Two-component (2K) curable adhesive composition

Abstract

The present invention is directed to a curable, peelable two-part (2K) hybrid adhesive composition comprising: i) a first component comprising: a) an epoxy resin; b) a (meth)acrylate monomer; c) an electrolyte; d) a solubilizer; and e) a filler; and ii) a second component comprising: a) a curing agent consisting of at least one compound having at least two epoxy-reactive groups per molecule; b) an accelerator; and c) a filler.

Description

Technical Field

[0001] The present invention is directed to an adhesive composition that can be peeled off from a specific substrate coated with the adhesive composition. More specifically, the present invention relates to a curable and peelable two-component (2K) hybrid adhesive composition.

Background Art

[0002] Adhesive bonding and polymer coating are generally used in the assembly and finishing of manufactured products. These are used as alternatives to mechanical fasteners such as screws, bolts, and rivets, reducing machining costs and providing more adaptable joints in the manufacturing process. Bonding with adhesives distributes stress evenly, reduces the possibility of fatigue, and shields the joint from corrosive species.

[0003] Although adhesives thus offer many advantages over mechanical fasteners, when practically required, it tends to be difficult to disassemble articles joined by adhesion. Removal of adhesives by mechanical processes such as sandblasting or wire brushing is often excluded because, for one, the adhesive is located between the substrates and thus cannot be accessed or polished without damaging the substrate surface. Decomposition by the application of chemicals and / or high temperatures, as disclosed in U.S. Patent No. 4,171,240 (Wong) and U.S. Patent No. 4,729,797 (Linde et al.), may be effective but can be time-consuming and complex to implement. Furthermore, the required aggressive chemicals or harsh conditions can damage the substrates being separated and render them unsuitable for subsequent applications.

[0004] With such problems in mind, certain authors have attempted to develop a peelable adhesive composition in which a cured composition acts to break the adhesion at the adhesive-substrate interface by the flow of an electric current.

[0005] U.S. Patent No. 7,465,492 (Gilbert) describes a peelable composition comprising a matrix functionality including a monomer selected from the group consisting of acrylic, methacrylic, and combinations thereof; a free radical initiator; and an electrolyte, wherein the electrolyte imparts sufficient ionic conductivity to the composition to assist in a Faraday reaction in a bond formed between the composition and a conductive surface, thereby enabling the composition to be peeled from the surface.

[0006] U.S. Patent Application Publication 2007 / 0269659 (Gilbert) describes an adhesive composition peelable at two interfaces, comprising (i) a polymer and an electrolyte; (ii) facilitating the joining of two surfaces; and (iii) peeling from both the anodic interface and the cathodic interface in response to a voltage applied across both surfaces to form the anodic interface and the cathodic interface.

[0007] U.S. Patent Application Publication 2008 / 0196828 (Gilbert) describes a hot melt adhesive composition comprising a thermoplastic component; and an electrolyte, wherein the electrolyte provides sufficient ionic conductivity to the composition to enable a Faraday reaction in a bond formed between the composition and a conductive surface, thereby enabling the composition to be peeled from the surface.

[0008] International Application Publication No. 2017 / 133864 (Henkel AG & Co. KGaA) describes a method for reversibly bonding a first and a second substrate, wherein at least the first substrate is an electrically non-conductive substrate, comprising: a) coating the surface of the electrically non-conductive substrate with a conductive ink; b) applying an electrically peelable hot melt adhesive composition to the surface of the first substrate and / or the second substrate coated with the conductive ink; c) bringing the first substrate into contact with the second substrate such that the electrically peelable hot melt adhesive composition is interposed between the two substrates; d) forming an adhesive bond between the two substrates to provide a bonded substrate; and e) applying a voltage to the bonded substrate, thereby substantially weakening the adhesion at at least one interface between the electrically peelable hot melt adhesive composition and the substrate surface.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0010] It can be easily applied to the surface of the substrate to be followed, and can provide an effective bond within the composite structure including the substrate during its curing. However, there still exists a technical need to provide an adhesive composition that can be effectively peeled off from those substrates by easily applying a potential to the cured adhesive.

Means for Solving the Problems

[0011] According to the first aspect of the present invention, a) an epoxy resin, b) a (meth)acrylate monomer, c) an electrolyte; d) a solubilizer; and e) a filler; a first component containing the same, and a) a curing agent composed of at least one compound having at least two epoxide-reactive groups per molecule, b) an accelerator; and c) a filler a second component containing the same A curable and peelable two-component (2K) hybrid adhesive composition containing the same is provided.

[0012] In an important embodiment of the present invention, the two-component (2K) hybrid adhesive composition is Based on the weight of the first component, · 15 to 60% by weight, preferably 15 to 50% by weight of the epoxy resin; · 5 to 50% by weight, preferably 10 to 30% by weight of the (meth)acrylate monomer; · 2.5 to 25% by weight, preferably 5 to 20% by weight of the electrolyte; · 0.5 to 20% by weight, preferably 1 to 15% by weight of the solubilizer; and, · the filler; a first component containing the same, and, Based on the weight of the second component, · a curing agent composed of at least one compound having at least two epoxide-reactive groups per molecule, · 0.1 to 15% by weight, preferably 2 to 10% by weight, of an accelerator; and, · said filler, a second component containing the same.

[0013] In the first component of the adhesive composition, the electrolyte is 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium methylsulfate, 1-hexyl-3-methylimidazolium 2-(2-fluoroanilino)-pyridinate, 1-hexyl-3-methylimidazolium imide, 1-butyl-1-methylpyrrolidinium 2-(2-fluoroanilino)-pyridinate, 1-butyl-1-methyl-pyrrolidinium imide, trihexyl(tetradecyl)phosphonium 2-(2-fluoroanilino)-pyridinate, cyclohexyltrimethylammonium bis(trifluoromethylsulfonyl)imide, di(2-hydroxyethyl)ammonium trifluoroacetate, N,N-dimethyl(2-hydroxyethyl)ammonium octanoate, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, N-ethyl-N-N-N-N-tetramethylguanidinium trifluoromethanesulfonate, guanidinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium bromide, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-hydroxymethylpyridinium ethylsulfate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-ethyl-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-propyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,It is preferably selected from the group consisting of 3-dimethylimidazolium hexafluorophosphate, 1-butylimidazole, 1-methylimidazolium tetrafluoroborate, tetrabutylphosphonium tris(pentafluoroethyl) trifluorophosphate, trihexyl(tetradecyl)phosphonium tetrafluoroborate, and mixtures thereof. It is particularly preferred to use at least one of 1-ethyl-3-methylimidazolium methanesulfonate and 1-ethyl-3-methylimidazolium methylsulfate.,

[0014] Separate from or in addition to the above-mentioned reference to the selection of the electrolyte in this first component, the solubilizer is preferably selected from polyphosphazene; polymethylene sulfide; polyoxyalkylene glycol; polyethyleneimine; silicone surfactant and fluorinated silicone surfactant; copolymer of functionalized polyalkylsilsioxane and epoxy resin; polyhydric alcohol; and sugar.

[0015] In the second component of the composition, the curing agent contains at least one polyamine having at least two amine hydrogens reacting with epoxy groups, the polyamine further contains primary amine groups and / or secondary amine groups, and it is preferably characterized by having an equivalent weight of 150 g / eq or less per primary amine group or secondary amine group. In this regard, the use of an ether group-containing aliphatic primary polyamine is particularly preferred.

[0016] Separate from or in addition to the above-mentioned reference to the selection of the curing agent in the second component of the composition, the accelerator is preferably selected from the group consisting of tertiary amines, quaternary ammonium salts, amidines, guanidines, and mixtures thereof. It is noted that it is particularly preferred to employ at least one accelerator selected from imidazole, methylimidazole, benzyldimethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,4-diazabicyclo(2,2,2)octane.

[0017] According to a second aspect of the present invention, ·a first material layer having a conductive surface; and ·a second material layer having a conductive surface are included, and a cured peelable two-component (2K) hybrid adhesive composition as defined herein and in the appended claims is disposed between the first material layer and the second material layer, and a bonding structure is provided.

[0018] According to a third aspect of the present invention, there is provided a method of peeling the bonding structure as defined herein and in the appended claims, i) applying a voltage across both surfaces to form an anode interface and a cathode interface; and ii) peeling the both surfaces is included. Step i) of this method preferably a) an applied voltage of 0.5 to 200 V; and b) a voltage applied for 1 second to 60 minutes is characterized by at least one of them.

Brief Description of Drawings

[0019]

Figure 1a

Figure 1b

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Figure 3b

Figure 4

Best Mode for Carrying Out the Invention

[0020] <Definition> As used herein, the singular forms "a", "an", and "the" include plural reference terms unless the context clearly dictates otherwise.

[0021] As used herein, the term "comprising" (including "comprises" and "comprised of") is synonymous with "including" (including "includes", "containing", or "contains"), is inclusive or open-ended, and does not exclude additional, unrecited members, elements, or method steps.

[0022] As used herein, the term "consisting" excludes unspecified elements, components, members, or method steps.

[0023] When amounts, concentrations, dimensions, and other parameters are expressed in the form of a range, a preferred range, an upper limit, a lower limit, or a preferred upper limit and a limiting value, any range obtained by any combination of any upper limit or preferred value and any lower limit or preferred value should be understood to be specifically disclosed, whether or not the resulting range is explicitly recited in the context.

[0024] Furthermore, in accordance with standard understanding, a weight range expressed as "0 to x" specifically includes 0% by weight. The component defined by the range may not be present in the composition or may be present in an amount up to x% by weight in the composition.

[0025] The terms "preferred", "preferably", "desirable" and "in particular" are frequently used herein to refer to embodiments of the present disclosure that may provide certain advantages under certain circumstances. However, the description of one or more preferred, preferable, desirable, or particular embodiments does not mean that other embodiments are not useful, nor is it intended to exclude those other embodiments from the scope of the present disclosure.

[0026] In this application, the word "may" is used in a permissive sense (i.e., it is possible), not in an obligatory sense.

[0027] As used herein, room temperature is 23 °C plus or minus 2 °C. As used herein, "ambient conditions" means the temperature and pressure surrounding the composition or the coating layer or the substrate of the coating layer where the composition is disposed.

[0028] In the context of the present invention, a "two-component (2K) composition" is understood to be a composition in which the first component (A) and the second component (B) must be stored in separate containers due to their (high) reactivity. The two components are mixed only immediately before application and then react, typically without additional activation, to form bonds, thereby forming a polymer network. Here, a higher temperature may be applied to accelerate the cross-linking reaction.

[0029] As used herein, the term "removable" means that after curing of the adhesive, the adhesion strength is reduced by at least 50% by applying a potential of 10 V to 75 V for 1 second to 60 minutes. The curable adhesive is applied between two substrates adhered by the adhesive such that current flows through the adhesive bond line. The adhesion strength is measured by a tensile lap shear (TLS) test in accordance with EN1465:2009 (German version), Measurement of tensile lap shear strength of adhesives - bonded assemblies, which is carried out at room temperature. The overlap of the adhesive is 25 mm × 10 mm and the thickness of the adhesive is about 150 μm.

[0030] As used herein, the term "monomer" means a substance that can undergo a polymerization reaction to contribute a structural unit to the chemical structure of a polymer. As used herein, the term "monofunctional" means having one polymerizable site. The term "polyfunctional" as used herein means having two or more polymerizable sites.

[0031] As used herein, the term "equivalent (eq.)" relates to the relative number of reactive groups present during a reaction, as is normal in chemical notation.

[0032] The term "electrolyte" is used herein, in accordance with its standard meaning in the art, to mean a substance containing free ions that can conduct electricity by the movement of charged charge carrier species. This term is intended to encompass molten electrolytes, liquid electrolytes, semi-solid electrolytes and solid electrolytes in which at least one of the cationic or anionic components of the electrolyte structure is essentially free to move and thus acts as a charge carrier.

[0033] The curable adhesive composition of the present invention and the cured adhesive obtained therefrom have "electrolyte functionality" in that the adhesive substance enables the conduction of ions, anions or cations, or both. The electrolyte functionality is understood to be derived from the ability of the composition and the curable adhesive to solvate at least one polar ion.

[0034] As used herein, "(meth)acryl" is an abbreviation referring to "acryl" and / or "methacryl". Thus, the term "(meth)acrylamide" refers collectively to acrylamide and methacrylamide.

[0035] As used herein, "C 1- C nThe "alkyl" group is a monovalent group containing 1 to n carbon atoms, which is an alkane group and refers to those containing linear and branched organic groups. Thus, "C 1- C 30 alkyl" group refers to a monovalent group having 1 to 30 carbon atoms, which is an alkane group and includes linear and branched organic groups. Examples of alkyl groups include, but are not limited to, methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and 2-ethylhexyl. In the present invention, such an alkyl group may be unsubstituted or substituted with one or more substituents such as halo, nitro, cyano, amide, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide and hydroxy. When applicable, the selection for a given substituent is described herein. However, generally, attention should be paid to the selection for an alkyl group containing 1 to 18 carbon atoms (C 1- C 18 alkyl)-for example, an alkyl group containing 1 to 12 carbon atoms (C 1- C 12 alkyl) or an alkyl group containing 1 to 6 carbon atoms (C 1- C6 alkyl)-.

[0036] As used herein, the term "C 1- C 18 hydroxyalkyl" refers to an HO-(alkyl) group having 1 to 18 carbon atoms, the point of attachment of the substituent being via an oxygen atom, and the alkyl group being as defined above.

[0037] "Alkoxy group" refers to a monovalent group represented by -OA where A is an alkyl group, and non-limiting examples thereof are a methoxy group, an ethoxy group, and an isopropyloxy group. As used herein, the term "C 1- C 18 alkoxyalkyl" has an alkoxy substituent as defined above refers to the alkyl group to be used herein, , (alkyl - O - alkyl ) partThe moieties contain from 1 to 18 carbon atoms in total. Such moieties include methoxymethyl (-CH2OCH3), 2-methoxyethyl (-CH2CH2OCH3), 2-ethoxyethyl, and the like.

[0038] As used herein, the term "C 2- C4 alkylene" is defined as a saturated divalent hydrocarbon group having 2 to 4 carbon atoms.

[0039] As used herein, the term "C 3- C 30 cycloalkyl" is understood to mean an optionally substituted, saturated hydrocarbon group, monocyclic hydrocarbon group, bicyclic hydrocarbon group or tricyclic hydrocarbon group having 3 to 30 carbon atoms. Generally, a cycloalkyl group containing 3 to 18 carbon atoms (C 3- C 18 cycloalkyl group) should be noted. Examples of cycloalkyl groups include cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

[0040] As used herein, the term "C 6- C 18 aryl" group, used alone or as part of a larger moiety such as an "aralkyl group", means an optionally substituted, monocyclic ring system, bicyclic ring system and tricyclic ring system in which the monocyclic ring system is aromatic or at least one of the rings of the bicyclic ring system or tricyclic ring system is aromatic. The bicyclic ring system and tricyclic ring system include 2- to 3-membered carbocyclic rings fused to benzene. Exemplary aryl groups include phenyl; (C 1- C4) alkylphenyl such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthalenyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. The selection of the phenyl group may be noted.

[0041] As used herein, "C 2- C 20"Alkenyl" means a hydrocarbyl group having 2 to 20 carbon atoms and at least one unit of ethylenic unsaturation. The alkenyl group can be straight-chain, branched, or cyclic and can be optionally substituted. The term "alkenyl" also includes groups having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations, as understood by those skilled in the art. However, generally, preference is given to the selection of unsubstituted alkenyl groups containing 2 to 10 (C 2-10 ) or 2 to 8 (C 2-8 ) carbon atoms. The C 2- C 12 Examples of alkenyl groups include, but are not limited to, -CH=CH2; -CH=CHCH3; -CH2CH=CH2; -C(=CH2)(CH3); -CH=CHCH2CH3; -CH2CH=CHCH3; -CH2CH2CH=CH2; -CH=C(CH3)2; -CH2C(=CH2)(CH3); -C(=CH2)CH2CH3; -C(CH3)=CHCH3; -C(CH3)CH=CH2; -CH=CHCH2CH2CH3; -CH2CH=CHCH2CH3; -CH2CH2CH=CHCH3; -CH2CH2CH2CH=CH2; -C(=CH2)CH2CH2CH3; -C(CH3)=CHCH2CH3; -CH(CH3)CH=CHCH; -CH(CH3)CH2CH=CH2; -CH2CH=C(CH3)2; 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohex-3-enyl.

[0042] As used herein, "alkylaryl" means an alkyl-substituted aryl group, and "substituted alkylaryl" means an alkylaryl group further having one or more substituents as defined above. Further, "aralkyl" as used herein means an alkyl group substituted with an aryl group as defined above.

[0043] As used herein, the term "hetero" refers to a group or moiety containing one or more heteroatoms such as N, O, Si, and S. Thus, for example, "heterocyclic" refers to a cyclic group having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl", "heterocycloalkyl", and "heteroaryl" moieties mean, respectively, an alkyl group, a cycloalkyl group, and an aryl group as defined herein that contain N, O, Si, or S as part of their structure.

[0044] As used herein, the term "epoxide" represents a compound characterized by the presence of at least one cyclic ether group, i.e., a group in which an ether oxygen atom is bonded to two adjacent carbon atoms, thereby forming a cyclic structure. This term is intended to encompass monoepoxide compounds, polyepoxide compounds (having two or more epoxy groups), and epoxy-terminated prepolymers. The term "monoepoxide compound" is intended to denote an epoxide compound having one epoxy group. The term "polyepoxide compound" means an epoxide compound having at least two epoxy groups. The term "diepoxide compound" means an epoxide compound having two epoxy groups.

[0045] Epoxides may be unsubstituted or may be inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine, and phenyl.

[0046] As used herein, "primary amino group" refers to an NH2 group bonded to an organic group, and "secondary amino group" refers to an NH group bonded to two organic groups, which may also be part of a ring together. Thus, the term "tertiary amine" refers to a nitrogen having a site where the nitrogen atom is not bonded to a hydrogen atom. As used herein, the term "amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups.

[0047] As used herein, the term "equivalent weight" means the molecular weight divided by the number of the said function. Therefore, "epoxy equivalent weight" (EEW) represents the weight of the resin containing 1 equivalent of epoxy in grams.

[0048] "Amine equivalent weight" is a calculated value (g / eq.) obtained from the amine value. The amine value is determined by titrating amine acetate ions with a dilute, typically 1N hydrochloric acid solution. In the case of a pure substance, the amine value can be calculated using the molecular weight of the pure compound and KOH (56.1 g / mol).

[0049] As used herein, the term "Lewis acid" refers to a molecule or ion - often called an electrophile - that can bond to another molecule or ion by forming a covalent bond with two electrons from a second molecule or ion. Thus, a Lewis acid is an electron acceptor.

[0050] The molecular weights referred to herein can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards in accordance with ASTM 3536.

[0051] Unless otherwise specified, the viscosities of the compositions described herein were measured using an Anton Paar viscometer, model MCR301, under standard conditions of 25 °C and 50% relative humidity (RH). The viscometer is calibrated once a year and inspected by service. The calibration is performed using specific oils of known viscosities that vary from 5,000 cps to 50,000 cps (parallel plate PP25, 23 °C, shear rate 1( 1 / s ) ). The measurements of the compositions according to the invention are performed using parallel plate PP20 at different shear rates from 1.5 (1 / s) to 100 (1 / s).

[0052] <Detailed Description of the Invention> The two-component (2K) composition of the present invention is characterized in that fillers are present in both components. Since the composition of the filler in each component is determined independently, it may be the same or different in each component. Furthermore, the filler in each component may be composed of a conductive filler, a non-conductive filler, or a mixture thereof.

[0053] Generally speaking, there is no intention to particularly limit the shape of the particles employed as the conductive filler, and it is possible to use acicular, spherical, elliptical, columnar, bead-shaped, cubic, or plate-shaped particles alone or in combination. Furthermore, it is assumed that aggregates of two or more types of particles may be used. Similarly, there is no particular intention to limit the size of the particles employed as the conductive filler. Conventionally, however, such a conductive filler has an average volume particle diameter of 1 to 500 μm, for example 1 to 200 μm, measured by the laser diffraction / scattering method.

[0054] Exemplary conductive fillers include, but are not limited to, silver; copper; gold; palladium; platinum; nickel; gold or silver-coated nickel; carbon black; carbon fiber; graphite; aluminum; indium tin oxide; silver-coated copper; silver-coated aluminum; metal-coated glass spheres; metal-coated fillers; metal-coated polymers; silver-coated fibers; silver-coated spheres; antimony-doped tin oxide; conductive nanospheres; nano silver; nano aluminum; nano copper; nano nickel; carbon nanotubes; and mixtures thereof. It is preferable to use particulate silver and / or carbon black as the conductive filler.

[0055] In a particular important embodiment, the conductive filler should be included in the composition in an amount of 0 to 10% by weight, for example up to 5% by weight, based on the total weight of the composition.

[0056] Generally, there is no particular intention to limit the shape of the particles employed as the non-conductive filler, and particles such as acicular, spherical, elliptical, columnar, bead-shaped, cubic, or plate-shaped can be used alone or in combination. Furthermore, it is assumed that aggregates of two or more types of particles may also be used. Similarly, there is no particular intention to limit the size of the particles employed as the non-conductive filler. Conventionally, however, such non-conductive fillers have an average volume particle size of 0.1 to 1500 μm, for example 1 to 1000 μm, or 1 to 500 μm, as measured by the laser diffraction / scattering method.

[0057] Exemplary non-conductive fillers include calcium carbonate, calcium oxide, calcium hydroxide (lime powder), precipitated and / or pyrogenic silica, zeolite, bentonite, wollastonite, magnesium carbonate, diatomaceous earth, barium sulfate, alumina, clay, talc, sand, quartz, flint, mica, glass beads, glass powder, and other minerals, but are not limited thereto. It is also possible to add short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, and polyethylene fiber.

[0058] The pyrogenic and / or precipitated silica preferably has a BET surface area of 10 to 90 m 2 / g. When they are used, they do not cause a further increase in the viscosity of the composition according to the present invention, but contribute to the strengthening of the cured composition.

[0059] It is similarly conceivable to use pyrogenic and / or precipitated silica having a higher BET surface area, preferably 100 to 250 m 2 / g. Due to the larger BET surface area, the effect of strengthening the cured composition can be achieved with a smaller weight ratio of silica.

[0060] Also suitable as the non-conductive filler are hollow spheres having a mineral shell or a plastic shell. These may be, for example, hollow glass spheres commercially available under the trade name Glass Bubbles (registered trademark). Plastic-based hollow spheres such as Expancel (registered trademark) or Dualite (registered trademark) can be used and are described in EP 0 520 426 B1. These are composed of inorganic or organic substances and have a diameter of 1 mm or less, preferably 500 μm or less, more preferably 100 to 200 μm, respectively.

[0061] Non-conductive fillers that impart thixotropy to the composition may be preferred in many applications. Such fillers are also described as rheology aids, for example, hydrogenated castor oil, fatty acid amides, or swelling plastics such as PVC.

[0062] In a highly preferred embodiment, the filler of the first component and the filler of the second component may be the same or different and are independently selected from the group consisting of calcium carbonate, calcium oxide, talc, fumed silica, silica, wollastonite, barium sulfate, glass beads, and mixtures thereof.

[0063] The above fillers are preferred to impart desirable properties to the composition, such as improved adhesion properties (wollastonite); improved aging properties and removal of moisture (barium sulfate and calcium carbonate); ideal spacing (glass beads), and improved hydrophobicity and rheology (fumed silica).

[0064] In a highly preferred embodiment, the composition according to the invention contains fumed silica as a filler.

[0065] Hydrophobicity may be required for the electrolyte to dissolve in the composition and avoid phase separation. Preferred fillers, especially fumed silica, impart the necessary hydrophobicity to the composition, thus improving the solubility of the electrolyte and preventing phase separation. Furthermore, technical data indicate that the presence of non-conductive fillers improves the initial adhesion performance of the composition.

[0066] The desired viscosity of each component of the composition and the desired viscosity of the curable composition formed when the two components are combined can determine the amount of filler used. Considering the latter consideration, the total amount of fillers (both conductive and non-conductive) present in the composition should not prevent the composition from being easily extruded from a suitable dispensing device such as a tube. Conventionally, such extrudable curable compositions desirably have a viscosity of 3000 - 150,000, preferably 40,000 - 80,000 mPas, and more preferably 50,000 - 60,000 mPas.

[0067] Preferably, the first component of the composition contains 1 - 40 wt% filler based on the weight of the first component. Desirably, the filler constitutes 1 - 25 wt%, for example 1.5 - 18 wt% of the first component. Independently of this description of the selection, the second component of the composition desirably contains 10 - 30 wt%, preferably 15 - 13 wt% filler based on the weight of the second component.

[0068] <The first component of the two-component composition> The first component of the two-component (2K) composition contains an epoxy resin; a (meth)acrylate monomer; an electrolyte; a solubilizer; and a filler.

[0069] <Epoxy resin> The first component of the composition contains an epoxy resin typically present in an amount of 15 - 60 wt% based on the weight of the first component. Preferably, the epoxy resin occupies 15 - 50 wt%, more preferably 20 - 45 wt%, for example 25 - 40 wt% or 28 - 39 wt% of the first component.

[0070] If the amount of the epoxy resin is more than 60%, it may be disadvantageous to the adhesiveness and flexibility of the composition. On the other hand, if the amount is small, mainly less than 15%, the shrinkage rate may increase. Therefore, the amount of the epoxy resin as described above is preferable.

[0071] The epoxy resin used in the present specification may include a monofunctional epoxy resin, a polyfunctional (multi- or poly-) epoxy resin, and combinations thereof. The epoxy resin may be a pure compound, but may also be a mixture of epoxy-functional compounds, including a mixture of compounds having different numbers of epoxy groups per molecule. The epoxy resin may be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, and may be substituted. Further, the epoxy resin may be a monomer or a polymer.

[0072] Although not intended to limit the present invention, exemplary monoepoxide compounds include the following. Alkylene oxides; epoxy-substituted alicyclic hydrocarbons such as cyclohexene oxide, vinylcyclohexene monooxide, (+)-cis-limonene oxide, (+)-cis,trans-limonene oxide, (-)-cis,trans-limonene oxide, cyclooctene oxide, cyclododecene oxide and α-pinene oxide; epoxy-substituted aromatic hydrocarbons; monoepoxy-substituted alkyl ethers of monohydric alcohols or phenols such as glycidyl ethers of aliphatic, alicyclic and aromatic alcohols; monoepoxy-substituted alkyl esters of monocarboxylic acids such as glycidyl esters of aliphatic, alicyclic and aromatic monocarboxylic acids; monoepoxy-substituted alkyl esters of polycarboxylic acids in which other carboxy groups are esterified with alkanols; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxyalkyl ethers of polyhydric alcohols in which other OH groups are esterified or etherified with carboxylic acids or alcohols; and monoesters of polyhydric alcohols and epoxy monocarboxylic acids in which other OH groups are esterified or etherified with carboxylic acids or alcohols.

[0073] By way of example, the following glycidyl ethers may be mentioned as monoepoxide compounds that are particularly suitable for use herein. Methyl glycidyl ether; ethyl glycidyl ether; propyl glycidyl ether; butyl glycidyl ether; pentyl glycidyl ether; hexyl glycidyl ether; cyclohexyl glycidyl ether; octyl glycidyl ether; 2-ethylhexyl glycidyl ether; aryl glycidyl ether; benzyl glycidyl ether; phenyl glycidyl ether; 4-tert-butylphenyl glycidyl ether; 1-naphthyl glycidyl ether; 2-naphthyl glycidyl ether; 2-chlorophenyl glycidyl ether; 4-chlorophenyl glycidyl ether; 4-bromophenyl glycidyl ether; 2,4,6-trichlorophenyl glycidyl ether; 2,4,6-tribromophenyl glycidyl ether; pentafluorophenyl glycidyl ether; o-cresyl glycidyl ether; m-cresyl glycidyl ether; and p-cresyl glycidyl ether.

[0074] In an embodiment, the monoepoxide compound has the following formula (I): TIFF0007709975000001.tif26160[wherein R w , R x , R y and R z may be the same or different and are independently hydrogen, a halogen atom, a C 1- -C8 alkyl group, a C 3- -C 10 cycloalkyl group, a C 2- -C 12 alkenyl group, a C 6- -C 18 aryl group or a C 7- -C 18 aralkyl group, provided that at least one of R y and R z is not hydrogen] in accordance with.

[0075] R w , R x and Ry is hydrogen, and R z is preferably a phenyl group or a C 1- C8 alkyl group, more preferably a C 1- C4 alkyl group.

[0076] Regarding this embodiment, exemplary monoepoxides include: ethylene oxide; 1,2-propylene oxide (propylene oxide); 1,2-butylene oxide; cis-2,3-epoxybutane; trans-2,3-epoxybutane; 1,2-epoxypentane; 1,2-epoxyhexane; 1,2-heptylene oxide; decene oxide; butadiene oxide; isoprene oxide; and styrene oxide.

[0077] In the present invention, it is mentioned that at least one monoepoxide compound selected from the group consisting of ethylene oxide; propylene oxide; cyclohexene oxide; (+)-cis-limonene oxide; (+)-cis,trans-limonene oxide; (-)-cis,trans-limonene oxide; cyclooctene oxide; and cyclododecene oxide is used.

[0078] Here too, without intending to limit the present invention, suitable polyepoxide compounds may be liquids, solids, or solutions in a solvent. Further, such polyepoxide compounds should have an epoxy equivalent of 100 to 700 g / eq, for example 120 to 320 g / eq. Further, generally, diepoxide compounds having an epoxy equivalent of less than 500 g / eq, and further less than 400 g / eq are preferred. This is mainly from the perspective of cost because in their production, low molecular weight epoxy resins require limited treatment in purification.

[0079] Examples of the types or groups of polyepoxide compounds that can be polymerized in the present invention include: glycidyl ethers of polyhydric alcohols and polyhydric phenols; glycidyl esters of polycarboxylic acids; and epoxidized polyethylene unsaturated hydrocarbons, esters, ethers, and amides.

[0080] Suitable diglycidyl ether compounds may be essentially aromatic, aliphatic or cycloaliphatic and are derivable as such from dihydric phenols and dihydric alcohols. And useful classes of such diglycidyl ethers are the diglycidyl ethers of aliphatic and cycloaliphatic diols such as 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol and cyclohexanediol; bisphenol A-based diglycidyl ethers; bisphenol F diglycidyl ethers; diglycidyl o-phthalate, diglycidyl isophthalate and diglycidyl terephthalate; polyalkylene glycol-based diglycidyl ethers, especially polypropylene glycol diglycidyl ether; and polycarbonate diol-based glycidyl ethers. Other suitable diepoxides that may be mentioned are the diepoxides of double unsaturated fatty acid C 1- C 18 alkyl esters; butadiene diepoxide; polybutadiene diglycidyl ether; vinylcyclohexene diepoxide; and limonene diepoxide.

[0081] Further exemplary polyepoxide compounds include, but are not limited to, glycerol polyglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; diglycerol polyglycidyl ether; polyglycerol polyglycidyl ether; and sorbitol polyglycidyl ether.

[0082] And examples of very preferred polyepoxide compounds include the following. DER TM 331 and DER TM 383 and other bisphenol A epoxy resins; DER TM 354 and other bisphenol F epoxy resins; DER TM 353 and other bisphenol A / F epoxy resin blends; DER TMAliphatic glycidyl ethers such as 736; DER TM Polypropylene glycol diglycidyl ethers such as 732; DER TM 661 and DER TM Solid bisphenol A epoxy resins such as 664UE; DER TM Solutions of bisphenol A solid epoxy resins such as 671-X75, DEN TM Epoxy novolac resins such as 438; DER TM Brominated epoxy resins such as 542; ERISYS TM Castor oil triglycidyl ethers such as GE-35H, ERISYS TM Polyglycerol-3-polyglycidyl ethers such as GE-38, and ERISYS TM Sorbitol glycidyl ethers such as GE-60.

[0083] Separately from the above, the first component of the composition, in certain embodiments, has the formula: TIFF0007709975000002.tif1466 [wherein, each R is independently selected from methyl or ethyl; and, n is from 1 to 10] and may include glycidoxyalkylalkoxysilanes having.

[0084] Exemplary silanes include, but are not limited to, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltriethoxysilane; and 8-glycidoxyoctyltrimethoxysilane. When present, the epoxide-functional silane preferably constitutes less than 20% by weight, preferably less than 10% by weight or less than 5% by weight, based on the total weight of the epoxide compound.

[0085] The present invention also does not prevent the first component of the curable composition from further comprising one or more cyclic monomers selected from the group consisting of oxetane; cyclic carbonate; cyclic anhydride; and lactone. The disclosures of the following cited documents may be useful in disclosing suitable cyclic carbonate functional compounds. U.S. Patent No. 3,535,342; U.S. Patent No. 4,835,289; U.S. Patent No. 4,892,954; British Patent Application Publication No. 1,485,925; and European Patent Application Publication No. 0 119 840. However, such cyclic comonomers preferably constitute less than 20% by weight, more preferably less than 10% by weight or less than 5% by weight, based on the total weight of the epoxide compound.

[0086] <(meth)acrylate monomer> The first component of the composition typically comprises a (meth)acrylate monomer present in an amount of 5 to 50% by weight, based on the weight of the first component. Preferably, the (meth)acrylate monomer constitutes 7 to 40% by weight of the first component, such as 10 to 30% by weight or 15 to 27% by weight.

[0087] When the amount of the (meth)acrylate monomer exceeds 50%, the shrinkage rate of the composition may increase. On the other hand, when the amount is mainly less than 5%, the flexibility of the composition may deteriorate. Therefore, the above amount of the (meth)acrylate monomer is preferred.

[0088] In an alternative presentation of the composition selection, which is not intended to be mutually exclusive with what is shown above, the weight ratio of the epoxy resin to the (meth)acrylate monomer is desirably in the range of 4:1 to 1:1, preferably 4:1 to 2:1, such as 4:1 to 2.5:1.

[0089] There is no particular intention to limit the (meth)acrylate monomers useful herein, and it is considered that the (meth)acrylate monomers may be any esters of acrylic acid or methacrylic acid known in the art. That is, exemplary (meth)acrylic monomers include, but are not limited to, the following. · C alkyl esters of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate (all isomers), hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and n-stearyl (meth)acrylate; 1- C 18 alkyl esters; · C cycloalkyl esters of (meth)acrylic acid such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; 3- C 18 cycloalkyl esters; · C aryl esters of (meth)acrylic acid such as phenyl (meth)acrylate and tolyl (meth)acrylate; 6- C 18 aryl esters; · C aralkyl esters of (meth)acrylic acid such as benzyl (meth)acrylate; 7- C 24 aralkyl esters; · C alkoxyalkyl esters of (meth)acrylic acid such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 3-methoxybutyl (meth)acrylate; 1- C 18 alkoxyalkyl esters; · Fluoro-containing C 1- C 18 alkyl esters of (meth)acrylic acid, such as trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, perfluoromethyl (meth)acrylate, dipentafluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate; · C 1- C 18 hydroxyalkyl esters of (meth)acrylic acid, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; · Di / poly-esters of di / poly-functional alcohols, such as ethylene glycol di(meth)acrylate, 1,3 or 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate; · C 1- C 18 aminoalkyl esters of (meth)acrylic acid, such as 2-aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and (meth)acryloxyethoxyethylamine; · C 1- C 18 alkoxysilyl-containing alkyl esters of (meth)acrylic acid, such as γ-(meth)acryloyloxypropyltrimethoxysilane; · Ethylene oxide adducts or propylene oxide adducts of (meth)acrylic acid; and, · (Meth)acrylate esters formed by alcohols having other functional groups, such as tetrahydrofurfuryl (meth)acrylate.

[0090] To achieve completeness, it is not excluded that the first component of the composition comprises a macromonomer component consisting of one or more oligomers selected from the group consisting of urethane (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. However, it may be monofunctional or polyfunctional with respect to polymerizable (meth)acrylate functionality, but such oligomeric compounds based on urethane, ester, and ether subunits of the repeating structure should generally not be constituted to exceed 30% by weight of the total of (meth)acrylate monomers in the first component.

[0091] As is known in the art, urethane (meth)acrylate oligomers can be prepared by the reaction of a polyfunctional (meth)acrylate having a hydroxyl group with a polyisocyanate as defined above herein. In particular, the polyfunctional (meth)acrylate having a hydroxyl group can be selected from the group consisting of 2-hydroxyethyl (meth)acrylate; 2-hydroxyisopropyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; hydroxyethyl caprolactone (meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate; dipentaerythritol hexa(meth)acrylate; and combinations thereof.

[0092] Suitable polyester (meth)acrylate oligomers can be obtained by reacting (meth)acrylic acid with a polyester prepared from a polybasic acid or its anhydride and a polyhydric alcohol. Examples of polybasic acids include, but are not limited to, phthalic acid; succinic acid; adipic acid; glutaric acid; sebacic acid; isosebacic acid; tetrahydrophthalic acid; hexahydrophthalic acid; dimer acid; trimellitic acid; pyromellitic acid; pimelic acid; and azelaic acid. Examples of polyhydric alcohols include, but are not limited to, 1,6 - hexanediol; diethylene glycol; 1,2 - propylene glycol; 1,3 - butylene glycol; neopentyl glycol; dipropylene glycol; polyethylene glycol; and polypropylene glycol.

[0093] As is known in the art, polyether (meth)acrylate oligomers can be obtained by a transesterification reaction between a polyether and a (meth)acrylate ester such as ethyl methacrylate. Exemplary polyethers include polyethers obtained from ethoxylated or propoxylated trimethylolpropane, pentaerythritol, etc., or polyethers obtained by polyetherification of 1,4 - propanediol and the like.

[0094] In a preferred embodiment, the first component is methyl (meth) acrylate; ethyl (meth) acrylate; n-propyl (meth) acrylate; isopropyl (meth) acrylate; n-butyl (meth) acrylate; isobutyl (meth) acrylate; tert-butyl (meth) acrylate; n-pentyl (meth) acrylate; n-hexyl (meth) acrylate; cyclohexyl (meth) acrylate; n-heptyl (meth) acrylate; n-octyl (meth) acrylate; 2-ethylhexyl-(meth) acrylate; nonyl (meth) acrylate; decyl (meth) acrylate; dodecyl (meth) acrylate; phenyl (meth) acrylate; tolyl (meth) acrylate; benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate; 3-methoxybutyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate; stearyl (meth) acrylate; glycidyl (meth) acrylate; isobornyl (meth) acrylate; 2-aminoethyl (meth) acrylate; γ-(meth)acryloyloxypropyltrimethoxysilane; (meth)acrylic acid-ethylene oxide adduct; trifluoromethylmethyl (meth) acrylate; 2-trifluoromethylethyl (meth) acrylate; 2-perfluoroethylethyl (meth) acrylate; 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate; 2-perfluoroethyl (meth) acrylate; perfluoromethyl (meth) acrylate; dipentafluoroethylmethyl (meth) acrylate; 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate; 2-perfluorohexylethyl (meth) acrylate; 2-perfluorodecylethyl (meth) acrylate; 2-perfluorohexadecylethyl (meth) acrylate; ethoxylated trimethylolpropane triacrylate; trimethylolpropane trimethacrylate; dipentaerythritol monohydroxypentaacrylate; pentaerythritol triacrylate; ethoxylated trimethylolpropane triacrylate; 1,6-hexanediol diacrylate; neopentyl glycol diacrylate; pentaerythritol tetraacrylate;It contains at least one (meth)acrylate monomer selected from the group consisting of 1,2-butylene glycol diacrylate; trimethylolpropane ethoxylate tri(meth)acrylate; glyceryl propoxylate tri(meth)acrylate; trimethylolpropane tri(meth)acrylate; dipentaerythritol monohydroxypenta(meth)acrylate; tripropylene glycol di(meth)acrylate; neopentyl glycol propoxylate di(meth)acrylate; 1,4-butanediol di(meth)acrylate; triethylene glycol di(meth)acrylate; butylene glycol di(meth)acrylate and ethoxylated bisphenol A di(meth)acrylate.;

[0095] Good results were obtained when the first component contained at least one (meth)acrylate monomer selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, isobornyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate and trimethylolpropane triacrylate and mixtures thereof.;

[0096] The above (meth)acrylate monomers are preferred because the size of the monomers is thought to result in the formation of an ideal polymer network and enhance ion transport.;

[0097] <Copolymerize with (meth)acrylate monomer possible Acid monomer> The first component of the composition may optionally contain an acid monomer copolymerizable with the (meth)acrylate monomer. When so included, such copolymerizable acid preferably constitutes up to 50% by weight, preferably 10 - 40% by weight, based on the total weight of the (meth)acrylate monomer. For completeness, typically such monomers should be used in the form of the free acid, but partial or complete neutralization of the constituent acid groups of the monomer with a suitable base is not excluded as long as this does not impair their participation in the copolymerization.;

[0098] When the amount of the copolymerizable acid is more than 50%, it may cause corrosion problems and gas generation. On the other hand, when the amount is small, incomplete curing may occur, which may reduce the initial adhesiveness. Therefore, the amount of the copolymerizable acid is preferred.

[0099] Although there is no intention to limit the present invention, the copolymerizable acid monomer is preferably selected from ethylenically unsaturated carboxylic acids; ethylenically unsaturated sulfonic acids; and vinylphosphonic acid. Suitable ethylenically unsaturated sulfonic acids are, for example, vinylsulfonic acid, styrenesulfonic acid, and acrylamidomethylpropanesulfonic acid.

[0100] Preferably, the copolymerizable acid of this component is α,β-monoethylenically unsaturated monocarboxylic acid; α,β-monoethylenically unsaturated dicarboxylic acid; C 1- C6 alkyl half ester of α,β-monoethylenically unsaturated tricarboxylic acid; α,β-monoethylenically unsaturated tricarboxylic acid having at least one free carboxylic acid group and C 1- C6 alkyl ester thereof; and an ethylenically unsaturated carboxylic acid selected from the group consisting of these and mixtures thereof, or consisting of. In particular, the copolymerizable acid of this component contains, or consists of, at least one acid selected from methacrylic acid, acrylic acid, itaconic acid, maleic acid, aconitic acid, crotonic acid, and fumaric acid.

[0101] <Further vinyl monomer> Apart from or in addition to the presence of copolymerizable acids, the first component of the composition can optionally contain vinyl monomers copolymerizable with (meth)acrylate monomers, said vinyl monomers being styrene monomers such as styrene, vinyltoluene, α-methylstyrene and chlorostyrene; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; and vinyl chloride, vinylidene chloride, aryl chloride, aryl alcohol, selected from the group consisting of. However, when such vinyl comonomers are included, it is desirable that they be less than 40% by weight, preferably less than 20% by weight or less than 10% by weight, based on the total weight of the (meth)acrylate monomers.

[0102] <Electrolyte> The first component of the composition contains 2.5 to 25% by weight of electrolyte, based on the weight of the first component. The electrolyte can preferably constitute 4 to 23% by weight, for example 5 to 20% by weight, of the first component.

[0103] Amounts of these electrolytes above 25% may result in a good peeling effect, but may lead to incomplete curing and adversely affect the initial adhesion properties. On the other hand, small amounts, mainly less than 2.5%, may lead to a lack of peeling effect. Therefore, the amounts of the electrolytes described above are preferred.

[0104] The electrolyte preferably is TIFF0007709975000003.tif134165[wherein, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen, C 1- C 18 alkyl, C 3- C 18 cycloalkyl, C 6- C 18 aryl, C 7- C 24 aralkyl, C 2- C 20 alkenyl, -C(O)R q , -C(O)OH, -CN and -NO2, and R q is C 1- C6 alkyl] and contains at least one salt having a formula selected from the group consisting of

[0105] To complete, C 1- C 18 alkyl, C 3- C 18 cycloalkyl, C 6- C 18 aryl, C 7- C 24 aralkyl, C 2- C 20 The term alkenyl explicitly includes a group in which one or more hydrogen atoms are substituted with a halogen atom (e.g., C 1- C 18 haloalkyl) or a group substituted with a hydroxyl group (e.g., C 1- C 18 hydroxyalkyl). In particular, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen, C 1- C 12 alkyl, C 1- C 12 haloalkyl, C 1- C12 Hydroxyalkyl and C 3- C 12 Preferably selected from cycloalkyl. For example, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can independently be hydrogen, C 1- C6 alkyl, C 1- C6 haloalkyl and C 1- C6 hydroxyalkyl.

[0106] There is no particular intention to limit the counter anion (X - ) that can be employed in the electrolyte. Exemplary anions can be selected from the following. · Halide; · Formulas PF6 - , CF3SO3 - , (CF3SO3)2N - , CF3CO2 - and CCl3CO2 - pseudohalides and halogen-containing compounds of; · CN - , SCN - and OCN - ; · Phenate; · General formula SO4 2- , HSO4 - , SO3 2- , HSO3 - , R a OSO3 - , and R a SO3 - sulfates, sulfites, sulfonates of; · General formula PO4 3- , HPO4 2- , H2PO4 - , R a PO4 2- , HR a PO4 - and R a R b PO4 - phosphates of; · General formula Ra HPO3 - 、R a R b PO2 - およびR a R b PO3 - and phosphonates and phosphinates of; · General formula PO3 3- 、HPO3 2- 、H2PO3 - 、R a PO3 2- 、R a HPO3 - およびR a R b PO3 - and phosphites of; · General formula R a R b PO2 - 、R a HPO2 - 、R a R b PO - 、およびR a HPO - and phosphonites and phosphinites of; · General formula R a COO - and carboxylate anions of; · Hydroxycarboxylate anions and saccharate anions; · Saccharinate (salt of o-benzoic acid sulfimide); · General formula BO3 3- 、HBO3 2- 、H2BO3 - 、R a R b BO3 - 、R a HBO3 - 、R a BO3 2- 、B(OR a )(OR b )(OR C )(OR d ) - 、B(HSO4) - およびB(R a SO4) - and borates of; · General formula Ra BO₂ 2- and R a R b BO - boronate; · General formula HCO₃ - 、CO₃ 2- and R a CO₃ - carbonates and carbonic acid esters; · General formula SiO₄ 4- 、HSiO₄ 3- 、H₂SiO₄ 2- 、H₃SiO₄ - 、R a SiO₄ 3- 、R a R b SiO₄ 2- 、R a R b R c SiO₄ - 、HR a SiO₄ 2- 、H₂R a SiO₄ - and HR a R b SiO₄ - silicates and silicic acid esters; · General formula R a SiO₃ 3- 、R a R b SiO₂ 2- 、R a R b R c SiO - 、R a R b R c SiO₃ - 、R a R b R c SiO₂ - and R a R b SiO₃ 2- alkylsilanolates and arylsilanolates; · Pyridinates and pyrimidinates; · General formula: Carboxylic acid imides, bis(sulfonyl)imides and sulfonylimides of TIFF0007709975000004.tif2993; · General formula Methides of TIFF0007709975000005.tif2826; · Alkoxides and aryloxides of general formula R a O - ; and, · Sulfides, hydrogen sulfide, polysulfides, hydrogen polysulfides and thiolates of general formula S 2- , HS - , [S v 2- , [HS v - and [R a S] - wherein v is a positive integer from 2 to 10.] [Here, in the general formula v is a positive integer from 2 to 10. R a , R b , R c and R d are independently selected from hydrogen, C 1- C 12 alkyl, C 5- C 12 cycloalkyl, C 5- C 12 heterocycloalkyl, C 6- C 18 aryl and C 5- C 18 heteroaryl.]

[0107] Based on the definitions in the above list, preferred anions are halides; as defined above pseudohalides and and ha ​​It is selected from the group consisting of halogen-containing compounds; carboxylate anions, especially formate, acetate, propionate, butyrate and lactate; hydroxycarboxylate anions; pyridinate and pyrimidinate; carboxylic acid imides, bis(sulfonyl)imides and sulfonylimides; sulfates, especially methyl sulfate and ethyl sulfate; sulfites; sulfonates, especially methanesulfonate; and phosphates, especially dimethyl-phosphate, diethyl-phosphate and di-(2-ethylhexyl)-phosphate.

[0108] The electrolyte of the first component is preferably 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium methylsulfate, 1-hexyl-3-methylimidazolium 2-(2-fluoroanilino)-pyridinate, 1-hexyl-3-methylimidazolium imide, 1-butyl-1-methylpyrrolidinium 2-(2-fluoroanilino)-pyridinate, 1-butyl-1-methyl-pyrrolidinium imide, trihexyl(tetradecyl)phosphonium 2-(2-fluoroanilino)-pyridinate, cyclohexyltrimethylammonium bis(trifluoromethylsulfonyl)imide, di(2-hydroxyethyl)ammonium trifluoroacetate, N,N-dimethyl(2-hydroxyethyl)ammonium octanoate, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, N-ethyl-N-N-N-N-tetramethylguanidinium trifluoromethanesulfonate, guanidinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium bromide, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-hydroxymethylpyridinium ethylsulfate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-ethyl-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-propyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,It is selected from the group consisting of 3-dimethylimidazolium hexafluorophosphate, 1-butylimidazole, 1-methylimidazolium tetrafluoroborate, tetrabutylphosphonium tris(pentafluoroethyl)trifluorophosphate, trihexyl(tetradecyl)phosphonium tetrafluoroborate, and mixtures thereof. It is particularly preferred to use at least one of 1-ethyl-3-methylimidazolium methanesulfonate and 1-ethyl-3-methylimidazolium methylsulfate.,

[0109] The above electrolyte is preferred because it provides good stability and good initial adhesion strength to the composition and a better peeling effect when subjected to potential treatment.

[0110] <Solubilizer> The first component of the two-component (2K) composition necessarily contains a solubilizer, which is usually present in an amount of 0.5 to 20% by weight, based on the weight of the first component. Preferably, the solubilizer constitutes 1 to 15% by weight, for example, 1 to 13% by weight of the first component. The function of the solubilizer is not to improve or change the adhesion properties of the composition. The solubilizer increases the conductivity of the composition of the present invention. Furthermore, the solubilizer has a function of promoting the miscibility of the electrolyte in the adhesive composition formed upon mixing its two components. The solubilizer may or may not form part of the polymer matrix formed upon curing of the adhesive composition, but plays a role in promoting ion migration therein. The solubilizer is thus preferably a polar compound and desirably should be liquid at room temperature.

[0111] When the amount of the solubilizer exceeds 20%, it may have an adverse effect on the adhesiveness and curability. On the other hand, when the amount is mainly less than 0.5%, the first component of the composition becomes solid, which may inhibit the mixing of the first component and the second component. Therefore, these amounts are preferred.

[0112] Suitable classes of solubilizers include polyphosphazenes; polymethylene sulfides; polyoxyalkylene glycols; polyethyleneimine; silicone surfactants and fluorinated silicone surfactants, such as fluorinated polysilanes, polyalkylsiloxanes and polyoxyalkylene-modified polydimethylsiloxanes; copolymers of functionalized polyalkylsiloxanes and epoxy resins, such as copolymers of functionalized polydimethylsiloxane (PDMS) and epoxy resins; polyhydric alcohols; and saccharides.

[0113] Ethylene glycol, 1,3-propanediol, cyclohexanediol, hydroquinone, catechol, resorcinol, phloroglucinol, pyrogallol, hydroxyhydroquinone, tris(hydroxymethyl)benzene, tris(hydroxymethyl)benzene with three methyl or ethyl substituents bonded to the remaining carbon atoms of benzene, isosorbide, isomannide, isoidide, glycerol, cyclohexane-1,2,4-triol, 1,3,5-cyclohexanetriol, pentane-1,2,3-triol, hexane-1,3,5-triol, erythritol, 1,2,4,5-tetrahydroxybenzene, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, inositol, fructose, glucose, mannose, lactose, 1,1,1-tris(hydroxymethyl)propane, 1,1,1-tris(hydroxymethyl)ethane, di(trimethylolpropane), trimethylolpropane ethoxylate, 2-hydroxymethyl-1,3-propanediol, pentaerythritol aryl ether and pentaerythritol, and other polyhydric alcohols and saccharides.

[0114] Among the polyoxyalkylene glycols, the use of polyoxy(C 2- C3) alkylene glycols having a weight average molecular weight of 200 to 10,000 g / mol, for example 200 to 2,000 g / mol, may be particularly preferred.

[0115] <The second part of the two-component (2K) composition> The second component of the two-component composition includes a first curing agent, an accelerator, and a filler described above in this specification.

[0116] <Curing agent> The curing agent needs to consist of at least one compound having at least two epoxide-reactive groups per molecule. The curing agent particularly includes: i) at least one polyamine having at least two amine hydrogens that react with an epoxy group; ii) at least one mercapto compound having at least two mercapto groups that react with an epoxy group; and iii) one or more of at least one Mannich base may be included.

[0117] At least one polyamine having at least two amine hydrogens that react with an epoxy group particularly includes a primary amine group and / or a secondary amine group, and desirably has an equivalent weight of 150 g / eq. or less, more preferably 125 g / eq. or less per primary amine group or secondary amine group.

[0118] Suitable polyamines that can be used alone or in combination include, but are not limited to, the following. i) The following examples may be mentioned: aliphatic primary diamines, cycloaliphatic primary diamines or arylaliphatic primary diamines: 2,2-dimethyl-1,3-propanediamine; 1,3-pentanediamine (DAMP); 1,5-pentanediamine; 1,5-diamino-2-methylpentane (MPMD); 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine); 1,6-hexanediamine (hexamethylenediamine, HMDA); 2,5-dimethyl-1,6-hexanediamine; 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine; 1,7-heptanediamine; 1,8-octanediamine; 1,9-nonanediamine; 1,10-decanediamine; 1,11-undecanediamine; 1,12-dodecanediamine; 1,2-, 1,3- and 1,4-diaminocyclohexane; bis(4-aminocyclohexyl)methane; bis(4-amino-3-methylcyclohexyl)methane; bis(4-amino-3-ethylcyclohexyl)methane; bis(4-amino-3,5-dimethylcyclohexyl)methane; bis(4-amino-3-ethyl-5-methylcyclohexyl)methane; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA); 2- and / or 4-methyl-1,3-diaminocyclohexane; 1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (norbornanediamine, NBDA); 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]-decane (TCD-diamine); 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA); 1,8-menthanediamine; 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; and, 1,3-bis(aminomethyl)benzene (MXDA). ii) Tertiary amine group-containing polyamines having two or three primary aliphatic amine groups, of which the following specific examples may be mentioned: N,N'-bis(aminopropyl)-piperazine; N,N-bis(3-aminopropyl)methylamine; N,N-bis(3-aminopropyl)ethylamine; N,N-bis(3-aminopropyl)propylamine; N,N-bis(3-aminopropyl)cyclohexylamine; N,N-bis(3-aminopropyl)-2-ethylhexylamine; tris(2-aminoethyl)amine; tris(2-aminopropyl)amine; tris(3-aminopropyl)amine; and products from the double cyanoethylation of fatty amines derived from natural fatty acids and subsequent reduction, such as N,N-bis(3-aminopropyl)dodecylamine and N,N-bis(3-aminopropyl)tallow alkylamine, etc., commercially available as Triameen® Y12D and Triameen® YT (manufactured by Akzo Nobel). iii) Ether group-containing aliphatic primary polyamines, of which the following specific examples may be mentioned: bis(2-aminoethyl)ether; 3,6-dioxaoctane-1,8-diamine; 4,7-dioxadecane-1,10-diamine; 4,7-dioxadecane-2,9-diamine; 4,9-dioxadodecane-1,12-diamine; 5,8-dioxadodecane-3,10-diamine; 4,7,10-trioxatridecane-1,13-diamine and higher oligomers of these diamines; bis(3-aminopropyl)polytetrahydrofuran and other polytetrahydrofuran diamines; alicyclic ether group-containing diamines obtained from the propoxylation of 1,4-dimethylolcyclohexane and subsequent amination, such as materials commercially available as Jeffamine® RFD-270 (manufactured by Huntsman); polyoxyalkylene diamines or polyoxyalkylene triamines obtained as products from the amination of polyoxyalkylene diols and polyoxyalkylene triols 、This is commercially available under the name of Jeffamine® (manufactured by Huntsman), the name of polyetheramine (manufactured by BASF) or the name of PC Amines® (manufactured by Nitroil). The use of Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-600, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000, Jeffamine® EDR-104, Jeffamine® EDR-148 and Jeffamine® EDR-176, and the corresponding amines from BASF or Nitroil can be particularly preferably mentioned. iv) The following examples may be mentioned, primary diamines having a secondary amine group: 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT); diethylenetriamine (DETA); triethylenetetramine (TETA); tetraethylenepentamine (TEPA); pentaethylenehexamine (PEHA); higher homologues of linear polyethyleneamines such as polyethylene polyamines having 5 to 7 ethyleneamine units (so-called "higher ethylene polyamines" HEPA); dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-aminopentyl)-1,3-pentanediamine, N5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine or N,N'-bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, and products obtained from multiple cyanoethylation or cyanobutylation and subsequent hydrogenation of primary diamines and primary polyamines having at least two primary amine groups. v) Polyamines having one primary and at least one secondary amino group, examples of which may be mentioned: N-butyl-1,2-ethanediamine; N-hexyl-1,2-ethanediamine; N-(2-ethylhexyl)-1,2-ethanediamine; N-cyclohexyl-1,2-ethanediamine; 4-aminomethyl-piperidine; N-(2-aminoethyl)piperazine; N-methyl-1,3-propanediamine; N-butyl-1,3-propanediamine; N-(2-ethylhexyl)-1,3-propanediamine; N-cyclohexyl-1,3-propanediamine; 3-methylamino-1-pentylamine; 3-ethylamino-1-pentylamine; 3-cyclohexylamino-1-pentylamine; aliphatic diamines such as N-cocoalkyl-1,3-propanediamine; products from Michael type addition reactions of primary aliphatic diamines with acrylonitrile, maleic acid diesters or fumaric acid diesters, citraconic acid diesters, acrylic acid esters and methacrylic acid esters, acrylamide and methacrylamide, and itaconic acid diesters in a 1:1 molar ratio; products by partial reductive alkylation of primary polyamines with aldehydes or ketones, in particular pre-group polyamines having two primary amine groups, in particular 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, N-monoalkylation products of BHMT, DETA, TETA, TEPA, DPTA, N3-amine and N4-amine, where the preferred alkyl groups are benzyl, isobutyl, hexyl and 2-ethylhexyl; and partially styrenated polyamines such as those commercially available as Gaskamine® 240 (manufactured by Mitsubishi Gas Chemical Company). vi) a secondary diamine and, in particular, said polyamine having two primary amine groups, in particular 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, BHMT, DETA, TETA, TEPA, DPTA, the N,N'-dialkylation product of an N3-amine or an N4-amine, where the preferred alkyl groups are 2-phenylethyl, benzyl, isobutyl, hexyl and 2-ethylhexyl groups. vii) aromatic polyamines which may be mentioned below: m- and p-phenylenediamine; 4,4'-, 2,4' and 2,2'-diaminodiphenylmethane; 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA); 2,4- and 2,6-tolylenediamine; a mixture of 3,5-dimethylthio-2,4-tolylenediamine and 3,5-dimethylthio-2,6-tolylenediamine (available from Albermarle as Ethacure® 300); 3,5-diethyl-2,4- tolyleneMixture of diamine and 3,5 - diethyl - 2,6 - tolylenediamine (DETDA); 3,3’,5,5’ - tetraethyl - 4,4’ - diaminodiphenylmethane (M - DEA); 3,3’,5,5’ - tetraethyl - 2,2’ - dichloro - 4,4’ - diaminodiphenylmethane (M - CDEA); 3,3’ - diisopropyl - 5,5’ - dimethyl - 4,4’ - diaminodiphenylmethane (M - MIPA); 3,3’,5,5’ - tetraisopropyl - 4,4’ - diaminodiphenylmethane (M - DIPA); 4,4’ - diaminodiphenyl - sulfone (DDS); 4 - amino - N - (4 - aminophenyl)benzenesulfonamide; 5,5’ - methylenedianthranilic acid; dimethyl - (5,5’ - methylenedianthranilate); 1,3 - propylene - bis(4 - aminobenzoate); 1,4 - butylene - bis(4 - aminobenzoate); polytetramethyleneoxide - bis(4 - aminobenzoate) (available from Air Products as Versalink®); 1,2 - bis(2 - aminophenylthio)ethane, 2 - methylpropyl - (4 - chloro - 3,5 - diaminobenzoate); and Tert. butyl - (4 - chloro - 3,5 - diaminobenzoate). viii) An indicator member (displayed configuration) is a monovalent or polyvalent carboxylic acid or their esters, or their anhydrides, (especially dimer fatty acids) and aliphatic polyamines, alicyclic polyamines or aromatic polyamines, such as polyalkyleneamines such as DETA or TETA including the reaction product with 、 polyamideamine . Commercially available polyamideamines include Versamid® 100, 125, 140 and 150 (from Cognis); Aradur® 223, 250 and 848 (from Huntsman); Euretek® 3607 and 530 (from Huntsman); and Beckopox® EH651, EH654, EH655, EH661 and EH663 (from Cytec).

[0119] Among the polyamines having at least two primary aliphatic amine groups, preferred are isophoronediamine (IPDA); hexamethylenediamine (HMDA); 1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; bis(4-aminocyclohexyl)methane; bis(4-amino-3-methylcyclohexyl)methane; NBDA; and ether group-containing polyamines having a number average molecular weight (Mn) of at most 500 g / mol. Particularly preferred among the ether group-containing polyamines are Jeffamine® D-230 and D-600 (available from Huntsman).

[0120] As described above, the composition of the present invention may optionally contain at least one compound having at least two reactive mercapto groups per molecule. Suitable mercapto group-containing compounds that can be used alone or in combination include, but are not limited to, the following. · Liquid mercaptan-terminated polysulfide polymers, commercial examples of which include Thiokol® polymers (available from Morton Thiokol), particularly types LP-3, LP-33, LP-980, LP-23, LP-55, LP-56, LP-12, LP-31, LP-32 and LP-2; and Thioplast® polymers (from Akzo Nobel), particularly types G10, G112, G131, G1, G12, G21, G22, G44 and G4. · Mercaptan-terminated polyoxyalkylene ethers obtained by reacting polyoxyalkylene diols and polyoxyalkylene triols with epichlorohydrin or alkylene oxides, followed by reaction with sodium hydrogen sulfide. · Mercaptan-terminated compounds in the form of polyoxyalkylene derivatives known under the trade name Capcure® (from Cognis), particularly types WR-8, LOF and 3-800. ·Specific examples include pentaerythritol tetramercaptoacetate (PETMP); trimethylolpropane trimercaptoacetate (TMPMP); glycol dimercaptoacetate; and polyoxyalkylene diol. and Triol yl, Ethoxylated trimethylolpropane and polyester diol and esterification products with thiocarboxylic acids such as thioglycolic acid and 2- or 3-mercaptopropionic acid, Polyesters of thiocarboxylic acids, such as those mentioned above. ·2,4,6 - Trimercapto - 1,3,5 - triazine, 2,2'-(ethylenedioxy)-diethanethiol (triethylene glycol dimercaptan) and / or ethanedithiol.

[0121] The use of polyesters of thiocarboxylic acids, particularly the use of at least one of pentaerythritol tetramercaptoacetate (PETMP), trimethylolpropane trimercaptoacetate (TMPMP) and glycol dimercaptoacetate is considered to be suitable.

[0122] As described above, the curing agent may contain at least one Mannich base. Such compounds may be characterized by containing at least one phenalkamine, and in particular, phenalkamines obtained from the condensation of cardanol (CAS number: 37330 - 39 - 5), aldehyde and amine. The reactant amine in the condensation reaction is preferably ethylenediamine or diethyltriamine.

[0123] Mannich bases and phenalkamines are known in the art, and suitable examples include commercially available phenalkamines such as Cardolite® NC - 541, NC - 557, NC - 558, NC - 566, Lite2001 and Lite2002 (available from Cardolite), Aradur® 3440, 3441, 3442 and 3460 (available from Huntsman) and Beckopox® EH614, EH621, EH624, EH628 and EH629 (available from Cytec).

[0124] <Accelerator> A suitable accelerator is a substance that promotes the reaction between an epoxy group and an epoxy-reactive group, such as the reaction between an amine group or a thiol group and an epoxy group. Specific examples relate to the use of amine accelerators that function by deprotonating the existing reactive thiol group (-SH) to form a thiolate (-S″), and this thiolate reacts with the epoxy group by nucleophilic ring-opening polymerization.

[0125] Although there is no intention to limit the accelerators used in the present invention, the following suitable accelerators can be mentioned. i) Acids or compounds hydrolyzable by acids, particularly a) organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, and lactic acid; b) organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, and 4-dodecylbenzenesulfonic acid; c) sulfonic acid esters; d) inorganic acids such as phosphoric acid; e) Lewis acid compounds such as BF3 amine complexes, SbF6 sulfonium compounds, bisarene iron complexes; f) Bronsted acid compounds such as pentafluoroantimonic acid complexes; and e) mixtures of the above acids and acid esters; ii) Tertiary amines such as 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazole (including N-methylimidazole, N-vinylimidazole, and 1,2-dimethylimidazole), and salts of such tertiary amines; iii) Quaternary ammonium salts such as benzyltrimethylammonium chloride; iv) Amidines such as 1,8-diazabicyclo[5.4.0]undec-7-ene; v) Guanidines such as 1,1,3,3-tetramethylguanidine; vi) Phenols, particularly bisphenol; vii) Phenolic resins; and viii) Phosphites such as diphenyl phosphite and triphenyl phosphite.

[0126] Those skilled in the art will recognize that the selection of accelerators is not simply a matter of adding the fastest accelerators. Other critical factors in the selection of accelerators include cost; toxicity; solubility; processing effects such as working time, early gelation, thermal decomposition, expansion, and gas evolution; final properties such as glass transition temperature (Tg), modulus of elasticity, strength, elongation at break, and chemical resistance; regulatory matters; and ease of use.

[0127] In the present invention, it is preferable to employ an accelerator comprising at least one tertiary amine, at least one amidine, or a mixture thereof, or consisting of the foregoing. More specifically, the accelerator is preferably selected from the group consisting of imidazole, methylimidazole, benzyldimethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo(2,2,2)octane, and mixtures thereof.

[0128] The accelerator is typically desirably present in the composition in an amount of 0.1 to 15% by weight, based on the weight of the second component. The accelerator may preferably constitute 1 to 15% by weight, for example, 5 to 15% by weight of the second component.

[0129] When the amount of the accelerator exceeds 15%, the accelerator in the composition becomes excessive, which may adversely affect the curing process and adhesion properties. On the other hand, when the amount is mainly less than 0.1%, the physical effects may disappear. Therefore, these amounts of the accelerators are preferable.

[0130] <Additives and Auxiliary Components> The composition obtained in the present invention will typically further comprise auxiliaries and additives which can impart improved properties to these compositions. For example, the auxiliaries and additives can impart one or more of improved elastic properties; improved elastic recovery; longer effective processing time; faster curing time; and lower residual tack. Such auxiliaries and additives, which can be included in one or both components of a two-component (2K) composition, independently of each other, include: plasticizers; stabilizers including UV stabilizers; antioxidants; reinforcing agents; reactive diluents; desiccants; adhesion promoters; bactericides; flame retardants; rheology aids; colored pigments or colored pastes; and / or optionally, in small amounts, non-reactive diluents.

[0131] Such auxiliaries and additives can be used in the desired combinations and proportions, provided they do not adversely affect the nature and essential properties of the composition. Although there are exceptions in some cases, these auxiliaries and additives should not exceed 50% by weight of the total composition overall, and preferably should not account for more than 20% by weight of the composition.

[0132] To be complete, it is noted that generally, auxiliary materials and additives having reactive groups are incorporated into the appropriate component of the two-component (2K) composition to ensure their storage stability. Non-reactive materials can be incorporated into either one or both of the two components.

[0133] A "plasticizer" for the purposes of the present invention is a substance which reduces the viscosity of the composition and thus facilitates its processability. Here, the plasticizer can constitute up to 10% by weight or up to 5% by weight, based on the total weight of the composition, and preferably is diurethane; ethers of monofunctional, linear or branched C4-C16 alcohols such as Cetiol OE (Cognis Deutschland GmbH manufacture 、Duesseldor f); esters of abietic acid, butyric acid, thiobutyric acid, acetic acid, propionic acid and citric acid; esters consisting of nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of OH group-containing or epoxidized fatty acids; glycolic acid esters; benzoic acid esters; phosphate esters; sulfonic acid esters; trimellitic acid esters; polyether plasticizers such as end-capped polyethylene glycol or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. In principle, phthalic acid esters can be used as plasticizers, but it is noted that these are not preferred due to their toxicological potential.

[0134] The "stabilizer" for the purposes of the present invention is understood to be an antioxidant, a UV stabilizer, a heat stabilizer or a hydrolysis stabilizer. Here, the stabilizer can constitute up to 10% by weight or up to 5% by weight in total, based on the total weight of the composition. Standard commercially available examples of stabilizers suitable for use herein include sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; amines of the hindered amine light stabilizer (HALS) type; phosphorus; sulfur; and mixtures thereof.

[0135] Those compositions of the present invention can optionally contain reinforcing rubber in the form of core-shell particles dispersed in an epoxy resin matrix. The term "core-shell rubber" or CSR is used according to its standard meaning in the art to denote a rubber particle core formed by a polymer containing an elastomer or rubbery polymer as a main component and a shell layer formed by a polymer graft-polymerized to the core. The shell layer partially or entirely covers the surface of the rubber particle core in the graft polymerization step. By weight, the core desirably constitutes at least 50% by weight of the core-shell rubber particles.

[0136] The core polymer material desirably has a glass transition temperature (Tg) of 0 °C or lower, preferably -20 °C or lower, more preferably -40 °C or lower, and even more preferably -60 °C or lower. The shell polymer is a non-elastomer, thermoplastic or thermosetting polymer having a glass transition temperature (Tg) above room temperature, preferably above 30 °C, more preferably above 50 °C.

[0137] While not intending to limit the present invention, the core may include diene homopolymers, such as homopolymers of butadiene or isoprene; diene copolymers, such as copolymers of butadiene or isoprene with one or more ethylenically unsaturated monomers, such as vinyl aromatic monomers, (meth)acrylonitrile or (meth)acrylate; polymers based on (meth)acrylate monomers, such as polybutyl acrylate; and polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0138] Similarly, while not intending to limit the present invention, the shell may be composed of a polymer or copolymer of one or more monomers selected from (meth)acrylates, such as methyl methacrylate; vinyl aromatic monomers, such as styrene; vinyl cyanide, such as acrylonitrile; unsaturated acids and anhydrides, such as acrylic acid; and (meth)acrylamide. The polymer or copolymer used for the shell may have ionically crosslinked acid groups by forming metal carboxylates, particularly salts of divalent metal cations. Also, the shell polymer or copolymer may be covalently crosslinked by a monomer having two or more double bonds per molecule.

[0139] Some of the included core-shell rubber particles preferably have an average particle diameter (d50) of 10 nm to 300 nm, for example 50 nm to 250 nm. The particle diameter represents the diameter or maximum dimension of the particles in the particle distribution and is measured via dynamic light scattering. To be complete, this application does not exclude the presence of two or more types of core-shell rubber (CSR) particles with different particle size distributions in the composition in order to provide a balance of the main properties including the shear strength, peel strength, and resin fracture toughness of the resulting cured product.

[0140] The core-shell rubber can be selected from commercially available products, examples of which include Paraloid EXL 2650A, EXL 2655, and EXL2691 A (manufactured by Dow Chemical Company); Clearstrength® XT100 (manufactured by Arkema Inc.); Kane Ace® MX series, particularly MX 120, MX 125, MX 130, MX 136, MX 551, MX553 (manufactured by Kaneka Corporation); and METABLEN SX-006 (manufactured by Mitsubishi Rayon Co., Ltd.).

[0141] The core-shell rubber particles are desirably included in the composition in an amount of 0 to 15% by weight, for example 1 to 10% by weight, based on the total weight of the composition.

[0142] In an alternative expression of the selection that is not intended to be mutually exclusive with the above, the core-shell rubber particles desirably constitute 1 to 30% by weight, preferably 5 to 25% by weight, for example 5 to 20% by weight, of the first component of the composition.

[0143] The presence of solvents and non-reactive diluents in the composition of the present invention is not excluded either, provided that they can usefully adjust their viscosities. For example, but not by way of limitation, the composition can include one or more of the following. Xylene; 2-methoxyethanol; dimethoxyethanol; 2-ethoxyethanol; 2-propoxyethanol; 2-isopropoxyethanol; 2-butoxyethanol; 2-phenoxyethanol; 2-benzyloxyethanol; benzyl alcohol; ethylene glycol; ethylene glycol dimethyl ether; ethylene glycol diethyl ether; ethylene glycol dibutyl ether; ethylene glycol diphenyl ether; diethylene glycol; diethylene glycol monomethyl ether; diethylene glycol monoethyl ether; diethylene glycol mono-n-butyl ether; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; diethylene glycol di-n-butyryl ether; propylene glycol butyl ether; propylene glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol di-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropylnaphthalene; petroleum fractions such as Solvesso® products (manufactured by Exxon); alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecatrienylphenol; styrenated phenol; bisphenol; aromatic hydrocarbon resins, especially those containing phenolic groups such as ethoxylated phenol or propoxylated phenol; adipate; sebacate; phthalate; benzoate; organic phosphates or sulfonate esters; and sulfonamides, etc.

[0144] Separately from the above, it is preferred that the non-reactive diluent constitutes less than 10% by weight in total, particularly less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0145] <Exemplary embodiments of two-component (2K) compositions> In an exemplary embodiment of the present invention, the two-component (2K) adhesive composition Based on the weight of the first component, 20 to 45% by weight, preferably 25 to 40% by weight of an epoxy resin, the epoxy resin being selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, an alicyclic epoxy resin and mixtures thereof; 10 to 30% by weight of a (meth)acrylate monomer, the (meth)acrylate monomer being a C 1- C6 alkyl ester of (meth)acrylic acid, a C 3- C 12 cycloalkyl ester of (meth)acrylic acid, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate and mixtures thereof; 5 to 20% by weight of an electrolyte, the electrolyte being selected from 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium methylsulfate and mixtures thereof; and 1 to 15% by weight of a solubilizer, the solubilizer comprising a polyoxy(C 2- C3) alkylene glycol having a weight average molecular weight of 200 to 10000 g / mol, for example 200 to 2000 g / mol; and a filler; a first component comprising; and a curing agent comprising at least one compound having at least two epoxy-reactive groups per molecule, the curing agent comprising at least one polyamine having at least two amine hydrogens reacting with the epoxy groups, the polyamine further comprising a primary amine group and / or a secondary amine group, and the equivalent per primary amine group and / or secondary amine group being 150 g / eq or less; 5 to 15% by weight of an accelerator based on the weight of the second component, the accelerator being selected from the group consisting of tertiary amines, quaternary ammonium salts, amidines, guanidines and mixtures thereof; and Filler includes a second component.

[0146] The applicant has found that in the two-component curable composition according to the present invention, the combination of an epoxy resin and an acrylic resin brings about performance improvement and shrinkage reduction, particularly on the plastic surface. This is achieved by selecting an epoxy resin to provide good chemical resistance, a good temperature range, an ideal Tg value, good adhesion to the metal surface and low to nearly zero shrinkage, and selecting an acrylic resin to provide a high T-peel value, good adhesion to the plastic surface and fast curing.

[0147] <Method and Application> To form a defined two-component (2K) curable composition, the reactive components are brought together and mixed in a manner that induces their curing. The reactive compounds are preferably mixed under sufficient shear force to obtain a homogeneous mixture. It is believed that this can be achieved without special conditions or special equipment. However, suitable mixing devices can include static mixing devices; magnetic stir bar devices; wire whisk devices; augers; batch mixers; planetary mixers; C.W. Brabender or Banburry (registered trademark) style mixers; and high-shear mixers such as blade style blenders and rotating impellers, etc.

[0148] For small-scale applications where a volume of less than 2 liters is generally used, a preferred packaging for two-component (2K) compositions is a side-by-side double cartridge or a coaxial cartridge, in which typically two tubular chambers of equal volume are arranged side by side or one inside the other and sealed by pistons. The driving of these pistons enables the extrusion of the components from the cartridge and can advantageously be through a static, speed or dynamic mixer mounted in close proximity. For large-volume applications, the two components of the composition are preferably stored in drums or pallets. In this case, the two components are extruded by a hydraulic press, in particular a follower plate, and supplied via a pipeline to a mixing device that can ensure a fine and highly homogeneous mixing of the two components. In any case, for any package, it is important that the components are arranged in an airtight and moisture-free sealed state, whereby both components can be stored for a long time, ideally for more than 12 months.

[0149] Non-limiting examples of two-component dispensing devices and methods suitable for the present invention include those described in U.S. Patent No. 6,129,244 and U.S. Patent No. 8,313,006.

[0150] The first and second components of the composition are usually mixed in a weight ratio that achieves the desired ratio of epoxy groups to epoxy-reactive groups. By way of example, the weight ratio of the first component to the second component may be in the range of 12:1 to 2:1, preferably 10:1 to 2:1, such as 8:1 to 3:1 or 7:1 to 5:1.

[0151] Where applicable, the two-component (2K) curable composition is preferably prepared such that it exhibits an initial viscosity, measured immediately after mixing, for example within 2 minutes after mixing, of less than 200,000 mPa·s at 25°C, for example less than 100,000 mPa·s. Apart from or in addition to the viscosity characteristic, the two-component (2K) composition is preferably prepared such that it does not contain bubbles (foam) during mixing and subsequent curing.

[0152] In accordance with the broadest process aspect of the present invention, the above composition is applied to a layer of material(s) and then cured in situ. It is often desirable to pretreat the relevant surface to remove foreign matter therefrom prior to applying the composition. When applied, this step can promote the subsequent adhesion of the composition thereto. Such treatment is known in the art and can be carried out, for example, in a one-step or multi-step process consisting of one or more of the following uses. Etching treatment using an acid suitable for the substrate and optionally an oxidizing agent; ultrasonic treatment; plasma treatment, including, for example, chemical plasma treatment, corona treatment, atmospheric pressure plasma treatment and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent such as carbon tetrachloride or trichloroethylene; and rinsing with water, preferably deionized water or pure water. Of these examples, when using an aqueous alkaline degreasing bath, it is desirable to remove the degreasing agent remaining on the surface by rinsing the substrate surface with deionized water or pure water.

[0153] In some embodiments, the adhesion of the composition of the present invention to the preferably pretreated substrate can be promoted by applying a primer thereto. Indeed, a primer composition may be necessary to ensure an efficient setting time and / or curing time of the adhesive composition on an inert substrate. Those skilled in the art can select a suitable primer, and useful references for primer selection include, but are not limited to, the following. U.S. Patent No. 3,855,040; U.S. Patent No. 4,731,146; U.S. Patent No. 4,990,281; U.S. Patent No. 5,811,473; British Patent No. 2502554, and U.S. Patent No. 6,852,193.

[0154] Next, the composition is preferably applied to the pre-treated substrate by conventional coating methods as follows. Brushing; for example, roll coating using a 4-roll coater if the composition is solvent-free, or a 2-roll coater for solvent-containing compositions; doctor blade coating; printing methods; and, without limitation, spray methods such as air atomizing spray, air-assisted spray, airless spray and high volume low pressure spray.

[0155] As described above, the present invention includes a first material layer having a conductive surface; and a second material layer having a conductive surface, and a cured, peelable two-component (2K) adhesive composition as defined herein and in the appended claims is provided between the first material layer and the second material layer. To produce such a structure, the adhesive composition may be applied to at least one inner surface of the first material layer and / or the second material layer, and subsequently the two layers may be brought into contact, optionally under pressure, such that an electrically peelable hot melt adhesive composition is interposed between the two layers.

[0156] The composition is preferably applied to the surface with a wet film thickness of 10 - 500 μm. Applying a thinner layer within this range is more economical and results in a reduced likelihood of harmful thick cured regions. However, when applying a thinner coating or layer, excellent control must be exercised to avoid the formation of a discontinuous cured film.

[0157] The curing of the coating composition of the present invention typically occurs at a temperature in the range of 40°C to 200°C, preferably 50°C to 175°C, particularly 75°C to 175°C. The appropriate temperature depends on the specific compounds present and the desired curing rate and can be determined in individual cases by those skilled in the art using simple preliminary tests as necessary. Of course, curing at a lower temperature within the above range is advantageous as it eliminates the need to substantially heat or cool the mixture from the normal ambient temperature. However, where applicable, the temperature of the mixture formed from each component of a two-component (2K) composition may be raised above the mixing temperature and / or the application temperature using conventional methods including microwave induction.

[0158] The present invention will be described with reference to the following accompanying drawings.

[0159] As shown in the attached Figure 1a, a bonding structure is provided in which a layer (10) of cured adhesive is disposed between two conductive substrates (11). A layer (12) of non-conductive material may be disposed on the conductive substrate (11) to form a more complex bonding structure as depicted in Figure 1b. Each layer of the conductive substrate (11) is in electrical contact with a power source (13) which may be a battery or an AC drive source for direct current (DC). The positive and negative terminals of the power source (13) are shown in one fixed position, but those skilled in the art will of course recognize that the polarity of the system can be reversed.

[0160] The two conductive substrates (11) are shown, in particular, in the form of layers that can be constituted by a metal film; a metal sheet; a metal mesh or grid, vapor-deposited metal particles, a resin material made conductive by conductive elements disposed therein, or a conductive oxide layer. Exemplary conductive elements include silver filaments, single-walled carbon nanotubes, and multi-walled carbon nanotubes. Exemplary conductive oxides include doped indium oxides such as indium tin oxide (ITO); doped zinc oxide; antimony tin oxide; cadmium stannate, and zinc stannate. Apart from the selection of the conductive material, those skilled in the art will recognize that if the conductive substrate (11) is in the form of a grid or mesh that limits contact with the cured adhesive layer (10), the effectiveness of the peeling operation may be reduced.

[0161] When a voltage is applied between the respective conductive substrates (11), a current is supplied to the adhesive composition (10) disposed therebetween. This causes an electrochemical reaction at the interface between the substrate (11) and the adhesive composition, and 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 thought to weaken the adhesive bond between the substrates and make it possible to easily peel off the composition that can be peeled from the substrates.

[0162] As shown in FIGS. 2a and 2b, peeling occurs at the anodic interface, which is the interface between the adhesive composition (10) and the conductive surface (11) in electrical contact with the positive electrode. By reversing the direction of the current before separating the substrates, the adhesive bond can be weakened at the interface of both substrates.

[0163] However, it is noted that the composition of the adhesive layer (10) can be adjusted such that delamination occurs either from one or both of the positive or negative interfaces, or simultaneously from both. In some embodiments, when a voltage is applied across both surfaces to form an anode interface and a cathode interface, delamination occurs simultaneously at both the anode and cathode adhesive / substrate interfaces. In another embodiment, when the composition does not react to direct current at both interfaces, reverse polarity can be used to delaminate both substrate / adhesive interfaces simultaneously. The current can be applied with any suitable waveform, provided that sufficient total time at each polarity is allowed for delamination to occur. In that case, sine waves, rectangular waves, and triangular waves are suitable and can be applied from a controlled voltage source or a controlled current source.

[0164] While not intended to limit the invention, it is believed that the delamination operation can be effectively performed when at least one, preferably both, of the following conditions occur: a) an applied voltage of 0.5 to 200 V; and, b) a voltage applied for a period of 1 second to 120 minutes, for example 1 second to 60 or 30 minutes. When delamination of the conductive substrate from the cured adhesive is facilitated, for example, by the application of force via a weight or a spring, only an application of a potential on the order of a few seconds may be required.

[0165] The following examples illustrate the invention and are not intended to limit the scope of the invention in any way.

Example

[0166] In the examples, the following materials were used. · Cab-O-Sil 720: Fumed silica surface-treated with polydimethylsiloxane (PDMS) (manufactured by Cabot Corporation) · Casiflux G20: Granular wollastonite (manufactured by Sibelco) · Barbituric acid: Pyrimidine-2,4,6(1H,3H,5H)-trione (manufactured by Merck) · 1-Ethyl-3-methylimidazolium methanesulfonate: (manufactured by TCI America Inc.) · Kane Ace (Registered Trademark) MX-153: Core-shell rubber particles dispersed in bisphenol A epoxy resin, (manufactured by Kaneka Corporation) · DER 337: Intermediate epoxy equivalent semi-solid resin based on bisphenol A epoxy, (manufactured by Olin) · DER 331: Liquid epoxy resin, reaction product of epichlorohydrin and bisphenol A, (manufactured by Olin) · Erisys GE-30: Low-viscosity high-epoxy functionality resin (EEW, 135 - 150 g / eq), (manufactured by CVC Thermosets) · EOTMPTA Ac 50: Silica-containing ethoxylated trimethylolpropane triacrylate, (manufactured by Nissan Chemical Industries) · Jeffamine (Registered Trademark) D-2000: Ether group-containing aliphatic primary polyamine, (manufactured by Huntsman) · Jeffamine (Registered Trademark) EDR-176: Ether group-containing aliphatic primary polyamine, (manufactured by Huntsman) · Shieldex AC 3: Rust preventive pigment, (manufactured by Grace Davison) · PEG400: Polyethylene glycol, (manufactured by Sigma Aldrich) · Albiflex296: Bisphenol A-epoxy-silicone block copolymer resin, (manufactured by Evonik Industries) · Tris[2-(acryloyloxy)ethyl] isocyanurate: Acrylate monomer, (manufactured by Sigma Aldrich) · Tegopren5843: Polyether siloxane / 100% active silicone surfactant, (manufactured by Evonik) · 4,7,10-Trioxa-1,13-tridecanediamine: Curing agent, (manufactured by Sigma Aldrich) · Tetraethylenepentamine: Curing agent, (manufactured by Acros) · Capcure 3-800: Liquid curing agent, (manufactured by Cognis) ·N,N,N’,N’-tetramethyleneethylenediamine: curing agent, manufactured by Merck ·PEGGE (Mn = 380): solubilizer, poly(propylene glycol) diglycidyl ether having an average Mn ≒ 380, manufactured by Sigma Aldrich

[0167] Examples 1, 2, and 3 The liquid (A) of three two-component (2K) compositions was prepared according to Table 1 below.

[0168]

Table 1

[0169] The liquid (B) was identically prepared according to Table 2 below for each of the three two-component (2K) compositions.

[0170]

Table 2

[0171] In each example, the liquids (A, B) were loaded into separate compartments of a 50 g cartridge and sealed at both ends. Next, the cartridge was loaded into a cartridge gun and a mixing tip was attached to the front end. By applying a constant pressure to the trigger, the two liquids were pushed into the mixing tip to ensure sufficient mixing before applying to the described substrate. The weight ratio of liquid A to liquid B in the examples was 6.5:1 (Example 1); 7.5:1 (Example 2); and 4.5:1 (Example 3).

[0172] The substrates were aluminum (AA6016, thickness 1.25 mm) and stainless steel (1.4301, thickness 1.5 mm) each having a respective substrate thickness, and each was cut into a size of 2.5 cm × 10 cm (1 inch × 4 inches) and subjected to a tensile test.

[0173] The tensile lap shear (TLS) test was carried out according to the test method described on page 5.

[0174] The applied two-component adhesive composition was applied at a temperature of 150 °C for 30 minutes to the overlapping portion and cured. Thereafter, the sample was stored in a constant temperature chamber at 25 °C and a humidity of 20%. Further, the bonded structure was stored for a specific number of days shown in Table 3 below.

[0175] Regarding the base materials described, the tensile lap shear strength after the storage period was investigated for both the untreated adhesive base material and the adhesive base material treated by applying a constant potential of 50 V for 20 minutes to the adhesive layer. The results are shown in Table 3 below.

[0176]

Table 3

[0177] Figure 4 is a diagram showing the results of a lap shear strength test of an aluminum base material bonded with the curable adhesive of Example 1.

[0178] Examples 4, 5, 6, 7 According to Table 4 below, liquid (A) of four types of two-component (2K) compositions was prepared.

[0179]

Table 4

[0180] Liquid (B) was prepared identically for each of the four types of two-component (2K) compositions according to Table 5 below.

[0181]

Table 5

[0182] As in Examples 1 to 3 above, example compositions and samples were prepared, and the same test method was used for the test. The results are described in Table 6 below.

[0183]

Table 6

[0184] Figure 3a shows the peeling when different potentials are applied for 20 minutes, and Figure 3b shows the peeling when 75V is applied over time.

[0185] Example 8 According to Table 7 below, liquid (A) of four two-component (2K) compositions was prepared.

[0186] [Table 7]

[0187] As in Examples 1 to 3 above, example compositions and samples were prepared, and the same test method was used for the tests. The results are described in Table 8 below.

[0188] [Table 8]

[0189] Considering the foregoing description and examples, it will be apparent to those skilled in the art that equivalent changes can be made without departing from the scope of the claims. Preferred embodiments of the present specification include at least the following. [1] a) An epoxy resin; b) A (meth)acrylate monomer; c) An electrolyte; d) A solubilizer; and e) A filler; a first component containing the same, and a) A curing agent composed of at least one compound having at least two epoxide-reactive groups per molecule; b) A promoter; and c) A filler a second component containing the same A curable and peelable two-component hybrid adhesive composition containing the same. [2] The epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, alicyclic epoxy resin, and mixtures thereof. Preferably, the epoxy resin is bisphenol A type epoxy resin. The curable and peelable two-component hybrid adhesive composition according to [1]. [3] The epoxy resin is present in an amount of 15 to 60% by weight, preferably 15 to 50% by weight, more preferably 20 to 45% by weight, more preferably 25 to 40% by weight, and even more preferably 28 to 39% by weight based on the total weight of the first component. The curable and peelable two-component hybrid adhesive composition according to [1] or [2]. [4] The (meth)acrylate monomer is methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl-(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, isobornyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(meth)acryloyloxypropyltrimethoxysilane, (meth)acrylic acid-ethylene oxide adduct, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, dipentafluoroethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, 1,Selected from the group consisting of 6 - hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,2 - butylene glycol diacrylate, trimethylolpropane ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, 1,4 - butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate and mixtures thereof; preferably, the (meth)acrylate monomer is selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, isobornyl methacrylate, isobornyl acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate and mixtures thereof, a curable and peelable two - component hybrid adhesive composition according to any one of [1] to [3]., [5] The (meth)acrylate monomer is present in an amount of 5 to 50% by weight, preferably 7 to 40% by weight, more preferably 10 to 30% by weight, and even more preferably 15 to 27% by weight based on the total weight of the first component. The curable and peelable two-component hybrid adhesive composition according to any one of [1] to [4]. [6] The electrolyte is 11-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium methylsulfate, 1-hexyl-3-methylimidazolium 2-(2-fluoroanilino)-pyridinate, 1-hexyl-3-methylimidazolium imide, 1-butyl-1-methylpyrrolidinium 2-(2-fluoroanilino)-pyridinate, 1-butyl-1-methyl-pyrrolidinium imide, trihexyl(tetradecyl)phosphonium 2-(2-fluoroanilino)-pyridinate, cyclohexyltrimethylammonium bis(trifluoromethylsulfonyl)imide, di(2-hydroxyethyl)ammonium trifluoroacetate, N,N-dimethyl(2-hydroxyethyl)ammonium octanoate, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, N-ethyl-N-N-N-N-tetramethylguanidinium trifluoromethanesulfonate, guanidinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium bromide, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-hydroxymethylpyridinium ethylsulfate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-ethyl-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-propyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,A curable and peelable two-component hybrid adhesive composition according to any one of [1] to [4], selected from the group consisting of 3-dimethylimidazolium hexafluorophosphate, 1-butylimidazole, 1-methylimidazolium tetrafluoroborate, tetrabutylphosphonium tris(pentafluoroethyl) trifluorophosphate, trihexyl(tetradecyl)phosphonium tetrafluoroborate, and mixtures thereof, preferably selected from 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium methylsulfate, and mixtures thereof., [7] The electrolyte is present in a total amount of 2.5 to 25% by weight, preferably 4 to 23% by weight, and more preferably 5 to 20% by weight based on the total weight of the composition. The curable and peelable two-component hybrid adhesive composition according to any one of [1] to [6]. [8] The filler of the first component and the filler of the second component may be the same or different, and independently, are selected from the group consisting of calcium carbonate, calcium oxide, talcum, fumed silica, silica, wollastonite, barium sulfate, glass beads, and mixtures thereof, and the curable and peelable two-component hybrid adhesive composition according to any one of [1] to [7]. [9] The filler is present in the first component in an amount of 1 to 40% by weight, preferably 1 to 25% by weight, more preferably 1.5 to 18% by weight, based on the total weight of the first component, and the filler is present in the second component in an amount of 10 to 30% by weight, preferably 15 to 23% by weight, based on the total weight of the second component, and the curable and peelable two-component hybrid adhesive composition according to any one of [1] to [8].

[10] The solubilizer is selected from polyphosphazene; polymethylene sulfide; polyoxyalkylene glycol; polyethyleneimine; silicone surfactant and fluorinated silicone surfactant; copolymer of functionalized polyalkylsiloxane and epoxy resin; polyhydric alcohol; and sugar, and the curable and peelable two-component hybrid adhesive composition according to any one of [1] to [9].

[11] The solubilizer is present in an amount of 0.5 to 20% by weight, preferably 1.0 to 15% by weight, more preferably 1.3 to 13% by weight, based on the total weight of the first component, and the curable and peelable two-component hybrid adhesive composition according to any one of [1] to

[10] .

[12] The first component further contains a copolymerizable acid in an amount of preferably 1 to 10% by weight, preferably 1.5 to 8% by weight, more preferably 2 to 7% by weight, based on the total weight of the first component, and the curable and peelable two-component hybrid adhesive composition according to any one of [1] to

[11] .

[13] The first component further contains a reinforcing agent in an amount of preferably 1 to 30% by weight, preferably 5 to 25% by weight, more preferably 5 to 21% by weight, based on the total weight of the first component, and the curable and peelable two-component hybrid adhesive composition according to any one of [1] to

[12] .

[14] The curable and peelable two-component hybrid adhesive composition according to any one of [1] to

[13] , wherein the curing agent contains at least one polyamine having at least two amine hydrogens that react with an epoxy group, the polyamine further contains a primary amine group and / or a secondary amine group, and has an equivalent weight of 150 g / eq or less per primary amine group or secondary amine group.

[15] The curable and peelable two-component hybrid adhesive composition according to any one of [1] to

[14] , wherein the accelerator is selected from the group consisting of a tertiary amine, a quaternary ammonium salt, an amidine, a guanidine, and mixtures thereof, and the accelerator is preferably selected from the group consisting of imidazole, methylimidazole, benzyldimethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo(2,2,2)octane, and mixtures thereof.

[16] The curable and peelable two-component hybrid adhesive composition according to any one of [1] to

[15] , wherein the accelerator is present in an amount of 0.1 to 15% by weight, preferably 1 to 15% by weight, more preferably 5 to 15% by weight based on the total weight of the second component.

[17] ·A first material layer having a conductive surface; ·A second material layer having a conductive surface; comprising The curable and peelable two-component hybrid adhesive composition according to any one of [1] to

[16] is disposed between the first material layer and the second material layer. Adhesive structure.

[18] 1) A step of applying a voltage across both surfaces to form an anode interface and a cathode interface, and 2) A step of peeling the both surfaces comprising The voltage applied in step 1 is preferably 0.5 to 200 V, and the voltage is preferably applied for 1 second to 60 minutes.

[17] A method for peeling the adhesive structure described.

Claims

1. a) an epoxy resin; b) a (meth)acrylate monomer; c) an electrolyte; d) a solubilizer for solubilizing the electrolyte; and e) a filler; a first component comprising, and a) a curing agent comprising at least one compound having at least two epoxide-reactive groups per molecule; b) a reaction accelerator for the reaction between the epoxy group and the epoxide-reactive group; and c) a filler a second component comprising comprising, wherein the solubilizer is present in an amount of 0.5 to 20% by weight based on the total weight of the first component, a curable and peelable two-component hybrid adhesive composition.

2. The curable and peelable two-component hybrid adhesive composition according to claim 1, wherein the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, alicyclic epoxy resin, and mixtures thereof.

3. The curable and peelable two-component hybrid adhesive composition according to claim 1 or 2, wherein the epoxy resin is present in an amount of 15 to 60% by weight based on the total weight of the first component.

4. The (meth)acrylate monomer includes methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl-(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, isobornyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(meth)acryloyloxypropyltrimethoxysilane, (meth)acrylic acid-ethylene oxide adduct, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, dipentafluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,The curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 3, which is selected from the group consisting of 2-butylene glycol diacrylate, trimethylolpropane ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and mixtures thereof.,

5. The curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 4, wherein the (meth)acrylate monomer is present in an amount of 5 to 50% by weight based on the total weight of the first component.

6. The electrolyte is 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium methylsulfate, 1-hexyl-3-methylimidazolium 2-(2-fluoroanilino)-pyridinate, 1-hexyl-3-methylimidazolium imide, 1-butyl-1-methylpyrrolidinium 2-(2-fluoroanilino)-pyridinate, 1-butyl-1-methyl-pyrrolidinium imide, trihexyl(tetradecyl)phosphonium 2-(2-fluoroanilino)-pyridinate, cyclohexyltrimethylammonium bis(trifluoromethylsulfonyl)imide, di(2-hydroxyethyl)ammonium trifluoroacetate, N,N-dimethyl(2-hydroxyethyl)ammonium octanoate, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, N-ethyl-N-N-N-N-tetramethylguanidinium trifluoromethanesulfonate, guanidinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium bromide, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-hydroxymethylpyridinium ethylsulfate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-ethyl-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-propyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,The curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 4, which is selected from the group consisting of 3-dimethylimidazolium hexafluorophosphate, 1-butylimidazole, 1-methylimidazolium tetrafluoroborate, tetrabutylphosphonium tris(pentafluoroethyl) trifluorophosphate, trihexyl(tetradecyl)phosphonium tetrafluoroborate, and mixtures thereof.,

7. The curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 6, wherein the electrolyte is present in a total amount of 2.5 to 25% by weight based on the total weight of the composition.

8. The curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 7, wherein the filler in the first component and the filler in the second component may be the same or different and are independently selected from the group consisting of calcium carbonate, calcium oxide, talcum, fumed silica, silica, wollastonite, barium sulfate, glass beads, and mixtures thereof.

9. The curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 8, wherein the filler in the first component is present in an amount of 1 to 40% by weight based on the total weight of the first component, and the filler in the second component is present in an amount of 10 to 30% by weight based on the total weight of the second component.

10. The solubilizing agent is selected from polyphosphazene; polymethylene sulfide; polyoxyalkylene glycol; polyethyleneimine; silicone surfactants and fluorinated silicone surfactants; copolymers of functionalized polyalkylsiloxane and epoxy resin; polyhydric alcohols; and sugars, and is a curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 9.

11. The solubilizing agent is present in an amount of 1.0 to 15% by weight based on the total weight of the first component, and is a curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 10.

12. The first component further contains a copolymerizable acid in an amount of 1 to 10% by weight based on the total weight of the first component, and is a curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 11.

13. The first component further contains a reinforcing agent in an amount of 1 to 30% by weight based on the total weight of the first component, and is a curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 12.

14. The curing agent contains at least one polyamine having at least two amine hydrogens that react with an epoxy group, the polyamine further contains a primary amine group and / or a secondary amine group, and has an equivalent weight of 150 g / eq or less per primary amine group or secondary amine group, and is a curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 13.

15. The accelerator is selected from the group consisting of tertiary amines, quaternary ammonium salts, amidines, guanidines, and mixtures thereof, and is a curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 14.

16. The accelerator is present in an amount of 0.1 to 15% by weight based on the total weight of the second component, and is a curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 15.

17. ・A first material layer having a conductive surface; ・A second material layer having a conductive surface; comprising A curable and peelable two-component hybrid adhesive composition according to any one of claims 1 to 16 is disposed between the first material layer and the second material layer. Adhesive structure.

18. 1) A step of applying a voltage across both surfaces to form an anode interface and a cathode interface, and 2) A step of peeling the both surfaces including, the voltage applied in Step 1 is 0.5 to 200 V, and the voltage is applied for 1 second to 60 minutes, A method for peeling the adhesive structure according to claim 17.

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