing, substrates were cut into 2.5 cm by 10 cm (1 inch by 4 inch) sized samples. Room temperature tensile lap shear (TLS) tests were performed according to "ISO 4587 Adhesives - Determination of Tensile Lap Shear Strength of Bonded Assemblies of Rigid Substrates (International Organization for Standardization, 2003)". The bond overlap area for each substrate was 2.5 cm x 1.0 cm and the adhesive thickness was 0.1 cm (40 mils). A Zwick Z020 with a 20 kN cell was employed.
The applied adhesive composition was cured in the overlapping areas by application of 80° C. for 15 minutes and 120° C. for 30 minutes. The bonded structures were then stored at room temperature for 24 hours before the first tensile test.

重合性イオン性化合物を含有する組成物ＥＤＡ１５～ＥＤＡ１８は初期接合強度を維持する一方で、組成物ＥＤＡ１７は初期強度の低下を示した。非重合性イオン液体を含有する組成物ＥＤＡ１９は、５０％の初期強度低下を示した。重合性イオン性化合物と非イオン性マトリックスモノマーとの共重合に基づく組成物の接合強度は、電圧の印加後に低下する。 Example 4
After the 24 hour storage time, the tensile lap shear strength was measured before and after applying a constant potential of 50 V to the adhesive layer for 30 minutes. The results are shown in Table 6 below.

Compositions EDA15-EDA18 containing a polymerizable ionic compound maintained initial bond strength, while composition EDA17 exhibited a decrease in initial strength. Composition EDA19 containing a non-polymerizable ionic liquid showed an initial strength loss of 50%. The bond strength of compositions based on copolymerization of polymerizable ionic compounds and nonionic matrix monomers decreases after application of voltage.

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

重合性イオン性化合物と非イオン性マトリックスモノマーとの共重合に基づく組成物ＥＤＡ１５は、３ヶ月後に接合強度がわずかに低下している（１２％）。非重合性イオン液体と非イオン性マトリックスモノマーとの混合物に基づく組成物は、アルミニウムおよびステンレス鋼の両方について、２ヶ月後に３０％という接合強度のより高い低下を示している。全ての組成物は、電圧の印加後に接合強度の低下を示す。

The composition EDA15, based on the copolymerization of polymerizable ionic compounds and nonionic matrix monomers, shows a slight decrease in bond strength (12%) after 3 months. Compositions based on mixtures of non-polymerizable ionic liquids and non-ionic matrix monomers show a higher bond strength loss of 30% after 2 months for both aluminum and stainless steel. All compositions show a decrease in bond strength after application of voltage.

In view of the above description and examples, it will be apparent to those skilled in the art that they can be equivalently modified without departing from the scope of the claims.

10 Cured Adhesive Layer 11 Conductive Substrate 12 Non-Conductive Material Layer 13 Power Supply

Claims (15)

A curable, electrochemically releasable adhesive composition comprising, based on the weight of the composition,
40-99% by weight of a) at least one ethylenically unsaturated nonionic monomer;
0.9 to 50% by weight of b) at least one polymerizable ionic compound;
0.1 to 10% by weight of c) at least one free radical initiator, the polymerizable ionic compound comprising:
b1) at least one of general formula IV:

and/or b2) at least one of general formula V:

_{C2 -} ^C8 alkenyl; _C1 - _{C30 heteroalkyl} ; _C3 - _C30 cycloalkyl _{; C6 - C18} aryl _{; C7} - _C18 alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a _C1 - _C6 alkylene group; R ^b is a _C1 - _C6 alkyl group];
Each ^R8 is independently H, _C1 - _C18 alkyl, _C1 - _C18 heteroalkyl, _C3 - _C18 cycloalkyl, _C6 - _C18 aryl, _C1 - _C9 heteroaryl, _{C7 -C18} alkylaryl or _C2 - _C5 heterocycloalkyl;
^R9 is H or _C1 - _C4 alkyl;
_{C1 - C30} ^heteroalkyl _{; C3} - _C30 cycloalkyl; _{C6 - C18} aryl; _C1 - _C9 heteroaryl; ₁₈ alkylaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a C ₁ -C ₆ alkylene group and R ^b is a C ₁ -C ₆ alkyl groups];
A is a non-polymerizable anion;
T is an ethylenically unsaturated anion;
d and m are each an integer having a value of at least 1;
e and n are such that the compound is electrically neutral;

is a covalent bond, _C1 - _C2 alkylene, _{-CH2OC (} =O)-, _-CH2CH2OC (=O)-, p-benzyl or p-tolyl]
An adhesive composition comprising a compound represented by 45-95% by weight of a) said at least one ethylenically unsaturated nonionic monomer;
5-30% by weight b) said at least one polymerizable ionic compound;
2. The adhesive composition of claim 1, comprising 0.1-5% by weight of c) said at least one free radical initiator; and 0-10% by weight of d) a solubilizer. Part a) comprises 40 to 95% by weight, based on the weight of the composition, of a1) at least one of formula (I):
_H2C = _CGCO2R1 ( ^I )
[wherein G is hydrogen, halogen or a _C1 - _C4 alkyl group;
_C2 - _C30 heteroalkyl; _C3 ^- _C30 cycloalkyl; _{C2 - C8} heterocycloalkyl; _{C2 -C20 alkenyl} ; and _C2 - _C12 alkynyl selected from]
The adhesive composition according to claim 1 or 2, comprising a (meth)acrylate monomer represented by 4. Any of claims 1 to 3, wherein part a) comprises up to 50% by weight, preferably 5 to 25% by weight, based on the weight of the composition, of a3) at least one (meth)acrylate functionalized oligomer. The adhesive composition according to 1. An adhesive composition according to any preceding claim, wherein part a) comprises at least one α,β-ethylenically unsaturated monocarboxylic acid having 3 to 5 carbon atoms. in part b)
_C2 - _C4 alkenyl; _C1 - _C8 heteroalkyl; _C3 - _{C12 cycloalkyl} ; _C6 - _{C18 aryl} ; ^C1 _{- C9} heteroaryl; _C2 - _C5 heterocycloalkyl; or -R ^a -C( ₌ O)-R ^b where R ^a is _{a C1} - _C4 alkylene group and R ^b is a C is a ₁ - _C4 alkyl group];
each ^R8 is preferably independently selected from H or _C1 - _C2 alkyl;
R ⁹ is H or methyl;
_C1 - _C8 heteroalkyl; _C3 - _C12 ^cycloalkyl ; _C6 - _C18 aryl; _{C1 - C9} heteroaryl; _C7 - _C18 alkylaryl _{; C2} - _C5 heterocycloalkyl; or -R ^a -C(=O)-R ^b where R ^a is a _C1 - _C4 alkylene group and R ^b is a _C1 - _C4 alkyl group. is selected from
The adhesive composition according to any one of claims 1-5. Part b) is
b1) 1H-imidazolium, 3-ethenyl-1-methyl-, iodide; 1H-imidazolium, 3-ethenyl-1-methyl-, chloride; 1H-imidazolium, 3-ethenyl-1-methyl-, bromide; 1H-imidazolium, 3-ethenyl-1-methyl-, methanesulfonate; 1H-imidazolium, 3-ethenyl-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl] Methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl- 1-methyl-, hexafluorophosphate; 1H-imidazolium, 3-ethenyl-1-methyl-, 4-methylbenzenesulfonate; 1H-imidazolium, 3-ethenyl-1-methyl-, tetrafluoroborate; 1H-imidazo Lithium, 3-ethenyl-1-ethyl-, iodide; 1H-imidazolium, 3-ethenyl-1-ethyl-, bromide; 1H-imidazolium, 3-ethenyl-1-ethyl-, 1,1,1-tri Fluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-ethenyl-1-ethyl-, hexafluorophosphate; 1H-imidazolium, 3-ethenyl-1-ethyl-, tetrafluoro Borate; 1H-imidazolium, 3-ethenyl-1-(1-methylethyl)-, bromide; 1H-imidazolium, 3-(1,1-dimethylethyl)-1-ethenyl-, bromide; 1H-imidazolium , 3-ethenyl-1-propyl-, bromide; 1H-imidazolium, 3-ethenyl-1-(phenylmethyl)-, bromide; 1H-imidazolium, 1-ethenyl-3-(4-methylphenyl)-, Chloride; 1H-imidazolium, 3-ethenyl-1-(1-methylpropyl)-, chloride; 1H-imidazolium, 1-butyl-3-ethenyl-, bromide; 3-[(4-ethenylphenyl)methyl ]-1-methyl-, iodide; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, chloride; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl ]-1-methyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1- Methyl-, hexafluorophosphate; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl]-1-methyl-, tetrafluoroborate; 1H-imidazolium, 3-[(4-ethenylphenyl)methyl ]-1-ethyl-, chloride; 1H-imidazolium, 1-[(4-ethenylphenyl)methyl]-3-ethyl-, 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl ] methanesulfonamide; 1H-imidazolium, 1-(3-aminopropyl)-3-[(4-ethenylphenyl)methyl]-, chloride; 1H-imidazolium, 1-butyl-3-[( 4-ethenylphenyl)methyl]-, chloride; and/or b2) 1H-imidazolium, 1-methyl-3-hexyl-, 4-ethenylbenzenesulfonate; 1H -imidazolium, 1-dodecyl-3-ethenyl-, 4-ethenylbenzenesulfonate; 1H-imidazolium, 1-methyl-3-propyl-, 4-ethenylbenzenesulfonate; and 1H-imidazolium, 3-ethyl 6. The adhesive composition according to any one of claims 1 to 5, comprising at least one compound selected from the group consisting of -1-methyl-, 4-(1-methylethenyl)benzenesulfonate. Part b) is 1H-imidazolium, 3-methyl-1-hexyl-4-ethenylbenzenesulfonate; 1H-imidazolium, 3-ethenyl-1-ethyl-1,1,1-trifluoro-N-[ (trifluoromethyl)sulfonyl]methanesulfonamide; and 1H-imidazolium, 3-methyl-1-butyl-1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide The adhesive composition according to any one of claims 1 to 5, comprising at least one compound selected from Azoesters; azoamides; azoamidines; azoimidazolines; and macroazoinitiators. adhesive composition. Said composition comprises a solubilizer d) in an amount up to 10% by weight based on the weight of the composition, said solubilizer being a polyoxyalkylene glycol; a silicone surfactant; a polyhydric alcohol; The adhesive composition according to any one of claims 1 to 9, selected from the group consisting of sugars. An adhesive composition according to any preceding claim, wherein the composition comprises electrically conductive particles in an amount up to 10% by weight based on the weight of the composition. 12. The adhesive composition of claim 11, wherein said conductive particles are selected from the group consisting of silver, carbon black and mixtures thereof. a first material layer having an electrically conductive surface; and a second material layer having an electrically conductive surface;
comprising
A curable, electrochemically releasable adhesive composition according to any one of claims 1 to 12 is disposed between a first material layer and a second material layer,
junction structure. 14. A method of exfoliating a bonded structure according to claim 13, comprising the steps of 1) applying a voltage to both surfaces to form an anodic interface and a cathodic interface; and 2) exfoliating these surfaces. 15. The method according to claim 14, wherein the voltage applied in step 1 is 0.5-200V and the voltage is preferably applied for 1 second to 30 minutes.

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