Peelable, curable two-component (2K) thermally conductive adhesive composition

Abstract

The present invention relates to a peelable, curable, two-component thermal conductive adhesive composition comprising a first component comprising an epoxy resin, an electrolyte, and a thermally conductive filler, and a second component comprising a curing agent and a thermally conductive filler, wherein the composition further comprises a conductive filler. The composition according to the present invention can be used in battery modules of electric vehicles. Furthermore, the composition according to the present invention facilitates the rapid repair and reuse of battery modules of electric vehicles.

Description

[Technical Field]

[0001] The present invention relates to a peelable, curable, two-component thermally conductive adhesive composition that, after curing, integrally bonds a substrate and can support loads within the bonded composite structure, but can also be peeled from the substrate to which the composition is applied. [Background technology]

[0002] Adhesive bonding and polymer coatings are commonly used in the assembly and finishing of manufactured goods. They are used as an alternative to mechanical fasteners such as screws, bolts, and rivets, providing a bond that reduces processing costs and offers greater adaptability in the manufacturing process. Adhesive bonding evenly distributes stress, reduces the possibility of fatigue, and seals the joint from corrosive substances.

[0003] While adhesive bonding offers many advantages over mechanical fasteners, certain drawbacks must also be acknowledged. Firstly, disassembling objects bonded with adhesive tends to be difficult, which is a practical requirement. Secondly, when adhesive is cured in situ to bond two substrates together, a cross-linked chemical network is formed. After disassembling an object bonded with adhesive, this chemical network cannot be reused as an adhesive in most situations. This drawback is particularly noteworthy in resource-intensive industries where recycling, reuse, or repurposing manufactured goods for other purposes would be beneficial.

[0004] Regarding the initial drawbacks, removal of adhesives through mechanical processes such as sandblasting or wire brushing is often impossible. This is partly because the adhesive is positioned between the substrates, making it impossible or difficult to polish without damaging the substrate surface. Demolition using chemicals and / or high temperatures may be effective, but it can be time-consuming and complicated, especially if you want to preserve the substrate surface with residual adhesive. The strong chemicals and / or harsh conditions required often remove virtually all of the adhesive, potentially damaging the substrate to be separated and rendering it unsuitable for subsequent use.

[0005] State-of-the-art thermally conductive structural adhesives are not electrochemically or thermally detachable. In recent years, several electrochemically detachable adhesive compositions based on different chemical properties have been developed for various applications, including systems for electrically detaching batteries from electronic devices that have an electroadhesive layer within the bond between the battery and the electronic device. However, these developments are not useful when thermal conductivity is required.

[0006] Therefore, despite the useful development of electrochemically peelable adhesive compositions, there is still a need for curable, peelable, and thermally conductive adhesive compositions. [Overview of the project]

[0007] The present invention relates to a peelable, curable, two-component thermally conductive adhesive composition comprising a first component and a second component, wherein the first component comprises a) an epoxy resin, b) an electrolyte in an amount of 0.1 to 20% by weight based on the total weight of the first component, selected from the group consisting of 1-ethyl-3-methyl-imidazolium methyl sulfate, tributyl(ethyl)phosphonium diethyl phosphate, a mixture of choline chloride and ethylene glycol, and combinations thereof, and c) a thermally conductive filler, the second component comprises a) a curing agent, and b) a thermally conductive filler, and the composition further comprises a conductive filler, the conductive filler being i) 0.02 to 0.3% by weight based on the total weight of the composition in the form of carbon nanostructures or carbon nanotubes, or ii) 12 to 17% by weight based on the total weight of the composition in the form of spheroidal graphite, or iii) 1 to 4% by weight based on the total weight of the composition in the form of flake graphite.

[0008] The present invention also relates to the use of the peelable, curable, two-component thermally conductive adhesive composition according to the present invention in battery modules within electric vehicles, electronic devices, and electronic components (or parts).

[0009] The present invention comprises a bonding structure comprising a first material layer having a conductive surface and a second material layer having a conductive surface, wherein the peelable, curable two-component thermally conductive adhesive composition according to the present invention is disposed between the first material layer and the second material layer.

[0010] The present invention also includes a method for delaminating the bonded structure according to the present invention, the method comprising: i) applying a voltage across both surfaces to form a cathode interface and an anode interface; and ii) delaminating the surfaces. [Brief explanation of the drawing]

[0011] [Figure 1a] The bonded structure according to the present invention is shown. [Figure 1b] The bonded structure according to the present invention is shown. [Figure 2a] This shows the initial delamination of the bonded structure when an electric current is passed across the bonded structure according to the present invention. [Figure 2b] This shows the initial delamination of the bonded structure when an electric current is passed across the bonded structure according to the present invention. [Modes for carrying out the invention]

[0012] [Detailed description of the invention] The present invention will be described in more detail below. Each of the embodiments described herein may be combined with any one or more other embodiments unless otherwise explicitly stated. In particular, any feature described as preferred or advantageous may be combined with any one or more other features described as preferred or advantageous.

[0013] In the context of this disclosure, terms used shall be interpreted according to the following definitions unless otherwise specified.

[0014] As used herein, the singular forms "a," "an," and "the" include both singular and plural forms unless otherwise explicitly stated in the context.

[0015] As used herein, the terms “comprising,” “comprises,” and “comprised of” are synonymous with “including,” “includes,” or “containing,” and are comprehensive or non-exclusive, and do not exclude any additional elements, components, or steps of the method not described herein.

[0016] As used herein, the term "consisting of" excludes any unspecified components, constituent materials, elements, or steps of the method.

[0017] The terms “preferred,” “preferably,” “desirably,” and “particularly” are frequently used herein to refer to embodiments of the Disclosure that may provide a particular benefit under certain circumstances. However, the description of one or more preferred, preferred, 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 Disclosure.

[0018] The term "may" as used throughout this specification is used in a permissive sense, meaning "possible" or "possible," rather than in a compulsory sense.

[0019] As used herein, the term "epoxide" refers to a compound characterized by having at least one cyclic ether group, i.e., a compound in which an ether oxygen atom is bonded to two adjacent carbon atoms to form a ring structure. This term encompasses monoepoxide compounds, polyepoxide compounds (having two or more epoxide groups), and epoxide-terminated prepolymers. The term "monoepoxide compound" refers to an epoxide compound having one epoxy group. The term "polyepoxide" refers to an epoxide compound having at least two epoxy groups. The term "diepoxide" refers to an epoxide compound having two epoxide groups.

[0020] The epoxide may be unsubstituted or inertly substituted. Examples of inert substituents include chlorine, bromine, fluorine, and phenyl.

[0021] The notation of endpoints for numerical values ​​includes all numerical values ​​and percentages within each range, as well as the notated endpoints themselves.

[0022] All percentages, quantities, ratios (or proportions) mentioned herein are based on weight unless otherwise specified.

[0023] When expressing a quantity, concentration, or other value or parameter in the form of a range, preferred range, or preferred upper and lower limits, any range obtained by combining either upper or preferred value with either lower or preferred value should be understood to be clearly disclosed, regardless of whether the obtained range is explicitly stated in the context.

[0024] The term "electrolyte" is used herein in accordance with the standard meaning in the art to refer to a substance containing free ions that can conduct electricity through the movement of charged carrier species. This term encompasses molten electrolytes, liquid electrolytes, semi-solid electrolytes, and solid electrolytes, wherein at least one of the cationic or anionic components of the electrolyte structure is essentially mobile and therefore functions as a charged carrier.

[0025] The curable thermally conductive adhesive composition of the present invention and the cured adhesive obtained thereby have an "electrolyte function" in that the adhesive material enables the conduction of anions, cationics, or both ions. The electrolyte function is understood to derive from the ability of the composition and the cured adhesive to solvate at least one polar ion.

[0026] As used herein, room temperature is 23°C, plus or minus 2°C. As used herein, “ambient conditions” means the temperature and pressure of the environment in which the composition is placed, or the environment in which the coating layer or the substrate of the coating layer is placed.

[0027] In the context of this disclosure, a "two-component (2K) composition" is understood to be a composition in which the first component (A) and the second component (B) need to be stored in separate containers due to their (high) reactivity. The two components are mixed shortly before application and react to form bonds, usually without additional activation, thereby forming a polymer network. In this case, a higher temperature may be applied to accelerate the crosslinking reaction.

[0028] In the context of this disclosure, a "one-component (1K) composition" is understood to be a composition in which the curing resin is stored together with the curing agent (i.e., in a single component). In this case, it is required that the curing agent is inactive (not reactivated) under storage conditions.

[0029] As used herein, the term “peelable” means that after curing the adhesive, applying a potential of 10–75V for 1 second–60 minutes can reduce the adhesive strength by at least 50%. The cured adhesive is applied between the two substrates to be bonded by the adhesive, and an electric current flows through the adhesive bond line. The bond strength is measured by a tensile lap-shear (TLS) test performed at room temperature based on EN1465:2009 (German version) Based on Adhesives - Determination of tensile lap-shear strength of bonded assemblies. The bonded overlap area was 20 mm × 10 mm, and the bond thickness was approximately 1000 μm.

[0030] All references cited herein are incorporated herein in their entirety by reference.

[0031] Unless otherwise specified, all terms used in the disclosure of this invention, including technical and scientific terms, have meanings that are generally understood by those skilled in the art to which this invention pertains. For further guidance, definitions of terms are included to better understand the teachings of this invention.

[0032] The present invention relates to a peelable, curable, two-component thermally conductive adhesive composition comprising a first component and a second component, wherein the first component comprises a) an epoxy resin, b) an electrolyte in an amount of 0.1 to 20% by weight based on the total weight of the first component, selected from the group consisting of 1-ethyl-3-methyl-imidazolium methyl sulfate, tributyl(ethyl)phosphonium diethyl phosphate, a mixture of choline chloride and ethylene glycol, and combinations thereof, and c) a thermally conductive filler, the second component comprises a) a curing agent and b) a thermally conductive filler, and the composition further comprises a conductive filler, the conductive filler being i) 0.02 to 0.3% by weight based on the total weight of the composition in the form of carbon nanostructures or carbon nanotubes, or ii) 12 to 17% by weight based on the total weight of the composition in the form of spheroidal graphite, or iii) 1 to 4% by weight based on the total weight of the composition in the form of flaky graphite (graphite flakes).

[0033] The applicant has found that the peelable, curable, and thermally conductive adhesive composition according to the present invention provides high adhesive strength and high thermal conductivity, while also allowing the adhesive bond to be peeled off by the application of electrical stimulation.

[0034] The first component of the composition contains an epoxy resin.

[0035] Epoxy resins, as used herein, may include monofunctional epoxy resins, multifunctional or polyfunctional epoxy resins, and combinations thereof. Epoxy resins may be compounds, mixtures of epoxy-functional compounds, and mixtures of compounds with different numbers of epoxide groups per molecule. Epoxy resins may be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, and may be substituted. Furthermore, epoxy resins may be monomers or polymers.

[0036] Without intending to limit the present invention, exemplary monoepoxide compounds include: 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 carboxyl groups are esterified with alkanols; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxy alkyl 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.

[0037] By way of example, monoepoxide compounds particularly suitable for use herein may include the following glycidyl ethers: 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; allyl 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.

[0038] In one embodiment, the monoepoxide compound is represented by the following formula (I):

Chemical Formula

[0039] R w , R x and R y are hydrogen, and R zIt is preferably a phenyl group or a C1-C8 alkyl group, and more preferably a C1-C4 alkyl group.

[0040] In consideration of 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.

[0041] 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.

[0042] Again, without intent to limit this disclosure, suitable polyepoxide compounds may be in liquid, solid, or dissolved state in a solvent. Furthermore, such polyepoxide compounds may have an epoxide equivalent of 100–700 g / eq., for example, 120–320 g / eq. Generally, diepoxide compounds having an epoxide equivalent of less than 500 g / eq., or even less than 400 g / eq., are preferred. This is mainly from the standpoint of cost in their manufacture, as lower molecular weight epoxy resins require more limited processes for purification.

[0043] Examples of 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.

[0044] Suitable diglycidyl ether compounds can be aromatic, aliphatic, or alicyclic, and therefore can be derived from dihydric phenols and dihydric alcohols. Useful types of such diglycidyl ethers include diglycidyl ethers of aliphatic and alicyclic diols such as 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol, and cyclohexanediol; diglycidyl ethers of bisphenol A; diglycidyl ethers of bisphenol F; diglycidyl o-phthalate, diglycidyl isophthalate, and diglycidyl terephthalate; diglycidyl ethers of polyalkylene glycols, particularly polypropylene glycol diglycidyl ethers; and glycidyl ethers of polycarbonate diols. Other suitable diepoxides that can be mentioned include biunsaturated fatty acids C1-C 18 Examples include alkyl ester diepoxides, butadiene diepoxides, polybutadiene diglycidyl ethers, vinylcyclohexene diepoxides, and limonene diepoxides.

[0045] Furthermore, 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.

[0046] The epoxy resin is preferably 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, alicyclic epoxy resin, and combinations thereof, and more preferably the epoxy resin is bisphenol A epoxy resin.

[0047] Bisphenol A epoxy resin is preferred because it exhibits good storage stability characteristics.

[0048] Suitable commercially available epoxy resins for use in this invention include, but are not limited to, Kukdo YD 128 from Kukdo Chemical (Kunshan) Co. Ltd. and DER331 from Olin.

[0049] The epoxy resin may be present in an amount of 2 to 10% by weight, preferably 3 to 9% by weight, and more preferably 4 to 8% by weight, of the total weight of the first component of the composition.

[0050] If the amount of epoxy resin is greater than 10%, it may negatively affect the thermal conductivity of the adhesive. However, if the amount is small, mainly below 2%, it may lead to a decrease in initial adhesion properties, viscosity, and tackiness. Therefore, the amount of epoxy resin described above is preferable.

[0051] The first component of the composition contains an electrolyte.

[0052] In another embodiment, the second component of the composition contains an electrolyte, while the first component of the composition does not contain an electrolyte.

[0053] In another embodiment, the first and second components of the composition include an electrolyte.

[0054] The electrolyte is given by formula (I), formula (II), or formula (III): [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 is hydrogen, C1-C 18 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 24 Aralkil, C2C 20 Alkenyl, C1-C 18 Hydroxyalkyl, -C(O)R q Independently selected from -C(O)OH, -CN, or -NO2, R q It is a C1-C6 alkyl, X - [This is an anti-anion.] It contains, or consists of, at least one salt by [the specified agent].

[0055] Counter-anions (X) that can be used in electrolytes - There is no intention to specifically limit the anions. Exemplary anions may be selected from the following: • Halides; ·Formula PF6 - CF3SO3 - , (CF3SO3)2N - CF3CO2 - and CCl3CO2 - Pseudohalides and halogen-containing compounds ·CN - SCN - and OCN - ; • Fenate; ·General formula SO4 2- HSO4 - , SO3 2- HSO3 - , R a OSO3 - and R a SO3 - Sulfates, sulfites, and sulfonates of; ·General formula PO4 3- HPO4 2- H2PO4 - , R a PO4 2- , HR a PO4 - and R a R b PO4 - phosphates; ·General formula R a HPO3 - , R a R b PO2 - and R a R b PO3 - Phosphosphates and phosphinates; ·General formula PO33- , HPO3 2- , H2PO3 - , R a PO3 2- , R a HPO3 - and R a R b PO3 - phosphite; · general formula R a R b PO2 - , R a HPO2 - , R a R b PO - and R a HPO - phosphonites and phosphinites; · general formula R a COO - carboxylic acid anions; · hydroxycarboxylic acid anions and sugar acid anions; · saccharinates (salts of o-sulfimide benzoic acid); · general formula BO3 3- , HBO3 2- , H2BO3 - , R a R b BO3 - , R a HBO3 - , R a BO3 2- , B(OR a )(OR b )(OR c )(OR d ) - , B(HSO4) - and B(R a SO4) - borates · general formula R a BO2 2- and R a R b BO - boronates; · general formula HCO3 - , CO3 2- and R a CO3 -Carbonates and carbonate esters of; ·General formula SiO4 4- HSiO4 3- H2SiO4 2- H3SiO4 - , R a SiO4 3- , R a R b SiO4 2- , R a R b R c SiO4 - , HR a SiO4 2- H2R a SiO4 - and HR a R b SiO4 - Silicates and silicic acid esters of; ·General formula R a SiO3 3- , R a R b SiO2 2- , R a R b R c SiO - , R a R b R c SiO3 - , R a R b R c SiO2 - and R a R b SiO3 2- Alkyl- and arylsilanolates; • Pyridine salts and pyrimidine salts; ·General formula: [ka] Carboxylic acid imides, bis(sulfonyl)imides, and sulfonylimides; ·General formula: [ka] Methido; ·General formula R a O- Alkoxides and aryl oxides of; and ·General formula S 2- HS - [S v ] 2- [HS v ] - and [R a S] - Sulfides, hydrogen sulfides, polysulfides, polyhydrosulfides, and thiolates; [In the general formula, v is a positive integer from 2 to 10, and R a , R b , R c and R d is hydrogen, C1-C 12 Alkyl, C5-C 12 Cycloalkyl, C5-C 12 Heterocycloalkyl, C6-C 18 Aryl and C5-C 18 [Selected independently of heteroaryls].

[0056] The electrolyte is selected from the group consisting of 1-ethyl-3-methylimidazolium methyl sulfate, tributyl(ethyl)phosphonium diethyl phosphate, a mixture of choline chloride and ethylene glycol, and combinations thereof.

[0057] A preferred electrolyte provides a good peeling effect in the thermally conductive composition.

[0058] Suitable commercially available electrolytes for use in the present invention include, but are not limited to, 1-ethyl-3-methylimidazolium methyl sulfate (EMIM MS) from Basionics, ethaline from Henkel, and Cyphos IL 169 from Solvay.

[0059] The electrolyte is present in an amount of 0.1 to 20% by weight, preferably 0.5 to 18% by weight, more preferably 0.75 to 17% by weight, and even more preferably 1 to 16% by weight, of the total weight of the first component of the composition.

[0060] In other embodiments, the electrolyte is present in an amount of 0.1 to 20% by weight, preferably 0.5 to 18% by weight, more preferably 0.75 to 17% by weight, and even more preferably 1 to 16% by weight, of the total weight of the second component of the composition.

[0061] If the amount of electrolyte is greater than 20%, a good peeling effect can be obtained, but curing may be incomplete, which can negatively affect the initial adhesive properties. On the other hand, if the amount is too little, the peeling effect may be insufficient, so the above amount is preferable.

[0062] The thermally conductive filler is present in both the first and second components of the composition. The thermally conductive filler may consist of only one type of filler, or it may be a combination of two or more different types of fillers.

[0063] The thermally conductive fillers in the first and second components may be the same or different, and may be independently selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum hydroxide oxide, boron nitride, magnesia, zinc oxide, graphene, graphite, silica, fumed silica, talc, chalk, calcium carbonate, and combinations thereof. Preferably, the thermally conductive fillers are selected from aluminum hydroxide, aluminum oxide, and combinations thereof.

[0064] The above-mentioned thermally conductive filler is preferred because it provides ideal thermal conductivity relative to the filling ratio.

[0065] Appropriate thermally conductive fillers may be coated. Coating further reduces the viscosity of the composition, potentially allowing for the inclusion of more thermally conductive fillers.

[0066] The typical particle size for thermal conductive fillers used in building adhesives is 30 μm to 110 μm. For applications requiring thin films, a suitable particle size is 5 μm to 50 μm. Thermal fillers suitable for use in this invention may have a particle size of 80 μm to 100 μm, preferably 85 μm to 95 μm, and the particle size is measured by laser diffraction.

[0067] As used above, the term "particle size" in the context of thermally conductive fillers refers to the D of the cumulative volume distribution curve. 90 This refers to a value where 90% by volume of particles have a diameter smaller than that value. In this invention, the average particle size is measured by laser diffraction, preferably using a Microtrac S3000 / S3500 available from Microtrac MRB. In this technique, the size of particles in a suspension or emulsion is measured using the diffraction of a laser beam, based on the application of Mie theory. In this invention, Mie theory or a modified Mie theory for non-spherical particles is applied, and the particle size is related to diffusion measurements at an angle of 0.02 to 135 degrees with respect to the incident laser beam.

[0068] The particle size of a thermally conductive filler primarily affects viscosity; smaller particle sizes result in higher viscosity. Therefore, particle size can directly influence the maximum filler capacity and thermal conductivity.

[0069] Suitable commercially available thermally conductive fillers for use in the present invention include, but are not limited to, Martinal TM 2590 from Huber Martinswerk and SFADW-45 from CMP Advanced Materails.

[0070] The thermally conductive filler may be present in the first component of the composition in an amount of 40 to 90% by weight, preferably 42 to 87% by weight, and more preferably 45 to 83% by weight, of the total weight of the first component.

[0071] The thermally conductive filler may be present in the second component of the composition in an amount of 70-90% by weight, preferably 80-90% by weight, and more preferably 83-88% by weight, of the total weight of the second component.

[0072] In other embodiments, the thermally conductive filler may be present in the second component in an amount of 60-80% by weight, preferably 65-78% by weight, and more preferably 68-73% by weight, of the total weight of the second component.

[0073] While a thermally conductive filler amount exceeding 90% can yield good thermal conductivity, it may negatively affect initial adhesion properties. Conversely, if the amount is too low, thermal conductivity may be poor; therefore, the aforementioned amount is preferable.

[0074] The second component of the composition contains a curing agent.

[0075] The curing agent necessarily consists of at least one compound having at least two epoxide-reactive groups per molecule. The curing agent may particularly include one or more of the following: i) at least one polyamine having at least two amine hydrogens reactive to epoxide groups; ii) at least one tertiary polyamide compound having at least two amine hydrogens reactive to epoxide groups; iii) at least one polyamine compound having at least two amine hydrogens reactive to epoxide groups; iv) at least one poly(amideamine) compound having at least two amine hydrogens reactive to epoxide groups; and v) at least one polyetheramine compound having at least two amine hydrogens reactive to epoxide groups.

[0076] Examples of curing agents suitable for use in the present invention include polymers of 9,12-octadecadienoic acid (9Z,12Z)-dimer, 3,3-oxybis(2,1-ethanediyloxy)bis-1-propanamine, condensation products of dimer acid and diethylene glycol diaminopropyl ether, 2,4,6-tris-(dimethylaminomethyl)phenol, and combinations thereof.

[0077] Suitable commercially available curing agents for use in the present invention include, but are not limited to, Ancamide 910 and Ancamide K54 from Evonik.

[0078] The curing agent may be present in an amount of 10 to 20% by weight, preferably 11 to 18% by weight, and more preferably 12 to 16% by weight, of the total weight of the second component of the composition.

[0079] The above-mentioned range of amounts is based on the amount of epoxy resin in the first component of the composition and is preferred because it allows for a complete reaction without leaving any unreacted epoxy resin in the composition.

[0080] The first and / or second component of the composition comprises a conductive filler. The conductive filler is selected from i) carbon nanostructures or carbon nanotubes, ii) spheroidal graphite, and iii) flake graphite.

[0081] Carbon nanostructures and carbon nanotubes suitable for use in the present invention may have a tube diameter of preferably 1 nm to 25 nm, preferably 2 nm to 20 nm, and more preferably 3 nm to 15 nm, and the particle size is measured by laser diffraction.

[0082] Spheroidal graphite suitable for use in the present invention may have a particle size of preferably 10 μm to 30 μm, preferably 12 to 29 μm, and more preferably 15 μm to 28 μm, and the particle size is measured by laser diffraction.

[0083] The flake graphite suitable for use in the present invention may have a particle size of preferably 40 μm to 120 μm, preferably 60 to 100 μm, and more preferably 70 μm to 90 μm, and the particle size is measured by laser diffraction.

[0084] The particle size of conductive fillers primarily affects viscosity; the smaller the particle size, the higher the viscosity. Therefore, particle size can directly influence the maximum filler capacity and conductivity.

[0085] As used above, the term "particle size" in the context of conductive fillers refers to the D of the cumulative volume distribution curve. 50 This value indicates that 50% of the particles by volume have a particle size less than that value. In this invention, the average particle size is measured by laser diffraction, preferably using a Microtrac S3000 / S3500 available from Microtrac MRB. In this technique, the size of particles in a suspension or emulsion is measured using the diffraction of a laser beam, based on the application of Mie theory. In this invention, Mie theory or Mie theory modified for non-spherical particles is applied, and the particle size is related to scattering measurements at angles of 0.02 to 135 degrees with respect to the incident laser beam.

[0086] Suitable commercially available conductive fillers for use in the present invention include, but are not limited to, GPX801 from Cabot, SG 22 from Unimate, and Timrex C-Therm 011 from Imerys.

[0087] If present, carbon nanostructures or carbon nanotubes are included in an amount of 0.02 to 0.3% by weight, preferably 0.03 to 0.2% by weight, based on the total weight of the composition.

[0088] If present, spheroidal graphite is included in an amount of 12-17% by weight, preferably 13-16% by weight, based on the total weight of the composition.

[0089] If present, flake graphite is included in an amount of 1 to 4% by weight, preferably 1.5 to 3.5% by weight, based on the total weight of the composition.

[0090] Too much conductive particles can adversely affect the rheology of the composition, while too little can reduce the peeling effect; therefore, these amounts are preferable.

[0091] The composition according to the present invention may further contain core-shell rubber particles. The core-shell rubber particles may be dispersed in a resin matrix. The core-shell rubber particles may be present in the first and / or second component of the composition, and may be the same or different in the first and second components of the composition.

[0092] The terms “core-shell rubber” or “CSR” are used herein in accordance with the standard meaning in the art, referring to a rubber particle core formed of a polymer mainly comprising an elastomer or rubbery polymer, and a shell layer formed of a polymer graft-polymerized onto the core. In the graft polymerization process, the shell layer partially or entirely covers the surface of the rubber particle core. The core should constitute at least 50% by weight of the core-shell rubber particles.

[0093] The core polymer material 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, non-thermoplastic or non-thermosetting polymer having a glass transition temperature (Tg) higher than room temperature, preferably higher than 30°C, and more preferably higher than 50°C.

[0094] Without intending to limit the present invention, the core may consist of a diene homopolymer, such as a homopolymer of butadiene or isoprene; a diene copolymer, such as a copolymer of butadiene or isoprene with one or more ethylenically unsaturated monomers, such as a vinyl aromatic monomer, (meth)acrylonitrile or (meth)acrylate; a polymer based on (meth)acrylic acid ester monomers, such as polybutyl acrylate; and a polysiloxane elastomer, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0095] Similarly, without intent to limit the present invention, the shell may consist of a polymer or copolymer of one or more monomers selected from (meth)acrylates such as methyl methacrylate, vinyl aromatic monomers such as styrene, vinyl cyanides such as acrylonitrile, unsaturated acids and acid anhydrides such as acrylic acid, and (meth)acrylamide. The polymer or copolymer used for the shell may have acid groups that are crosslinked by ions through the formation of metal carboxylates, particularly salts of divalent metal cations. The shell polymer or copolymer may be covalently crosslinked by monomers having two or more double bonds per molecule.

[0096] The included core-shell rubber particles preferably have an average particle size (d50) of 10 nm to 300 nm, for example, 50 nm to 250 nm. The particle size refers to the diameter or maximum dimension of the particles in the particle size distribution and is measured by dynamic light scattering. For completeness, this application does not preclude the blending of two or more types of core-shell rubber (CSR) particles having different particle size distributions in the composition to balance important properties of the resulting cured product, including shear strength, peel strength, and resin fracture toughness.

[0097] Examples of commercially available core-shell rubber particles suitable for use in the present invention include, but are not limited to, Kane Ace MX-154 from Kaneka, Paraloid EXL 2650A, EXL 2655 and EXL2691A available from The Dow Chemical Company, Clearstrength® XT100 available from Arkema Inc., and the Kane Ace® MX series available from Kaneka Corporation, particularly MX 120, MX 125, MX 130, MX 136, MX 154, MX 551 and MX553.

[0098] Core-shell rubber particles may be present in an amount of 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1 to 7% by weight, of the total weight of the first or second component of the composition.

[0099] The core-shell rubber particle content is preferable because if it is less than 0.1%, none of the technical advantages may be obtained, while if it is more than 10%, the viscosity of the composition may become too high.

[0100] The composition according to the present invention may further contain a reactive diluent. The reactive diluent may be present in the first and / or second component of the composition, and may be the same or different in the first and second components of the composition.

[0101] Suitable reactive diluents for use in the present invention include, for example, methyl ethyl ketone (MEK), dimethylformamide (DMF), ethyl alcohol, propylene glycol methyl ether, propylene glycol methyl ether acetate, dibutyl phthalate, dioctyl phthalate, styrene, low molecular weight polystyrene, styrene oxide, allyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, vinylcyclohexene oxide, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether poly(propylene glycol) diglycidyl ether, thiodiglycol diglycidyl ether, cardanol glycidyl ether, epsilon caprolactam, butyrolactone, acrylonitrile, and combinations thereof.

[0102] Examples of commercially available reactive diluents include, but are not limited to, DER 732 and DER 736 from Palmer Holland, Cardolite NC 513 from Cardura, E10P from Exion, and Efka 5381 from BASF.

[0103] The reactive diluent may be present in an amount of 1 to 15% by weight, preferably 2 to 12% by weight, and more preferably 3 to 12% by weight, of the total weight of the first or second component of the composition.

[0104] This amount is preferable because too little can lead to cohesive failure and reduced adhesive strength, while too much can cause curing to be too fast, negatively impacting the open time.

[0105] The composition according to the present invention may further contain a silane coupling agent. The silane coupling agent may be present in the first and / or second component of the composition, and may be the same or different in the first and second components of the composition.

[0106] Suitable silane coupling agents for use in the present invention include, but are not limited to, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacrylateoxypropyltrimethoxysilane, γ-glycidoxypropyl-trimethoxysilane, and phenyltrimethoxysilane.

[0107] Examples of commercially available silane coupling agents include, but are not limited to, Silkquest A-186, Silkquest A-187, Silkquest A-1110, Silkquest A-1120, Silkquest A-1170, and Silkquest A-2120 from Momentive.

[0108] The silane coupling agent may be present in an amount of 0.01 to 3% by weight, preferably 0.05 to 2% by weight, and more preferably 0.1 to 1% by weight, of the total weight of the first or second component of the composition.

[0109] The above amounts are preferable because they improve the adhesive properties of the composition.

[0110] To form a predetermined peelable two-component thermally conductive curable composition, the reactive components are mixed in a manner that brings them together and induces their curing. The reactive compounds must be mixed under sufficient shear force to obtain a homogeneous mixture. This is considered achievable without the use of special conditions or equipment. Nevertheless, suitable mixing devices include static mixers, magnetic stirrers, wire whisks, augers, speed mixers, batch mixers, planetary mixers, CWBrabender or Banburry® type mixers, and high-shear mixers such as blade blenders and rotary impellers.

[0111] The first and second components of the composition are typically mixed by weight to achieve a desired ratio of epoxide groups to epoxide-reactive groups. Preferably, the first and second components are mixed in a ratio of 1.1:1 to 1:1.1, preferably 1.05:1 to 1:1.05, and more preferably 1:1, where this ratio is a stoichiometric ratio.

[0112] The composition according to the present invention preferably has a thermal conductivity higher than 1.20 W / mK. Thermal conductivity is measured according to C177.

[0113] The composition according to the present invention is preferably 1.0 × 10 6 ~1.0×10 4 It has a volume resistivity, which is measured according to the test method described in the examples.

[0114] The present invention encompasses the use of the peelable, curable, two-component thermally conductive adhesive composition according to the present invention in battery modules of electric vehicles, electronic devices, and electronic elements (or components).

[0115] The composition according to the present invention facilitates the rapid repair and reuse of battery modules in electric vehicles.

[0116] The composition according to the present invention is applied (or coated) onto a material layer and subsequently cured in situ. Before applying the composition, it is often recommended to perform a pretreatment to remove foreign matter from the relevant surfaces. This step can promote the subsequent adhesion of the composition to them, where applicable. Such treatments are known in the art and may be carried out in one-step or multi-step methods consisting of, for example, one or more of the following: etching the substrate with a suitable acid and optionally an oxidizing agent; ultrasonic treatment; plasma treatment including chemical plasma treatment, corona treatment, atmospheric plasma treatment and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent such as carbon tetrachloride or trichloroethylene; and preferably rinsing with deionized or desalineated water. In these examples, when using an aqueous alkaline degreasing bath, it is desirable to remove any remaining grease on the surface by rinsing the substrate surface with deionized or desalineated water.

[0117] Next, the composition is applied to a preferably pre-treated substrate surface by, for example, one of the following conventional application methods: brush application; roll coating (e.g., using a four-roll coating device for solvent-free compositions or a two-roll coating device for solvent-containing compositions); doctor blade coating; printing method; spraying method, including but not limited to air atomizing spray, air-assisted spray, airless spray and high-volume low-pressure spray.

[0118] The present invention relates to a bonded structure having a first material layer having a conductive surface and a second material layer having a conductive surface, wherein the peelable, curable two-component thermally conductive adhesive composition according to the present invention is placed between the first and second material layers. To create such a structure, the adhesive composition may be applied to at least one inner surface of the first and / or second material layers, and then the two material layers are brought into contact so that the peelable, curable adhesive composition according to the present invention is placed between the two layers.

[0119] The composition is recommended to be applied to the surface in a wet film state with a thickness of 10 to 1000 μm. Applying thinner layers within this range is more economical and reduces the possibility of thick cured areas that could have an impact. However, good control is required when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0120] The curing of the applied composition according to the present invention is typically carried out at temperatures in the range of 35°C to 120°C, preferably 40°C to 100°C, and particularly 45°C to 75°C. Appropriate temperatures, depending on the specific compounds present and the desired curing rate, can be determined by those skilled in the art on a case-by-case basis, with simple preliminary testing if necessary. Of course, curing at lower temperatures within the aforementioned range is advantageous because it eliminates the need to substantially heat or cool the mixture from normal ambient temperature. However, where applicable, the temperature of the mixture formed from the relevant components of a two-component composition can be raised above the mixing temperature and / or application temperature using conventional means, including microwave induction.

[0121] As shown in the attached Figure 1a, a bonded structure is provided in which a curing adhesive layer (10) is placed between two conductive substrates (11). A non-conductive material layer (12) may be placed on top of the conductive substrates (11) to form a more complex bonded structure as shown in Figure 1b. Each layer of the conductive substrates (11) is electrically connected to a power source (13), which may be a battery or an AC power source for direct current (DC). The positive and negative terminals of the power source (13) are shown in a fixed state, but those skilled in the art will recognize that the polarity of the system can be reversed.

[0122] The two conductive substrates (11) may be represented in the form of a layer, which may consist of, among other things, a metal film; a metal sheet; a metal mesh or grid; attached (or deposited) metal particles; a resin material made conductive by conductive elements placed therein; or a conductive oxide layer. Exemplary conductive elements may include silver filaments, single-walled carbon nanotubes, and multi-walled carbon nanotubes. Exemplary conductive oxides may include doped indium oxide, such as indium tin oxide (ITO); doped zinc oxide; antimony tin oxide; cadmium stanate; and zinc stanate. Apart from the choice of conductive material, those skilled in the art will recognize that the effectiveness of the peeling operation is reduced if the conductive substrate (11) is in the form of a grid or mesh with limited contact with the cured adhesive layer (10).

[0123] The present invention also relates to a method for peeling off the bonded structure according to the present invention, the method comprising the steps of i) applying a voltage across both surfaces to form a cathode interface and an anode interface, and ii) peeling off the surfaces.

[0124] When a voltage is applied between each conductive substrate (11), an electric current is supplied to the adhesive composition (10) placed between them. This induces an electrochemical reaction at the interface between the substrate (11) and the adhesive composition, which is understood as an oxidation reaction at the positively charged, or anode, interface and a reduction reaction at the negatively charged, or cathode interface. This reaction is thought to weaken the adhesive bond between the substrates, allowing the peelable composition to be easily removed from the substrates.

[0125] As shown in Figures 2a and 2b, delamination occurs at the positive electrode interface, i.e., between the adhesive composition (10) and the conductive surface (11) that is electrically in contact with the positive electrode. By reversing the current before separating the substrate, the adhesive bond at both adhesive interfaces can be weakened.

[0126] Furthermore, the composition of the adhesive layer (10) can be adjusted, resulting in delamination occurring simultaneously from either the positive or negative interface, or both. In some embodiments, a voltage is applied across both surfaces to form an anode interface and a cathode interface, causing simultaneous delamination at both the anode and cathode adhesive / substrate interfaces. In another embodiment, if the composition does not react to DC at both interfaces, the opposite polarity can be used to simultaneously delaminate at both adherend / adhesive interfaces. The current may be applied in any suitable waveform, as long as the total duration is sufficient to cause delamination at each polarity. In this regard, sine waves, square waves, and triangular waves may be suitable and can be applied from controlled voltage and controlled current sources.

[0127] Without intending to limit the present invention, the peeling operation is considered to be effectively carried out when at least one, preferably both, of the following conditions are met: a) an applied voltage of 0.5 to 100 V; and b) a voltage applied for 1 second to 60 minutes. If the peeling of the conductive substrate from the cured adhesive is facilitated by applying a force, for example, by a weight or spring, then an application of potential on the order of seconds may be necessary. In some embodiments, a potential of 5 V for 10 minutes is sufficient to obtain the peeling effect, while in some embodiments, a potential of 3.5 V for 30 minutes is sufficient.

[0128] After peeling, it is desirable that the adhesive composition be present only in the first or second substrate, meaning that one of the substrates is substantially free of adhesive.

[0129] The composition according to the present invention can be used in all applications requiring thermal management and comprising two conductive substrates. In electric vehicles, it can be used between a cooling plate and a cell, or between a cooling plate and a module, or between a battery case and a cover (or lid). In electronic elements such as ADAS sensors, it can be used in, for example, cameras, lidar, radar, or power converters, or in handheld devices, mobile phones, tablets, etc.

[0130] The following examples are illustrative of the present invention and are not intended to limit the scope of the invention in any way.

[0131] [Examples] The compositions were prepared according to Table 1. The compositions of Examples 1-9 and Comparative Example 1 were prepared by mixing the components together and then mixing the first and second components together shortly before use.

[0132] The substrate to which all formulations were applied was aluminum (AA3003). The aluminum was cut into pieces measuring 2.5 cm × 10 cm and 2.0 mm thick. SBR tape was used as a spacer to control the thickness of the coating composition applied between the two substrates. The tensile lap-shear (TLS) of the bonded assemblies was measured at room temperature according to EN1465:2009 (German version) Based on Adhesives - Determination of tensile lap-shear strength of bonded assemblies.

[0133] The adhesive overlap area of ​​each specified substrate was 2.5 cm × 2.0 cm, the adhesive thickness was 1 mm (40 mil), and the adhesive line width was 1.0 cm. The applied adhesive composition was cured in the overlap area by applying a temperature of 60°C for 48 hours. Subsequently, the bonded structure was stored at room temperature for 24 hours, after which the first tensile test was performed. The tensile lap shear strength was measured both before and after applying a constant potential of 30 V across the adhesive layer for 20 minutes, and after 24 hours of storage.

[0134] The lap shear test [MPa] was measured according to ISO 4587-03.

[0135] The thermal conductivity [W / mK] was measured according to ASTM C177.

[0136] Volume resistivity (VR) was measured according to the following test method: A sample of the composition was prepared according to the above example and placed on a glass plate (by the drawdown method, with material strips approximately 5 cm long, 5 mm wide, and 50 μm thick on the surface of the glass slide), and cured and dried (150°C for 15 minutes in a box oven). The glass plate was cooled to room temperature before measurement.

[0137] The volume resistivity (VR) was calculated using the formula VR = (Sample width (cm) × Sample thickness (cm) × Resistance (ohms)) / Sample length (cm). The resistance (ohms) in the formula was measured using a Keithley 2010 multimeter and a two-point resistance probe. The unit of volume resistivity is Ohm / cm.

[0138] [Table 1] [Table 2]

[0139] [Table 3]

[0140] [Table 4]

[0141] [Table 5]

[0142] The composition according to the present invention exhibited good thermal conductivity and resistance. Furthermore, the composition showed good initial adhesive strength and peeled off once a voltage was applied. In fact, the adhesive according to the present invention was able to exhibit good thermal conductivity while simultaneously reducing the lap shear strength of the adhesive by more than 50% of the initial adhesive strength.

Claims

1. A peelable, curable, two-component thermally conductive adhesive composition comprising a first component and a second component, The first component is, a) Epoxy resin, b) An electrolyte comprising 0.1 to 20% by weight on a total weight basis of the first component, selected from the group consisting of 1-ethyl-3-methyl-imidazolium methyl sulfate, tributyl(ethyl)phosphonium diethyl phosphate, a mixture of choline chloride and ethylene glycol, and combinations thereof, and c) Thermally conductive filler Includes, The second component is, a) Hardener, b) Thermally conductive filler Includes, The composition further comprises a conductive filler, the conductive filler is i) 0.02 to 0.3% by weight of the composition of carbon nanostructures or carbon nanotubes, ii) 12 to 17% by weight of spheroidal graphite, or iii) 1 to 4% by weight of the composition in flake graphite One of them is an adhesive composition.

2. The peelable, curable, two-component thermal conductive adhesive composition according to claim 1, wherein the second component comprises 0.1 to 20% by weight of an electrolyte based on the total weight of the second component, where the electrolyte is selected from the group consisting of 1-ethyl-3-methyl-imidazolium methyl sulfate, tributyl(ethyl)phosphonium diethyl phosphate, a mixture of choline chloride and ethylene glycol, and combinations thereof, and the first component does not contain an electrolyte.

3. The epoxy resin is 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 combinations thereof, and preferably the epoxy resin is bisphenol A epoxy resin, the peelable curable two-component thermal conductive adhesive composition according to claim 1 or 2.

4. The peelable, curable, two-component thermally conductive adhesive composition according to any one of claims 1 to 3, wherein the epoxy resin is present in an amount of 2 to 10% by weight, preferably 3 to 9% by weight, and more preferably 4 to 8% by weight, of the total weight of the first component.

5. The peelable, curable, two-component thermally conductive adhesive composition according to any one of claims 1 to 4, wherein the electrolyte is present in an amount of 0.5 to 18% by weight, preferably 0.75 to 17% by weight, and more preferably 1 to 16% by weight, of the total weight of the first component.

6. The thermally conductive filler in the first component and the thermally conductive filler in the second component may be the same or different, and may be independently selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum hydroxide oxide, boron nitride, magnesia, zinc oxide, graphene, graphite, silica, fumed silica, talc, chalk, calcium carbonate, and combinations thereof, and preferably the thermally conductive filler may be selected from aluminum hydroxide, aluminum oxide, and combinations thereof, as described in any one of claims 1 to 5.

7. The peelable curable two-component thermal conductive adhesive composition according to any one of claims 1 to 6, wherein the filler is present in the first component in an amount of 40 to 90% by weight, preferably 42 to 87% by weight, more preferably 45 to 83% by weight of the total weight of the first component; or the filler is present in the second component in an amount of 70 to 90% by weight, preferably 80 to 90% by weight, more preferably 83 to 88% by weight of the total weight of the second component; or the filler is present in the second component in an amount of 60 to 80% by weight, preferably 65 to 78% by weight, more preferably 68 to 73% by weight of the total weight of the second component.

8. The peelable, curable, two-component thermally conductive adhesive composition according to any one of claims 1 to 7, wherein the curing agent is selected from the group consisting of polyamides, tertiary polyamides, polyamines, poly(amideamines), polyetheramines, and combinations thereof.

9. The peelable, curable, two-component thermal conductive adhesive composition according to any one of claims 1 to 8, wherein the curing agent is present in an amount of 10 to 20% by weight, preferably 11 to 18% by weight, and more preferably 12 to 16% by weight, of the total weight of the second component.

10. The peelable, curable, two-component thermal conductive adhesive composition according to any one of claims 1 to 9, wherein the composition further comprises core-shell rubber particles, wherein the core-shell rubber particles are preferably present in an amount of 0.1 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1 to 7% by weight, of the total weight of the first or second component of the composition.

11. The peelable, curable, two-component thermally conductive adhesive composition according to any one of claims 1 to 10, wherein the composition further comprises a reactive diluent, wherein the reactive diluent is preferably present in an amount of 1 to 15% by weight, preferably 2 to 12% by weight, and more preferably 3 to 12% by weight, of the total weight of the first or second component.

12. The peelable, curable, two-component thermal conductive adhesive composition according to any one of claims 1 to 11, further comprising a silane coupling agent, wherein the silane coupling agent is preferably present in an amount of 0.01 to 3% by weight, preferably 0.05 to 2% by weight, and more preferably 0.1 to 1% by weight, of the total weight of the first or second component.

13. The conductive filler is, i) 0.03 to 0.2% by weight of the total weight of the composition, or ii) 13 to 16% by weight of spheroidal graphite, or iii) 1.5 to 3.5% by weight of the composition in flake graphite One of the present inventions is the peelable, curable, two-component thermally conductive adhesive composition according to any one of claims 1 to 12.

14. The peelable, curable, two-component thermally conductive adhesive composition according to any one of claims 1 to 13, wherein the first component and the second component are mixed in a ratio of 1.1:1 to 1:1.1, preferably 1.05:1 to 1:1.05, and more preferably 1:1, and the ratio is a stoichiometric ratio.

15. Use of the peelable, curable, two-component thermally conductive adhesive composition according to any one of claims 1 to 14 in battery modules for electric vehicles, electronic devices, and electronic elements.

16. A first material layer having a conductive surface, and Second material layer having a conductive surface A binding structure having, A bonding structure in which a peelable, curable two-component thermally conductive adhesive composition according to any one of claims 1 to 14 is disposed between a first material layer and a second material layer.

17. A method for peeling off the bonded structure according to claim 16, i) A step of applying a voltage across both surfaces to form a cathode interface and an anode interface; and ii) The process of peeling off that surface A peeling method including

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