Adhesive composition

Abstract

The present specification provides a two-component thermally conductive acrylic epoxy adhesive composition.

Description

Technical Field

[0001] The present invention relates to the field of epoxy - acrylic adhesive compositions.

Background Art

[0002] When assembling an electric vehicle battery pack, there are many different design philosophies. However, currently, most are assembled in a modular fashion where multiple pack sub - assemblies or modules are constructed and placed in the pack. Each module contains an array of battery cells, which are thermally connected via a thermal interface material (TIM) to some form of cooling unit having active liquid cooling (cooling channels, cold plates, etc.). The thermal connection between the cells and the cooling unit is important for managing the heat generated during charging and discharging of the cells, thereby enabling the cells to have higher performance efficiency and longer life.

[0003] Currently, three different cell types are commonly used: prismatic cells, pouch cells, and cylindrical cells. Prismatic cells and pouch cells often have a polymer coating on the outside of the cell, which can facilitate the bonding of the cell to a thermally conductive adhesive. Such coatings allow the use of a wide range of chemicals in bonding applications. However, cylindrical cells often have a can (outer wall) constructed using nickel-plated steel. Nickel is well-known for being difficult to bond for the following reasons: (1) Nickel is an inherently inert material, which means it has a low surface energy compared to other metals, (2) the nickel-plated surface has a low surface roughness, and (3) the nickel plating process is known to provide surfaces with various characteristics. Additionally, cylindrical cell designs may require adhesives with a rapid curing rate to shorten cycle times. In the design where an array of cells is bonded to both the top and bottom of a single cold plate, cycle time is particularly important because the adhesive needs to reach handling strength before the cold plate is flipped over in the process.

[0004] Finally, cylindrical cells are most commonly used because in the future, their manufacturing processes may be more rationalized and potentially cost-reduced. They are also often used in designs where engineers want to use the mechanical rigidity of the cells to impart rigidity to the vehicle structure. In this type of design, high-strength / high-modulus adhesives are ideal to help transfer the rigidity of the cells to the vehicle structure.

[0005] When combined with a thermally conductive filler package, polyurethanes, silicones, and epoxies can have several individual advantages in the assembly of cylindrical cell-based designs. However, such adhesives often cure slowly and / or have insufficient adhesion to nickel-plated steel, especially when they contain the high filler loadings required to make them thermally conductive. SUMMARY OF THE INVENTION

Means for Solving the Problem

[0006] In a first aspect, the present invention is a two-component thermally conductive epoxy-acrylic hybrid adhesive, comprising: Part A ai) at least one methacrylate monomer; aii) at least one elastomer reinforcing agent; aiii) a phosphorus-containing compound having a monoester of phosphonic acid, phosphonic acid, and mono- and diesters of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) a tertiary amine radical initiator; av) 0.0025 to 0.065% by weight of diethylhydroxylamine; Part B bi) at least one epoxy resin; bii) an oxidizing agent; wherein Part A and / or Part B contains a thermally conductive filler, and as a result, when Part A and Part B are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 90% by weight of a thermally conductive filler, an adhesive is provided.

[0007] In a second aspect, the present invention is a method for bonding two or more substrates, comprising: (1) Part A ai) at least one methacrylate monomer; aii) at least one elastomer reinforcing agent; aiii) a phosphorus-containing compound having a monoester of phosphonic acid, phosphonic acid, and mono- and diesters of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) a tertiary amine radical initiator; av) 0.0025 to 0.065% by weight of diethylhydroxylamine; Part B bi) at least one epoxy resin; bii) an oxidizing agent; including, wherein the A part and / or the B part contains a heat conductive filler, and as a result, when the A part and the B part are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 90% by weight of the heat conductive filler, providing a two-component heat conductive epoxy-acrylic hybrid adhesive; (2) mixing the A part and the B part to obtain an adhesive mixture; (3) applying the adhesive mixture to the first substrate, the second substrate, or both; (4) adhesively contacting the first substrate and the second substrate; and (5) curing the adhesive mixture, a method is provided.

Embodiments for Carrying Out the Invention

[0008] The inventors have found that it is possible to obtain an epoxy-acrylic adhesive having good adhesion to nickel-plated steel, an open time exceeding 16 minutes, and storage stability.

[0009] Definitions and Abbreviations THFMA Tetrahydrofurfuryl methacrylate CHMA Cyclohexyl methacrylate ATH Aluminum trihydroxide MAA Methacrylic acid HEMA Hydroxyethyl methacrylate phosphate SEC Size exclusion chromatography RH Relative humidity CF Cohesive failure AF Adhesive failure

[0010] Equivalents and molecular weights are measured by gel permeation chromatography (GPC) using the methods and apparatus listed in the items of the examples.

[0011] at least one methacrylate monomer (ai) The A part of the adhesive contains at least one methacrylate monomer. The methacrylate monomer is not particularly limited. Examples include the general structure of formula I:

[0012] [Chemical]

[0013] Examples of the monomer having (wherein R is an organic group) include.

[0014] In a preferred embodiment, R is H, a C1-C which may contain one or more heteroatoms 18 A substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group, and a C4-C which may contain one or more heteroatoms 18 Selected from aromatic hydrocarbon groups.

[0015] More preferably, R is selected from a C1-C substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group which may contain one or more heteroatoms, and in particular, R is cyclohexyl or CH2-THF (wherein THF is a 2- or 3-tetrahydrofurfuryl group). 18

[0016] Other examples of methacrylate monomers include isobornyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, and mixtures thereof.

[0017] In some embodiments, part A comprises two or more methacrylate monomers.

[0018] In a preferred embodiment, part A comprises tetrahydrofurfuryl methacrylate (CAS [2455-24-5]).

[0019] In another preferred embodiment, part A comprises cyclohexyl methacrylate (CAS [101-43-9]).

[0020] In another preferred embodiment, part A comprises methacrylic acid.

[0021] ​In a particularly preferred embodiment, part A comprises tetrahydrofurfuryl methacrylate and cyclohexyl methacrylate.

[0022] In another particularly preferred embodiment, part A comprises tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate and methacrylic acid.

[0023] In another preferred embodiment, part A comprises an adhesion promoter in the form of a divalent metal salt of methacrylic acid, particularly zinc dimethacrylate.

[0024] In another preferred embodiment, part A comprises a crosslinking agent. The crosslinking agent is a molecule having a molecular weight of 1,000 Da or less and two or more methacrylate groups. In a preferred embodiment, the crosslinking agent has a molecular weight of 900 Da or less.

[0025] In another preferred embodiment, the crosslinking agent has two methacrylate groups.

[0026] In another preferred embodiment, the crosslinking agent has a molecular weight of 900 Da or less and two methacrylate groups.

[0027] Examples of suitable crosslinking agents are the following general formula II:

[0028]

Chemical formula

[0029] (wherein x and y are independently selected from 2 to 10). In a preferred embodiment, both x and y are 5.

[0030] When used, the crosslinking agent is preferably present in an amount of 0.5 to 2.5% by weight, more preferably 0.6 to 1.25% by weight, particularly preferably 0.6 to 0.8% by weight, based on the total weight of part A.

[0031] In a preferred embodiment, the crosslinking agent has the general formula II and is present in an amount of 0.5 to 2.5% by weight, more preferably 0.6 to 1.25% by weight, and particularly preferably 0.6 to 0.8% by weight, based on the total weight of part A.

[0032] In another particularly preferred embodiment, part A contains tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, and a divalent metal salt of methacrylic acid, particularly zinc dimethacrylate.

[0033] Methacrylate monomers other than the adhesion promoter and the crosslinking agent preferably represent 10 to 30% by weight, more preferably 12 to 25% by weight, and particularly preferably 14 to 20% by weight of part A, based on the total weight of part A.

[0034] In a preferred embodiment, part A contains 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, based on the total weight of part A.

[0035] In a preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, and even more preferably 10 to 13% by weight of cyclohexyl methacrylate, based on the total weight of part A.

[0036] In a preferred embodiment, part A contains 1 to 6% by weight, more preferably 2 to 4% by weight of methacrylic acid, based on the total weight of part A.

[0037] In another preferred embodiment, part A contains 0.25 to 4% by weight, more preferably 0.5 to 1.5% by weight of a divalent metal salt of methacrylic acid, based on the total weight of part A.

[0038] In another preferred embodiment, part A contains 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight of zinc dimethacrylate, based on the total weight of part A.

[0039] In another preferred embodiment, part A contains 0.3 to 8% by weight, more preferably 0.5 to 5% by weight, of tetrahydrofurfuryl methacrylate based on the total weight of part A, and 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight, of cyclohexyl methacrylate based on the total weight of part A.

[0040] In another preferred embodiment, part A contains 0.3 to 8% by weight, more preferably 0.5 to 5% by weight, of tetrahydrofurfuryl methacrylate based on the total weight of part A, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight, of cyclohexyl methacrylate based on the total weight of part A, and 1 to 6% by weight, more preferably 2 to 4% by weight, of methacrylic acid based on the total weight of part A.

[0041] In another preferred embodiment, part A contains 0.3 to 8% by weight, more preferably 0.5 to 5% by weight, of tetrahydrofurfuryl methacrylate based on the total weight of part A, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight, of cyclohexyl methacrylate based on the total weight of part A, 1 to 6% by weight, more preferably 2 to 4% by weight, of methacrylic acid based on the total weight of part A, and 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight, of zinc dimethacrylate based on the total weight of part A.

[0042] At least one reinforcing agent (aii) Part A contains at least one elastomeric reinforcing agent.

[0043] The reinforcing agent may be any elastomer that is compatible with the adhesive matrix. Such reinforcing agents are preferably selected from chlorinated or chlorosulfonated polyethylene, block copolymers of styrene and conjugated diene (SBS, SIS), ethylene acrylic elastomers, core-shell graft copolymers, polyurethane-based reinforcing agents, polybutadiene, and butadiene-acrylonitrile-based reinforcing agents.

[0044] In a preferred embodiment, at least one reinforcing agent is selected from acrylate or methacrylate functional polyurethanes, vinyl-terminated polybutadiene, and vinyl-terminated butadiene-acrylonitrile.

[0045] Polyurethane-based reinforcing agent The polyurethane-based reinforcing agent is prepared by reacting a polyether polyol with a polyisocyanate in a ratio such that the resulting polymer is an NCO-capped polymer, followed by end-capping with a hydroxyalkyl ester of methacrylic acid or acrylic acid.

[0046] The polyether polyol is not particularly limited. It can be a diol or a triol, with a diol being preferred.

[0047] In a preferred embodiment, the polyol is a poly(C2-C6-alkylene oxide) diol, with C2, C3, and C4 being preferred, and C4 being particularly preferred [i.e., poly(tetramethylene oxide) glycol or PTMEG].

[0048] In another preferred embodiment, the polyether polyol is selected from PTMEG having a molecular weight of 1,000 - 3,000 Da, more preferably 2,000 Da.

[0049] The reinforcing agent may also include a low molecular weight (less than 250 Da) polyol having a functionality of 3 or 4, such as trimethylolpropane. When present, the low molecular weight polyol is preferably used at 0.1 - 3 wt%, more preferably 0.25 - 1 wt%, and particularly preferably 0.5 wt% based on the total weight of the reinforcing agent. In a preferred embodiment, the reinforcing agent contains 0.1 - 3 wt%, more preferably 0.25 - 1 wt%, and particularly preferably 0.5 wt% of trimethylolpropane based on the total weight of the reinforcing agent.

[0050] The polyisocyanate is not particularly restricted. It can be aliphatic or aromatic, with aliphatic being preferred.

[0051] The polyisocyanate is preferably a diisocyanate.

[0052] In a preferred embodiment, the polyisocyanate is an aliphatic diisocyanate. Examples include hexamethylene diisocyanate (HDI), isophorone diisocyanate, and methylene dicyclohexyl diisocyanate.

[0053] In a preferred embodiment, the polyether polyol is a diol and the polyisocyanate is a diisocyanate.

[0054] In another preferred embodiment, the polyether polyol is an aliphatic diol and the polyisocyanate is an aliphatic diisocyanate.

[0055] In another preferred embodiment, the polyether polyol is PTMEG and the polyisocyanate is HDI.

[0056] The hydroxyalkyl ester of methacrylic acid is preferably a C2-C6-hydroxyalkyl ester, more preferably a C2-C4-hydroxyalkyl, even more preferably a C2-C3-hydroxyalkyl, with C2-hydroxyalkyl being most preferred, especially hydroxyethyl methacrylate (HEMA):

[0057]

Chemical formula

[0058] is.

[0059] The reinforcing agent is preferably produced by reacting a polyether polyol with a polyisocyanate in the presence of a polyurethane catalyst to produce an NCO-terminated prepolymer. The prepolymer is then reacted with a hydroxyalkyl ester of methacrylic acid to produce an end cap.

[0060] In a preferred embodiment, the reinforcing agent is produced by reacting PTMEG with HDI in the presence of a polyurethane catalyst to produce an NCO-terminated prepolymer. The prepolymer is then reacted with HEMA to produce an end cap. The resulting reinforcing agent has the general formula III:

[0061]

Chemical formula

[0062] (wherein x has a value of 13 to 42, more preferably 27.8 (which corresponds to PTMEG having a molecular weight of 1,000 to 3,000 Da, more preferably 2,000 Da), and y has a value of 1.5 to 5 or 1.8 to 4.9, more preferably 2.6).

[0063] In a preferred embodiment, the reinforcing agent is of general formula III having a number average molecular weight (M n ) of 6,119 Da as determined by gel permeation chromatography (GPC) according to the method listed in the examples section.

[0064] In a preferred embodiment, the reinforcing agent is of general formula III, PTMEG has a molecular weight of 2,000 Da, and the reinforcing agent has a number average molecular weight (M n ) of 6,119 Da as determined by gel permeation chromatography (GPC) according to the method listed in the examples section.

[0065] In a preferred embodiment, the reinforcing agent is of general formula III having a weight average molecular weight (M w ) of 15,084 Da as determined by gel permeation chromatography (GPC) according to the method listed in the examples section.

[0066] In a preferred embodiment, the reinforcing agent is of the general formula III, the PTMEG has a molecular weight of 2,000 Da, and the reinforcing agent has a weight average molecular weight (M w ) of 15,084 Da as determined by gel permeation chromatography (GPC) according to the method listed in the items of the examples.

[0067] Rubber-based reinforcing agent A suitable rubber-based reinforcing agent is one having a rubber core terminated with a methacrylate or acrylate group.

[0068] The rubber is selected from, for example, silicone, polybutadiene, acrylonitrile-butadiene, polyacrylate or polymethacrylate, and mixtures thereof.

[0069] Content of elastomeric reinforcing agent In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of part A.

[0070] In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of part A, and the reinforcing agent is a rubber-based reinforcing agent terminated with a methacrylate group.

[0071] In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of part A, the reinforcing agent is a rubber-based reinforcing agent terminated with a methacrylate group, and the rubber is selected from polyurethane, silicone, polybutadiene, acrylonitrile-butadiene, polyacrylate or polymethacrylate and mixtures thereof.

[0072] In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of a reinforcing agent (aii) based on the total weight of part A, and the reinforcing agent is produced by reacting an aliphatic polyether diol with an aliphatic diisocyanate.

[0073] In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of a reinforcing agent (aii) based on the total weight of part A, and the reinforcing agent is produced by reacting an aliphatic polyether diol with an aliphatic diisocyanate and then end-capping with a C2-C6-hydroxyalkyl ester of methacrylic acid, more preferably a C2-C4-hydroxyalkyl, even more preferably a C2-C3-hydroxyalkyl ester, and most preferably a C2-hydroxyalkyl (2-hydroxyethyl methacrylate, HEMA).

[0074] In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of a reinforcing agent (aii) based on the total weight of part A, and the reinforcing agent is produced by reacting PTMEG and then end-capping with a C2-C6-hydroxyalkyl ester of methacrylic acid, more preferably a C2-C4-hydroxyalkyl, even more preferably a C2-C3-hydroxyalkyl ester, and most preferably a C2-hydroxyalkyl (2-hydroxyethyl methacrylate, HEMA).

[0075] In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of a reinforcing agent (aii) based on the total weight of part A, and the reinforcing agent is produced by reacting PTMEG with HDI and then end-capping with HEMA.

[0076] In another preferred embodiment, part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of a reinforcing agent (aii) based on the total weight of part A, and the reinforcing agent has the formula III:

[0077] [Chemical formula]

[0078] (wherein x has a value of 13 to 42, more preferably 27.73 (which corresponds to PTMEG having a molecular weight of 1,000 to 3,000 Da, more preferably 2,000 Da), and y has a value of 1.5 to 5 or 1.8 to 4.9, more preferably 2.6).

[0079] Phosphorus-containing compound (aiii) Part A contains a phosphorus-containing compound selected from monoesters of phosphonic acids, monoesters and diesters of phosphonic acids, and monoesters, diesters and triesters of phosphoric acids, in which one unit of vinyl or allyl unsaturation is present.

[0080] Preferably, the phosphorus-containing compound (aiii) has the formulas IV, V and VI:

[0081] [Chemical formula]

[0082] (wherein Ws are the same or different, each W is independently selected from H and a divalent organic group, at least one W is a divalent organic group, and at least one X is a vinyl group, and the others are either vinyl groups or absent (when W is H) or H).

[0083] In another preferred embodiment, the phosphorus-containing compound (aiii) has the formula VI.

[0084] In another preferred embodiment, the phosphorus-containing compound (aiii) is of formula VI, and one, two or three X groups are vinyl. Preferably, one X group is vinyl.

[0085] In another preferred embodiment, the phosphorus-containing compound (aiii) is of formula VI, and one, two, or three WX groups are of formula VII:

[0086]

Chemical formula

[0087] (wherein the dot represents the radical bonding point). When one or two WX groups are of formula VII, the remaining WX groups are preferably H. In a particularly preferred embodiment, one WX group is of formula VI, the remaining WX groups are H, and formula VIII is obtained.

[0088]

Chemical formula

[0089] In another particularly preferred embodiment, two WX groups are of formula VII, the remaining WX groups are H, and it is of formula IX.

[0090]

Chemical formula

[0091] In another preferred embodiment, the phosphorus-containing compound (aiii) is an approximately 2:1 mixture of formula VIII and formula IX.

[0092] Other examples of phosphorus-containing compounds include, but are not limited to, phosphoric acid; 2-methacryloyloxyethyl phosphate; bis-(2-methacryloyloxyxyethyl) phosphate; 2-acryloyloxyethyl phosphate; bis-(2-acryloyloxyethyl) phosphate; methyl-(2-methacryloyloxyethyl) phosphate; ethyl methacryloyloxyethyl phosphate; methyl acryloyloxyethyl phosphate; ethyl acryloyloxyethyl phosphate; propyl acryloyloxyethyl phosphate, isobutyl acryloyloxyethyl phosphate, ethylhexyl acryloyloxyethyl phosphate, halopropyl acryloyloxyethyl phosphate, haloisobutyl acryloyloxyethyl phosphate or haloethylhexyl acryloyloxyethyl phosphate; vinylphosphonic acid; cyclohexene-3-phosphonic acid; (α-hydroxybutene-2-phosphonic acid; 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid; 1-hydroxy-1-methyl-1-diphosphonic acid: 1-amino-1-phenyl-1,1-diphosphonic acid; 3-amino-3-hydroxypropane-1,1-diphosphonic acid; amino-tris(methylenephosphonic acid); gamma-amino-propylphosphonic acid; gamma-glycidoxypropylphosphonic acid; phosphoric acid-mono-2-aminoethyl ester; allylphosphonic acid; allylphosphinic acid; β-methacryloyloxyethylphosphinic acid; diallylphosphinic acid; β-methacryloyloxyethyl) phosphinic acid and allyl methacryloyloxyethyl phosphinic acid. Preferred phosphorus compounds are 2-hydroxyethyl methacrylate phosphate and phosphorylated (meth)acrylic monomers.

[0093] Tertiary amine radical initiator (aiv) Part A contains a tertiary amine radical initiator. The tertiary amine radical initiator is not particularly limited.

[0094] Preferred tertiary amine radical initiators are of the general formula X:

[0095] [Chemical formula]

[0096] (wherein, W is selected from the group consisting of hydrogen, hydroxy, amino, halogen, alkyl having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and alkoxy having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; R 1 and R 2 are independently selected from branched or straight-chain C1-4-alkyl; and b is 1 or 2).

[0097] Examples include N,N-dimethylaniline, N,N-dimethylaminomethylphenol, and N,N-dimethyl-p-toluidine.

[0098] In a particularly preferred embodiment, the tertiary amine radical initiator is N,N-dimethyl-p-toluidine.

[0099] The tertiary amine radical initiator is preferably used in an amount of 0.1 to 0.6% by weight, more preferably 0.2 to 0.4% by weight, based on the total weight of part A.

[0100] In a preferred embodiment, the tertiary amine radical initiator is used in an amount of 0.1 to 0.6% by weight, more preferably 0.2 to 0.4% by weight, based on the total weight of part A.

[0101] Diethylhydroxylamine (av) Part A contains 0.0025 to 0.065% by weight of diethylhydroxylamine.

[0102] In a preferred embodiment, diethylhydroxylamine is present in part A in an amount of 0.015 to 0.06% by weight, more preferably 0.2 to 0.055% by weight, based on the total weight of part A.

[0103] At least one epoxy resin (bi) Part B contains at least one epoxy resin.

[0104] Suitable epoxy resins include polyhydric phenol compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, diglycidyl ethers of tetramethyl bisphenol, diglycidyl ethers of aliphatic glycols and polyether glycols, e.g., C 2~24 alkyleneglycol and poly(ethylene oxide) or poly(propylene oxide) glycol diglycidyl ethers; polyglycidyl ethers of phenol-formaldehyde novolak resins, alkyl-substituted phenol formaldehyde resins (epoxy novolak resins), phenol hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and dicyclopentadiene-substituted phenol resins, and any combination thereof. Suitable diglycidyl ethers include diglycidyl ethers of bisphenol A resins, e.g., those sold under the names D.E.R.® 330, D.E.R.® 331, D.E.R.® 332, D.E.R.® 383, D.E.R.® 661 and D.E.R.® 662 resins by Olin Corporation.

[0105] In a preferred embodiment, at least one epoxy resin comprises the reaction product of epichlorohydrin and bisphenol A.

[0106] In another preferred embodiment, at least one epoxy resin comprises the liquid reaction product of epichlorohydrin and bisphenol A.

[0107] In a preferred embodiment, at least one epoxy resin comprises an epoxy resin which is a liquid reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent of 182 to 192 g / eq (measured in accordance with ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured in accordance with ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured in accordance with ASTM D-1652), and a viscosity at 25 °C of 11,000 to 14,000 mPas (measured in accordance with ASTM D-445).

[0108] In another preferred embodiment, at least one epoxy resin comprises a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq.

[0109] In a particularly preferred embodiment, at least one epoxy resin comprises a mixture of a liquid reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent of 182 to 192 g / eq (measured in accordance with ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured in accordance with ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured in accordance with ASTM D-1652), and a viscosity at 25 °C of 11,000 to 14,000 mPas (measured in accordance with ASTM D-445), and a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq.

[0110] In a preferred embodiment, at least one epoxy resin comprises a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPas (measured according to ASTM D-445), in an amount of 50 to 95% by weight, more preferably 60 to 80% by weight, based on the total weight of the epoxy resin in part B.

[0111] In another preferred embodiment, at least one epoxy resin comprises a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq in an amount of 5 to 50% by weight, more preferably 20 to 40% by weight, based on the total weight of the epoxy resin in part B.

[0112] In another preferred embodiment, at least one epoxy resin comprises a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPas (measured according to ASTM D-445), in an amount of 50 to 95% by weight, more preferably 60 to 80% by weight, based on the total weight of the epoxy resin in part B, and a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq in an amount of 5 to 50% by weight, more preferably 20 to 40% by weight.

[0113] Part B preferably comprises at least one epoxy resin in an amount of 10 to 30% by weight, more preferably 12 to 20% by weight, particularly preferably 14 to 16% by weight, based on the total weight of part B.

[0114] Oxidizing agent (bii) Part B contains an oxidizing agent. The oxidizing agent is not particularly limited.

[0115] Representative oxidizing agents include, but are not limited to, organic peroxides such as benzoyl peroxide and other diacyl peroxides, hydroperoxides such as cumene hydroperoxide, peresters such as β - butyl peroxybenzoate; ketone hydroperoxides such as methyl ethyl ketone hydroperoxide, organic salts of transition metals such as cobalt naphthenate, and compounds containing unstable chlorine such as sulfonyl chloride. The most preferred oxidizing agent is benzoyl peroxide.

[0116] The oxidizing agent, preferably an organic peroxide, is preferably present in Part B at 1.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total weight of Part B.

[0117] In a preferred embodiment, Part B contains benzoyl peroxide at 1.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total weight of Part B.

[0118] Thermally conductive filler The adhesive of the present invention contains a thermally conductive filler such that when Part A and Part B are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 90% by weight of the thermally conductive filler.

[0119] In a preferred embodiment, the adhesive of the present invention contains a thermally conductive filler such that when Part A and Part B are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 70% by weight of the thermally conductive filler.

[0120] The thermally conductive filler preferably comprises, consists essentially of, or consists entirely of one or more thermally conductive fillers having a thermal conductivity of about 3 W / mK to about 80 W / mK.

[0121] Examples of suitable thermal conductive fillers include aluminum hydroxide, aluminum oxide, aluminum powder, zinc oxide, boron nitride, and mixtures thereof. Particularly preferred fillers are selected from aluminum hydroxide, aluminum oxide, and mixtures thereof. Most particularly preferred is aluminum hydroxide.

[0122] The thermal conductive filler preferably has a Mohs hardness low enough so that the thermal conductive filler is generally non-abrasive. Preferably, the conductive filler has a Mohs hardness of about 7.0 or less, preferably about 5.0 or less, and most preferably about 4.0 or less. The conductive filler can have a Mohs hardness of about 0.5 or more, about 1.5 or more, or about 2.0 or more. An example of a non-abrasive conductive filler is typically aluminum hydroxide (i.e., ATH) powder having a Mohs hardness of 2.5 - 3. Aluminum hydroxide powder has a thermal conductivity of 3 - 80 W / mK, typically about 10 W / mK.

[0123] The adhesive mixture formed by mixing part A and part B contains a sufficient amount of thermal conductive filler such that the thermal conductivity of the adhesive mixture is at least about 0.9 W / mK or more, preferably about 1.0 W / mK or more after curing.

[0124] The thermal conductivity is measured on a thermal interface material tester made by ZFW Stuttgart according to ASTM5470 - 12. The test is carried out in the Spaltplus mode with a thickness of 1.8 - 1.2 mm. The described thermal interface material is considered to be type I (viscous liquid) as described in ASTM5470 - 12. The upper contact part is heated to about 40 °C, and the lower contact part is heated to about 10 °C, resulting in a sample temperature of about 25 °C.

[0125] In a preferred embodiment, the thermal conductive filler is ATH.

[0126] Particularly preferably, the thermally conductive filler is ATH having a multimodal particle size distribution. The expression multimodal particle size distribution means that when the particle size is plotted on the x-axis and the volume % on the y-axis, at least two main peaks are observed. When substantially only two main peaks are observed, the expression bimodal is used.

[0127] Particularly preferably, the thermally conductive filler is ATH having a bimodal particle size distribution.

[0128] The particle size distribution of aluminum trihydroxide is typically measured using laser diffraction, using water containing sodium pyrophosphate as a suspending agent.

[0129] In a preferred embodiment, the aluminum trihydroxide has the following particle size distribution: D 10 = 0.5 μm D 50 = 8 μm D 90 = 80 μm.

[0130] The thermally conductive filler is present in the adhesive mixture such that when two components are mixed (preferably in a volume ratio of 2:1 to 10:1, more preferably 4:1) in part A and / or part B to form the adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is at least 40% by weight based on the total weight of the adhesive mixture. In a preferred embodiment, the concentration of the thermally conductive filler in the adhesive mixture is 55 - 65% by weight based on the total weight of the adhesive mixture.

[0131] The thermally conductive filler may be present in part A, part B, or both. Preferably, both part A and part B contain the thermally conductive filler.

[0132] In a preferred embodiment, the concentration of the thermally conductive filler in part A is 40 - 90% by weight, more preferably 55 - 62% by weight, particularly preferably 44 - 57% by weight based on the total weight of part A.

[0133] In a preferred embodiment, the concentration of the heat-conductive filler in part B is 55 to 90% by weight, more preferably 60 to 70% by weight, and particularly preferably 44 to 57% by weight based on the total weight of part B.

[0134] In a preferred embodiment, the concentration of the heat-conductive filler in part A is 40 to 65% by weight, more preferably 55 to 62% by weight, and particularly preferably 44 to 57% by weight based on the total weight of part A, and the concentration of the heat-conductive filler in part B is 55 to 90% by weight, more preferably 60 to 70% by weight, and particularly preferably 44 to 57% by weight based on the total weight of part B.

[0135] Optional components The adhesive of the present invention may contain, for example, the following additional optional components.

[0136] To extend the shelf life of the unmixed portions, a stabilizer / free radical scavenger may be added to both part A and part B. Examples of stabilizers / free radical scavengers include 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, butylated hydroxytoluene (BHT), methyl ether of hydroquinone, hydroquinone, benzoquinone, naphthoquinone, and nitrile oxide.

[0137] Fillers such as wollastonite, talc, fumed silica, calcium carbonate, and glass.

[0138] Examples of additional optional components may include, for example, adhesion promoters, pigments, thixotropic agents, wetting agents, reactive diluents, antioxidants, inhibitors, and stabilizers.

[0139] Suitable adhesion promoters include mono- and polysiloxanes functionalized with functional groups capable of reacting with epoxy or methacrylate components, and trialkoxysilanes having epoxy, amine, or mercapto functional groups.

[0140] Manufacturing method The liquid components of Part A are typically mixed until homogeneous under vacuum or an inert atmosphere. Then, the solid components are added and the mixture is mixed until homogeneous. Next, a tertiary amine radical initiator is added. Part A can be stored under vacuum or an inert atmosphere until use.

[0141] Part B is typically manufactured by mixing the liquid components (excluding the oxidizing agent) until homogeneous under vacuum or an inert atmosphere. Then, the solid components are mixed and the oxidizing agent is added once the mixture has become homogeneous. Part B can be stored under vacuum or an inert atmosphere until use.

[0142] Method of Use During use, the adhesive Parts A and B are mixed until homogeneous and immediately applied to the substrate. The typical mixing ratio of A:B is 2:1 to 10:1, with 4:1 being particularly preferred.

[0143] Suitable substrates include, for example, electro-galvanized steel, hot-dip galvanized steel, cold-rolled steel, aluminum, nickel-plated steel, polymers, and polymer composites.

[0144] Advantages of the Invention The adhesive of the present invention preferably exhibits a lap shear strength of 10 MPa or more on cold-rolled steel using the following test method: Test specimens are prepared and tested in accordance with SAE J1523 [2012 02 01]. Test specimens measuring 25.4 mm × 101.6 mm are mated with a 12.7 mm overlap and a bond line thickness of 0.10 mm, and then cured at room temperature. The test specimens are tested at a rate of 12.7 mm / min.

[0145] The adhesive of the present invention preferably exhibits a lap shear strength of 10 MPa or more on nickel-plated steel using the following test method: Test specimens are prepared and tested in accordance with SAE J1523 [2012 02 01]. Test specimens measuring 25.4 mm × 101.6 mm are mated with a 12.7 mm overlap and a bond line thickness of 0.10 mm, and then cured at room temperature. The test specimens are tested at a rate of 12.7 mm / min.

[0146] When the adhesive of the present invention is tested as described above for lap shear strength, it preferably exhibits a cohesive failure mode of at least 90%, more preferably at least 95% on cold rolled steel.

[0147] When the adhesive of the present invention is tested as described above for lap shear strength, it preferably exhibits a cohesive failure mode of at least 50%, more preferably at least 80% on nickel-plated steel.

[0148] The adhesive of the present invention exhibits good storage stability as evidenced by no gelation of part A after heat aging at 54 °C for 2 weeks.

[0149] Particularly preferred embodiments The following are particularly preferred embodiments of the present invention.

[0150] 1. A two-component thermally conductive epoxy-acrylic hybrid adhesive, Part A ai) At least one methacrylate monomer; aii) At least one elastomer reinforcing agent; aiii) A phosphorus-containing compound having a monoester of phosphonic acid, a monoester and a diester of phosphonic acid and phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) A tertiary amine radical initiator; av) 0.0025 to 0.065% by weight of diethylhydroxylamine; Part B bi) At least one epoxy resin; bii) An oxidizing agent; comprising, wherein part A and / or part B contains a thermally conductive filler, and as a result, when part A and part B are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 90% by weight of a thermally conductive filler.

[0151] 2. A method of bonding two or more substrates, (1) Part A ai) At least one methacrylate monomer; aii) At least one elastomer reinforcing agent; aiii) A phosphorus-containing compound having a monoester of phosphonic acid, a phosphonic acid and a monoester and diester of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) A tertiary amine radical initiator; av) 0.0025 to 0.065% by weight of diethylhydroxylamine; Part B bi) At least one epoxy resin; bii) An oxidizing agent; comprising, wherein Part A and / or Part B contains a thermally conductive filler, such that when Part A and Part B are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 90% by weight of a thermally conductive filler, providing a two-component thermally conductive epoxy-acrylic hybrid adhesive; (2) Mixing Part A and Part B to obtain an adhesive mixture; (3) Applying the adhesive mixture to the first substrate, the second substrate, or both; (4) Adhesively contacting the first substrate and the second substrate; and (5) Curing the adhesive mixture, a method.

[0152] 3. At least one methacrylate monomer is of general formula I:

[0153] [Chemical formula]

[0154] (wherein R is an organic group), Embodiment 1 or 2.

[0155] 4. R is H, a C1-C which may contain one or more heteroatoms 18 substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group, and a C4-C which may contain one or more heteroatoms18 Embodiment 3, selected from aromatic hydrocarbon groups.

[0156] 5. R is selected from C1-C which may contain one or more heteroatoms 18 Selected from substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon groups, in particular R is cyclohexyl or CH2-THF (where THF is a 2- or 3-tetrahydrofurfuryl group), Embodiment 3.

[0157] 6. At least one methacrylate monomer is selected from isobornyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, and mixtures thereof, any one of the preceding embodiments.

[0158] 7. Part A contains two or more methacrylate monomers, any one of the preceding embodiments.

[0159] 8. Part A contains tetrahydrofurfuryl methacrylate (CAS [2455-24-5]), any one of the preceding embodiments.

[0160] 9. Part A contains cyclohexyl methacrylate (CAS [101-43-9]), any one of the preceding embodiments.

[0161] 10. Part A contains methacrylic acid, any one of the preceding embodiments.

[0162] 11. Part A contains tetrahydrofurfuryl methacrylate and cyclohexyl methacrylate, any one of the preceding embodiments.

[0163] 12. Part A contains tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate and methacrylic acid, any one of the preceding embodiments.

[0164] 13. Part A contains an adhesion promoter in the form of a divalent metal salt of methacrylic acid, in particular zinc dimethacrylate, any one of the preceding embodiments.

[0165] 14. Part A is any one of the preceding embodiments, including a crosslinking agent.

[0166] 15. In embodiment 14, the crosslinking agent is a molecule having a molecular weight of 1,000 Da or less and two or more methacrylate groups.

[0167] 16. In embodiment 14 or 15, the crosslinking agent has a molecular weight of 900 Da or less.

[0168] 17. In embodiment 14, 15 or 16, the crosslinking agent has two methacrylate groups.

[0169] 18. In embodiment 14, the crosslinking agent has a molecular weight of 900 Da or less and two methacrylate groups.

[0170] 19. Part A is any one of the preceding embodiments, including a crosslinking agent having the following general formula II:

[0171]

Chemical formula

[0172] (wherein x and y are independently selected from 2 to 10, and preferably, both x and y are 10).

[0173] 20. In any one of the preceding embodiments, based on the total weight of Part A, Part A contains 0.5 to 2.5 wt%, more preferably 0.6 to 1.25 wt%, and particularly preferably 0.6 to 0.8 wt% of the crosslinking agent.

[0174] 21. In any one of the preceding embodiments, Part A contains the crosslinking agent of general formula II and is present in an amount of 0.5 to 2.5 wt%, more preferably 0.6 to 1.25 wt%, and particularly preferably 0.6 to 0.8 wt% based on the total weight of Part A.

[0175] 22. Embodiment of any one of the preceding embodiments, wherein part A contains tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, and a divalent metal salt of methacrylic acid, particularly zinc dimethacrylate.

[0176] 23. Methacrylate monomers other than the adhesion promoter and the crosslinking agent represent 10 to 30% by weight, more preferably 12 to 25% by weight, particularly preferably 14 to 20% by weight of part A, based on the total weight of part A, according to any one of the preceding embodiments.

[0177] 24. Embodiment of any one of the preceding embodiments, wherein part A contains 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, based on the total weight of part A.

[0178] 25. Embodiment of any one of the preceding embodiments, wherein part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight of cyclohexyl methacrylate, based on the total weight of part A.

[0179] 26. Embodiment of any one of the preceding embodiments, wherein part A contains 1 to 6% by weight, more preferably 2 to 4% by weight of methacrylic acid, based on the total weight of part A.

[0180] 27. Embodiment of any one of the preceding embodiments, wherein part A contains 0.25 to 4% by weight, more preferably 0.5 to 1.5% by weight of a divalent metal salt of methacrylic acid, based on the total weight of part A.

[0181] 28. Embodiment of any one of the preceding embodiments, wherein part A contains 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight of zinc dimethacrylate, based on the total weight of part A.

[0182] The A part contains, based on the total weight of the A part, 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, and, based on the total weight of the A part, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight of cyclohexyl methacrylate, according to any one of the preceding embodiments.

[0183] The A part contains, based on the total weight of the A part, 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, and, based on the total weight of the A part, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight of cyclohexyl methacrylate, and, based on the total weight of the A part, 1 to 6% by weight, more preferably 2 to 4% by weight of methacrylic acid, according to any one of the preceding embodiments.

[0184] The A part contains, based on the total weight of the A part, 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, and, based on the total weight of the A part, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight of cyclohexyl methacrylate, and, based on the total weight of the A part, 1 to 6% by weight, more preferably 2 to 4% by weight of zinc methacrylate, and, based on the total weight of the A part, 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight of zinc dimethacrylate, according to any one of the preceding embodiments.

[0185] The reinforcing agent is selected from chlorinated or chlorosulfonated polyethylene, block copolymers of styrene and conjugated diene (SBS, SIS), ethylene acrylic elastomer, core-shell graft copolymer, polyurethane-based reinforcing agent, polybutadiene, and butadiene-acrylonitrile-based reinforcing agent, according to any one of the preceding embodiments.

[0186] The reinforcing agent is selected from acrylate or methacrylate functional polyurethane, vinyl-terminated polybutadiene, and vinyl-terminated butadiene-acrylonitrile, according to any one of the preceding embodiments.

[0187] 34. The reinforcing agent is selected from a polyurethane-based reinforcing agent and a rubber-based reinforcing agent, any one of the preceding embodiments.

[0188] 35. The reinforcing agent is a polyurethane-based reinforcing agent prepared by reacting a polyether polyol with a polyisocyanate in a ratio such that the resulting polymer is an NCO-capped polymer, followed by end-capping with a hydroxyalkyl ester of methacrylic acid or acrylic acid, any one of the preceding embodiments.

[0189] 36. The reinforcing agent is a rubber-based reinforcing agent, and the rubber is selected from silicone, polybutadiene, acrylonitrile butadiene, polyacrylate or polymethacrylate terminated with a vinyl, methacrylate or acrylate group, and mixtures thereof, any one of the preceding embodiments.

[0190] 37. Part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of Part A, any one of the preceding embodiments.

[0191] 38. Part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of Part A, and the reinforcing agent is a rubber-based reinforcing agent terminated with a methacrylate group, any one of the preceding embodiments.

[0192] 39. Part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of Part A, and the reinforcing agent is a rubber-based reinforcing agent terminated with a methacrylate group, and the rubber is selected from polyurethane, silicone, polybutadiene, acrylonitrile butadiene, polyacrylate or polymethacrylate, and mixtures thereof, any one of the preceding embodiments.

[0193] Part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, and particularly preferably 8 to 12% by weight of a reinforcing agent (aii) based on the total weight of Part A. The reinforcing agent is produced by reacting an aliphatic polyether diol with an aliphatic diisocyanate, followed by end-capping with a C2-C6-hydroxyalkyl ester of methacrylic acid, more preferably a C2-C4-hydroxyalkyl, even more preferably a C2-C3-hydroxyalkyl ester, and most preferably a C2-hydroxyalkyl (hydroxyethyl methacrylate, HEMA), according to any one of the preceding embodiments.

[0194] 41. The phosphorus-containing compound (aiii) is of formulas IV, V, and VI:

[0195]

Chemical formula

[0196] (wherein Ws are the same or different, each W is independently selected from H and a divalent organic group, at least one W is a divalent organic group, and at least one X is a vinyl group, and the others are either a vinyl group or absent (when W is H) or H), according to any one of the preceding embodiments.

[0197] 42. The phosphorus-containing compound (aiii) is of formula VI, according to any one of the preceding embodiments.

[0198] 43. The phosphorus-containing compound (aiii) is of formula VI and 1, 2, or 3 X groups are vinyl, according to any one of the preceding embodiments. Preferably, 1 X group is vinyl.

[0199] 44. The phosphorus-containing compound (aiii) is of formula VI and 1, 2, or 3 WX groups are of formula VII:

[0200]

Chemical formula

[0201] (In the formula, the dot represents a group-bonding point. When one or two WX groups are those of formula VII, the remaining WX groups are preferably H), any one of the preceding embodiments.

[0202] 45. The phosphorus-containing compound (aiii) has the formula VIII

[0203]

Chemical formula

[0204] any one of the preceding embodiments.

[0205] 46. The phosphorus-containing compound (aiii) has the formula IX

[0206]

Chemical formula

[0207] any one of the preceding embodiments.

[0208] 47. The phosphorus-containing compound (aiii) is a mixture of about 2:1 of formula VIII and formula IX, any one of the preceding embodiments.

[0209] 48. The phosphorus-containing compound is selected from any one of the preceding embodiments, which is phosphoric acid; 2-methacryloyloxyethyl phosphate; bis-(2-methacryloyloxyethyl) phosphate; 2-acryloyloxyethyl phosphate; bis-(2-acryloyloxyethyl) phosphate; methyl-(2-methacryloyloxyethyl) phosphate; ethyl methacryloyloxyethyl phosphate; methyl acryloyloxyethyl phosphate; ethyl acryloyloxyethyl phosphate; propyl acryloyloxyethyl phosphate, isobutyl acryloyloxyethyl phosphate, ethylhexyl acryloyloxyethyl phosphate, halopropyl acryloyloxyethyl phosphate, haloisobutyl acryloyloxyethyl phosphate or haloethylhexyl acryloyloxyethyl phosphate; vinylphosphonic acid; cyclohexene-3-phosphonic acid; (α-hydroxybutene-2-phosphonic acid; 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid; 1-hydroxy-1-methyl-1-diphosphonic acid: 1-amino-1-phenyl-1,1-diphosphonic acid; 3-amino-3-hydroxypropane-1,1-diphosphonic acid; amino-tris(methylenephosphonic acid); gamma-aminopropylphosphonic acid; gamma-glycidoxypropylphosphonic acid; phosphoric acid-mono-2-aminoethyl ester; allylphosphonic acid; allylphosphinic acid; β-methacryloyloxyethylphosphinic acid; diallylphosphinic acid; β-methacryloyloxyethyl) phosphinic acid and allyl methacryloyloxyethyl phosphinic acid.

[0210] 49. The tertiary amine radical initiator (Aiv) has the general formula X:

[0211]

Chemical formula

[0212] (wherein W is selected from the group consisting of hydrogen, hydroxy, amino, halogen, alkyl having 1 to 8, preferably 1 to 4 carbon atoms, and alkoxy having 1 to 8, preferably 1 to 4 carbon atoms; R 1 and R 2 are independently selected from branched or straight-chain C1-4-alkyl; and b is 1 or 2), any one of the preceding embodiments.

[0213] 50. The tertiary amine radical initiator is selected from N,N-dimethylaniline, N,N-dimethylaminomethylphenol, and N,N-dimethyl-p-toluidine, any one of the preceding embodiments.

[0214] 51. The tertiary amine radical initiator is N,N-dimethyl-p-toluidine, any one of the preceding embodiments.

[0215] 52. The tertiary amine radical initiator is used in an amount of 0.1 to 0.6% by weight, more preferably 0.2 to 0.4% by weight, based on the total weight of part A, any one of the preceding embodiments.

[0216] 53. The tertiary amine radical initiator is N,N-dimethyl-p-toluidine and is used in an amount of 0.1 to 0.6% by weight, more preferably 0.2 to 0.4% by weight, based on the total weight of part A, any one of the preceding embodiments.

[0217] 54. Diethylhydroxylamine is present in part A in an amount of 0.015 to 0.06% by weight, more preferably 0.2 to 0.055% by weight, based on the total weight of part A, any one of the preceding embodiments.

[0218] 55. At least one epoxy resin contains the reaction product of epichlorohydrin and bisphenol A, any one of the preceding embodiments.

[0219] 56. At least one epoxy resin includes an epoxy resin which is a liquid reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPas (measured according to ASTM D-445), in any one of the preceding embodiments.

[0220] 57. At least one epoxy resin includes a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, in any one of the preceding embodiments.

[0221] 58. At least one epoxy resin includes a mixture of a liquid reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPas (measured according to ASTM D-445), and a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, in any one of the preceding embodiments.

[0222] 59. At least one epoxy resin is 50 to 95% by weight, more preferably 60 to 80% by weight, based on the total weight of the epoxy resin in part B, with an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage ratio of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPas (measured according to ASTM D-445), and includes a liquid reaction product of epichlorohydrin and bisphenol A, according to any one of the preceding embodiments.

[0223] 60. At least one epoxy resin is 5 to 50% by weight, more preferably 20 to 40% by weight, based on the total weight of the epoxy resin in part B, and includes a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, according to any one of the preceding embodiments.

[0224] 61. At least one epoxy resin is 50 to 95% by weight, more preferably 60 to 80% by weight, based on the total weight of the epoxy resin in part B, with an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage ratio of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPas (measured according to ASTM D-445), and includes a liquid reaction product of epichlorohydrin and bisphenol A, and 5 to 50% by weight, more preferably 20 to 40% by weight, of a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, according to any one of the preceding embodiments.

[0225] 62. Part B includes at least one epoxy resin in an amount of 10 to 30% by weight, more preferably 12 to 20% by weight, particularly preferably 14 to 16% by weight, based on the total weight of part B, according to any one of the preceding embodiments.

[0226] 63. The oxidizing agent (bi) is selected from organic peroxides, according to any one of the preceding embodiments.

[0227] 64. The oxidizing agent (bi) is selected from diacyl peroxides, hydroperoxides, peresters, and ketone hydroperoxides, according to any one of the preceding embodiments.

[0228] 65. The oxidizing agent (bi) is selected from benzoyl peroxide, cumene hydroperoxide, β-butyl peroxybenzoate, and methyl ethyl ketone hydroperoxide, according to any one of the preceding embodiments.

[0229] 66. The oxidizing agent (bi) is benzoyl peroxide, according to any one of the preceding embodiments.

[0230] 67. The oxidizing agent (bi) is present in part B at 1.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total weight of part B, according to any one of the preceding embodiments.

[0231] 68. Part B contains 1.5 to 5% by weight, more preferably 2 to 4% by weight, of benzoyl peroxide, based on the total weight of part B, according to any one of the preceding embodiments.

[0232] 69. The thermally conductive filler comprises, consists essentially of, or consists entirely of one or more thermally conductive fillers having a thermal conductivity of from about 3 W / mK to about 80 W / mK, according to any one of the preceding embodiments.

[0233] 70. The thermally conductive filler is selected from aluminum hydroxide, aluminum oxide, aluminum powder, zinc oxide, boron nitride, and mixtures thereof, according to any one of the preceding embodiments.

[0234] 71. The thermally conductive filler is aluminum hydroxide, according to any one of the preceding embodiments.

[0235] 72. In any one of the preceding embodiments, the adhesive mixture formed by mixing part A and part B contains a sufficient amount of thermally conductive filler such that the thermal conductivity of the adhesive mixture, after curing, is at least about 0.9 W / mK or more, preferably about 1.0 W / mK or more.

[0236] 73. In any one of the preceding embodiments, the thermally conductive filler is ATH having a multimodal particle size distribution.

[0237] 74. In any one of the preceding embodiments, the thermally conductive filler is ATH having a bimodal particle size distribution.

[0238] 75. The thermally conductive filler has the following particle size distribution: D 10 = 0.5 μm D 50 = 8 μm D 90 = 80 μm and is aluminum trihydroxide in any one of the preceding embodiments.

[0239] 76. In any one of the preceding embodiments, the thermally conductive filler is present in part A and / or part B, and when the two components are mixed (preferably at a volume ratio of 2:1 to 10:1, more preferably 4:1) to form the adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is present such that it is at least 40% by weight based on the total weight of the adhesive mixture.

[0240] 77. In any one of the preceding embodiments, the thermally conductive filler is present in part A and / or part B, and when the two components are mixed (preferably at a volume ratio of 2:1 to 10:1, more preferably 4:1) to form the adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is present such that it is 55 - 65% by weight based on the total weight of the adhesive mixture.

[0241] 78. In any one of the preceding embodiments, the thermally conductive filler is present in part A, part B, or both.

[0242] 79. Both part A and part B are any one of the preceding embodiments that include a thermally conductive filler.

[0243] 80. The concentration of the thermally conductive filler in part A is 40 to 90% by weight, more preferably 55 to 62% by weight, and particularly preferably 44 to 57% by weight based on the total weight of part A, which is any one of the preceding embodiments.

[0244] 81. The concentration of the thermally conductive filler in part B is 55 to 90% by weight, more preferably 60 to 70% by weight, and particularly preferably 44 to 57% by weight based on the total weight of part B, which is any one of the preceding embodiments.

[0245] 82. The concentration of the thermally conductive filler in part A is 40 to 65% by weight, more preferably 55 to 62% by weight, and particularly preferably 44 to 57% by weight based on the total weight of part A, and the concentration of the thermally conductive filler in part B is 55 to 90% by weight, more preferably 60 to 70% by weight, and particularly preferably 44 to 57% by weight based on the total weight of part B, which is any one of the preceding embodiments.

[0246] 83. The adhesive of the present invention exhibits a lap shear strength of 10 MPa or more on cold-rolled steel using the following test method, which is any one of the preceding embodiments: Test specimens are prepared and tested in accordance with SAE J1523 [2012 02 01]. A 25.4 mm × 101.6 mm test specimen is fitted with a 12.7 mm overlap and a 0.10 mm bond line thickness, then cured at room temperature, and the test specimen is tested at a rate of 12.7 mm / min.

[0247] 84. The adhesive of the present invention exhibits a lap shear strength of 10 MPa or more on nickel-plated steel using the following test method, which is any one of the preceding embodiments: Test specimens are prepared and tested in accordance with SAE J1523 [2012 02 01]. A 25.4 mm × 101.6 mm test specimen is fitted with a 12.7 mm overlap and a 0.10 mm bond line thickness, then cured at room temperature, and the test specimen is tested at a rate of 12.7 mm / min.

[0248] 85. When the adhesive of the present invention is tested as described above for lap shear strength, any one of the preceding embodiments showing a failure mode of cohesive failure of at least 90%, more preferably at least 95% on cold-rolled steel.

[0249] 86. When the adhesive of the present invention is tested as described above for lap shear strength, any one of the preceding embodiments showing a failure mode of cohesive failure of at least 50%, more preferably at least 80% on nickel-plated steel.

[0250] 87. Any one of the preceding embodiments in which the adhesive of the present invention exhibits good storage stability, as demonstrated by the absence of gelation of part A after heat aging at 54°C for 2 weeks.

Examples

[0251] The components are listed in Table 1.

[0252]

Table 1

[0253]

Table 2

[0254]

Table 3

[0255] Preparation of the Adhesive Using a double asymmetric centrifuge FlackTek SpeedMixer (registered trademark) DAC 400 FVZ by Hauschild Engineering, all formulations were mixed using the following procedure.

[0256] The present invention and comparative samples were prepared using the components listed in Table 2.

[0257] Procedure of Part A The following procedure was carried out under vacuum. Acrylic monomers (THFMA, CHMA) were added to the mixture together with zinc dimethacrylate, MAA, HEMA, Hypro (strengthening agent), Dynasylan, SR480, Ethanox and DEHA, and the mixture was rapidly mixed at 2,300 rpm for 2 minutes. ATH, talc, glass beads and fumed silica were added, and the mixture was rapidly mixed at 2,300 rpm for 2 minutes. The walls of the container were scraped, and the mixture was rapidly mixed at 2,300 rpm for another 2 minutes. N,N-dimethyl-p-toluidine was added, and rapid mixing was continued at 2,100 rpm for another 1 minute. The sides of the container were scraped, and mixing was continued at 2,100 rpm for another 1 minute. Part A was stored in a cartridge under vacuum until use. Packaging was carried out using the material at about 40 °C to minimize the trapped air.

[0258] Procedure of Part B Epoxy resin and BHT were added to a speed mixer. This mixture was heated to 80 °C over 1 hour to dissolve BHT. All other liquids except Luperox (benzoyl peroxide) were added, and the mixture was rapidly mixed at 2,100 rpm for 2 minutes. Solid components were added, and the mixture was rapidly mixed at 2,100 rpm for 2 minutes. The sides of the container were scraped, and mixing was continued at 2,100 rpm for 2 minutes. The mixture was cooled to 40 - 50 °C, Luperox was added, and the mixture was rapidly mixed at 1,200 rpm for 30 seconds and then at 2,100 rpm for 2 minutes. Part B was stored in a cartridge under vacuum until use. Packaging was carried out using the material at about 40 °C to minimize the trapped air.

[0259] Dispensing and Use of the Adhesive At room temperature, Part A and Part B were dispensed using an air gun through a 16-element static mixer. Before using the adhesive, the beads of the two adhesives were purged through the mixer to the length of the mixer.

[0260] Open Time Two components were mixed at a volume ratio of 4:1 through a static mixer. Immediately after distributing beads with a length of approximately 8 cm × width of 8 mm × height of 5 mm, the timer was started, and after distributing the adhesive, the time until the center of the beads hardened in the solid / gel was recorded. Hardening was determined by piercing with a disposable popsicle stick. The results are listed in Table 2.

[0261] Lap shear strength Lap shear data were collected on either cold rolled steel (CRS) or plasma-treated nickel-plated steel (NPS). Test specimens were prepared and tested according to SAE J1523[2012 02 01]. Test specimens of 25.4 mm × 101.6 mm were mated with a 12.7 mm overlap and a bond line thickness of 0.10 mm, and then cured at room temperature. The test specimens were tested at a rate of 12.7 mm / min. The results are listed in Table 2.

[0262] A part aging test To test the storage stability of part A, the mixture was heated in an oven maintained at 54 °C, and the time until gelation was recorded. The results are listed in Table 2.

[0263] Thermal conductivity Thermal conductivity was measured according to ASTM D5470. A TIMTester from Linseis TIM was used for the test and it was carried out according to ASTM D5470. Measurements were made using the Type III method. In this method, a stack of 1.0 mm test specimens was used, and silicone oil was used on the surface of each sample to reduce the contact resistance during measurement. The bulk thermal conductivity λ (W / mK) was recorded. The results are listed in Table 2.

[0264]

Table 4

[0265]

Table 5

Claims

1. A two-component thermally conductive epoxy-acrylic hybrid adhesive, comprising: Part A ai) at least one methacrylate monomer; aii) at least one elastomer reinforcing agent terminated with a methacrylate group; aiii) a phosphorus-containing compound having a monoester of phosphonic acid, phosphonic acid and monoesters and diesters of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) a tertiary amine radical initiator; av) 0.0025 to 0.065% by weight of diethylhydroxylamine; Part B bi) at least one epoxy resin; bii) an oxidizing agent; wherein Part A and / or Part B contains a thermally conductive filler, such that when Part A and Part B are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 90% by weight of a thermally conductive filler.

2. A method of bonding two or more substrates, comprising: (1) providing a two-component thermally conductive epoxy-acrylic hybrid adhesive, said two-component thermally conductive epoxy-acrylic hybrid adhesive comprising: Part A ai) at least one methacrylate monomer; aii) at least one elastomer reinforcing agent terminated with a methacrylate group; aiii) a phosphorus-containing compound having a monoester of phosphonic acid, phosphonic acid and monoesters and diesters of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) a tertiary amine radical initiator; av) 0.0025 to 0.065% by weight of diethylhydroxylamine; Part B bi) at least one epoxy resin; bii) an oxidizing agent; wherein Part A and / or Part B contains a thermally conductive filler, such that when Part A and Part B are mixed together to form an adhesive mixture, the adhesive mixture contains 40 to 90% by weight of a thermally conductive filler; (2) mixing Part A and Part B to obtain an adhesive mixture; (3) applying said adhesive mixture to a first substrate, a second substrate, or both; (4) bringing said first substrate into adhesive contact with said second substrate; and (5) curing said adhesive mixture. A method comprising the above steps.

3. The at least one methacrylate monomer is of general formula I: 【Chemical 1】 (wherein R is an organic group), the adhesive or method according to claim 1 or 2.

4. R is a substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group which may contain H, one or more heteroatoms, and a C １ -C １８ substituted or unsubstituted, and a C which may contain one or more heteroatoms ４ -C １８ The adhesive or method according to claim 3, selected from aromatic hydrocarbon groups.

5. R is selected from substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon groups which may contain one or more heteroatoms, in particular R is cyclohexyl or CH １ -C １８ and in particular R is cyclohexyl or CH ２ -THF (wherein THF is a 2- or 3-tetrahydrofurfuryl group), the adhesive or method according to claim 3.

6. The at least one methacrylate monomer is selected from isobornyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, and mixtures thereof, the adhesive or method according to any one of claims 1 to 5.

7. Part A comprises two or more methacrylate monomers, the adhesive or method according to any one of claims 1 to 6.

8. Part A comprises tetrahydrofurfuryl methacrylate (CAS [2455-24-5]), the adhesive or method according to any one of claims 1 to 7.

9. Part A comprises cyclohexyl methacrylate (CAS [101-43-9]), the adhesive or method according to any one of claims 1 to 8.

10. Part A comprises methacrylic acid, the adhesive or method according to any one of claims 1 to 9.

11. Part A comprises tetrahydrofurfuryl methacrylate and cyclohexyl methacrylate, the adhesive or method according to any one of claims 1 to 10.

12. Part A comprises tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate and methacrylic acid, the adhesive or method according to any one of claims 1 to 11.

13. Part A comprises an adhesion promoter in the form of a divalent metal salt of methacrylic acid, especially zinc dimethacrylate, the adhesive or method according to any one of claims 1 to 12.

14. Part A comprises a crosslinking agent, the adhesive or method according to any one of claims 1 to 13.

15. The crosslinking agent is a molecule having a molecular weight of 2,000 Da or less, preferably 1,000 Da or less, and two or more methacrylate groups, the adhesive or method according to claim 14.

16. The crosslinking agent has a molecular weight of 900 Da or less, the adhesive or method according to claim 14 or 15.

17. The crosslinking agent has two methacrylate groups, the adhesive or method according to claim 14, 15 or 16.

18. The crosslinking agent has a molecular weight of 900 Da or less and two methacrylate groups, the adhesive or method according to claim 14.

19. Part A has the following general formula II: 【Chemical 2】 (wherein x and y are independently selected from 2 to 10, preferably, x and y are both 5) and comprises a crosslinking agent, the adhesive or method according to any one of claims 1 to 18.

20. The A part contains 0.5 to 2.5% by weight, more preferably 0.6 to 1.25% by weight, and particularly preferably 0.6 to 0.8% by weight of a crosslinking agent based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 19.

21. The A part contains a crosslinking agent of general formula II and is present in an amount of 0.5 to 2.5% by weight, more preferably 0.6 to 1.25% by weight, and particularly preferably 0.6 to 0.8% by weight based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 20.

22. The A part contains tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, and a divalent metal salt of methacrylic acid, particularly zinc dimethacrylate, and is the adhesive or method according to any one of claims 1 to 21.

23. The methacrylate monomer other than the adhesion promoter and the crosslinking agent represents 10 to 30% by weight, more preferably 12 to 25% by weight, and particularly preferably 14 to 20% by weight of the A part based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 22.

24. The A part contains 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 23.

25. The A part contains 5 to 20% by weight, more preferably 7 to 15% by weight, and even more preferably 10 to 13% by weight of cyclohexyl methacrylate based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 24.

26. The A part contains 1 to 6% by weight, more preferably 2 to 4% by weight of methacrylic acid based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 25.

27. The A part contains 0.25 to 4% by weight, more preferably 0.5 to 1.5% by weight of a divalent metal salt of methacrylic acid based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 26.

28. The A part contains 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight of zinc dimethacrylate based on the total weight of the A part, and is the adhesive or method according to any one of claims 1 to 27.

29. The A part contains, based on the total weight of the A part, 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, and, based on the total weight of the A part, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight of cyclohexyl methacrylate, the adhesive or method according to any one of claims 1 to 28.

30. The A part contains, based on the total weight of the A part, 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, and, based on the total weight of the A part, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight of cyclohexyl methacrylate, and, based on the total weight of the A part, 1 to 6% by weight, more preferably 2 to 4% by weight of methacrylic acid, the adhesive or method according to any one of claims 1 to 29.

31. The A part contains, based on the total weight of the A part, 0.3 to 8% by weight, more preferably 0.5 to 5% by weight of tetrahydrofurfuryl methacrylate, and, based on the total weight of the A part, 5 to 20% by weight, more preferably 7 to 15% by weight, even more preferably 10 to 13% by weight of cyclohexyl methacrylate, and, based on the total weight of the A part, 1 to 6% by weight, more preferably 2 to 4% by weight of methacrylic acid, and, based on the total weight of the A part, 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight of zinc dimethacrylate, the adhesive or method according to any one of claims 1 to 30.

32. The reinforcing agent is selected from a polyether-based reinforcing agent and a rubber-based reinforcing agent, the adhesive or method according to any one of claims 1 to 31.

33. The reinforcing agent is a polyether-based reinforcing agent prepared by reacting a polyether polyol with a polyisocyanate in a ratio such that the resulting polymer is an NCO-capped polymer, followed by end-capping with a hydroxyalkyl ester of methacrylic acid, the adhesive or method according to any one of claims 1 to 32.

34. The reinforcing agent is a rubber-based reinforcing agent, and the rubber is selected from polyurethane, silicone, polybutadiene, acrylonitrile butadiene, polyacrylate or polymethacrylate, and mixtures thereof, the adhesive or method according to any one of claims 1 to 33.

35. The A part contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of the A part, the adhesive or method according to any one of claims 1 to 34.

36. The A part contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of the A part, and the reinforcing agent is a rubber-based reinforcing agent terminated with a methacrylate group, the adhesive or method according to any one of claims 1 to 35.

37. The A part contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of the reinforcing agent (aii) based on the total weight of the A part, the reinforcing agent is a rubber-based reinforcing agent terminated with a methacrylate group, and the rubber is selected from polyurethane, silicone, polybutadiene, acrylonitrile-butadiene, polyacrylate or polymethacrylate, and mixtures thereof, the adhesive or method according to any one of claims 1 to 36.

38. Part A contains 5 to 20% by weight, more preferably 7 to 15% by weight, particularly preferably 8 to 12% by weight of a reinforcing agent (aii) based on the total weight of Part A, and the reinforcing agent is obtained by reacting an aliphatic polyether diol with an aliphatic diisocyanate, followed by C ２ to C ６ -hydroxyalkyl ester, more preferably C ２ to C ４ -hydroxyalkyl, even more preferably C ２ to C ３ -hydroxyalkyl ester, most preferably C ２ -hydroxyalkyl (2-hydroxyethyl methacrylate, HEMA) end-capped adhesive or method according to any one of claims 1 to 37.

39. The phosphorus-containing compound (aiii) is of formulae IV, V and VI: [Chemical Formula 3] (wherein Ws are the same or different, each W is independently selected from H and a divalent organic group, at least one W is a divalent organic group, and at least one X is a vinyl group, and the others are vinyl groups or do not exist (when W is H), or H), the adhesive or method according to any one of claims 1 to 38.

40. The phosphorus-containing compound (aiii) is of formula VI, the adhesive or method according to any one of claims 1 to 39.

41. The phosphorus-containing compound (aiii) is of formula VI, and 1, 2 or 3 X groups are vinyl, preferably 1 X group is vinyl, the adhesive or method according to any one of claims 1 to 40.

42. The phosphorus-containing compound (aiii) is of formula VI, and 1, 2 or 3 WX groups are of formula VII: [Chemical Formula 4] (wherein the dot represents a group bonding point, and when 1 or 2 WX groups are of formula VII, the remaining WX groups are preferably H), the adhesive or method according to any one of claims 1 to 41.

43. The phosphorus-containing compound (aiii) is of formula VIII: 【Chemical Formula 5】 The adhesive or method according to any one of claims 1 to 42, which is as described above.

44. The phosphorus-containing compound (aiii) is of formula IX: 【Chemical Formula 6】 The adhesive or method according to any one of claims 1 to 43, which is as described above.

45. The adhesive or method according to any one of claims 1 to 44, wherein the phosphorus-containing compound (aiii) is a mixture of about 2:1 of formula VIII and formula IX.

46. The phosphorus-containing compound is phosphoric acid; 2-methacryloyloxyethyl phosphate; bis-(2-methacryloyloxyloxyethyl) phosphate; 2-acryloyloxyethyl phosphate; bis-(2-acryloyloxyethyl) phosphate; methyl-(2-methacryloyloxyethyl) phosphate; ethyl methacryloyloxyethyl phosphate; methylacryloyloxyethyl phosphate; ethylacryloyloxyethyl phosphate; propylacryloyloxyethyl phosphate, isobutylacryloyloxyethyl phosphate, ethylhexylacryloyloxyethyl phosphate, halopropylacryloyloxyethyl phosphate, haloisobutylacryloyloxyethyl phosphate or haloethylhexylacryloyloxyethyl phosphate; vinylphosphonic acid; cyclohexene-3-phosphonic acid; (α-hydroxybutene-2-phosphonic acid; 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid; 1-hydroxy-1-methyl-1-diphosphonic acid: 1-amino-1-phenyl-1,1-diphosphonic acid; 3-amino-3-hydroxypropane-1,1-diphosphonic acid; Amino-tris(methylenephosphonic acid); gamma-amino-propylphosphonic acid; gamma-glycidoxypropylphosphonic acid; phosphoric acid-mono-2-aminoethyl ester; allylphosphonic acid; allylphosphinic acid; β-methacryloyloxyethylphosphinic acid; diallylphosphinic acid; The adhesive or method according to any one of claims 1 to 45, selected from β-methacryloyloxyethyl)phosphinic acid and allylmethacryloyloxyethylphosphinic acid.

47. The tertiary amine radical initiator (aiv) is of general formula X: 【Chemical Formula 7】 (wherein W is selected from the group consisting of hydrogen, hydroxy, amino, halogen, alkyl having 1 to 8, preferably 1 to 4 carbon atoms, and alkoxy having 1 to 8, preferably 1 to 4 carbon atoms; R １ and R ２ are independently selected from branched or straight-chain C １ to ４ -alkyl; and b is 1 or 2), the adhesive or method according to any one of claims 1 to 46.

48. The tertiary amine radical initiator is selected from N,N-dimethylaniline, N,N-dimethylaminomethylphenol, and N,N-dimethyl-p-toluidine, and the adhesive or method according to any one of claims 1 to 47.

49. The tertiary amine radical initiator is N,N-dimethyl-p-toluidine, and the adhesive or method according to any one of claims 1 to 48.

50. The tertiary amine radical initiator is used in an amount of 0.1 to 0.6% by weight, more preferably 0.2 to 0.4% by weight, based on the total weight of part A, and the adhesive or method according to any one of claims 1 to 49.

51. The tertiary amine radical initiator is N,N-dimethyl-p-toluidine and is used in an amount of 0.1 to 0.6% by weight, more preferably 0.2 to 0.4% by weight, based on the total weight of part A, and the adhesive or method according to any one of claims 1 to 50.

52. Diethylhydroxylamine is present in part A in an amount of 0.015 to 0.06% by weight, more preferably 0.2 to 0.055% by weight, based on the total weight of part A, and the adhesive or method according to any one of claims 1 to 51.

53. The at least one epoxy resin includes a reaction product of epichlorohydrin and bisphenol A, and the adhesive or method according to any one of claims 1 to 52.

54. The at least one epoxy resin includes an epoxy resin which is a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured according to ASTM D-445), and the adhesive or method according to any one of claims 1 to 53.

55. The at least one epoxy resin includes a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, and the adhesive or method according to any one of claims 1 to 54.

56. The at least one epoxy resin is a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured according to ASTM D-445), and a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, and is an adhesive or method according to any one of claims 1 to 55.

57. The at least one epoxy resin contains, based on the total weight of the epoxy resin in part B, 50 to 95% by weight, more preferably 60 to 80% by weight, of an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured according to ASTM D-445), and is an adhesive or method according to any one of claims 1 to 56.

58. The at least one epoxy resin contains, based on the total weight of the epoxy resin in part B, 5 to 50% by weight, more preferably 20 to 40% by weight, of a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, and is an adhesive or method according to any one of claims 1 to 57.

59. The at least one epoxy resin has an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide percentage of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured according to ASTM D-445), being 50 to 95% by weight, more preferably 60 to 80% by weight, based on the total weight of the epoxy resin in Part B, and is a liquid reaction product of epichlorohydrin and bisphenol A, and contains 5 to 50% by weight, more preferably 20 to 40% by weight, of a bisphenol A / F-based epoxy resin having an epoxide equivalent of 345 to 365 g / eq, the adhesive or method according to any one of claims 1 to 58.

60. Part B contains 10 to 30% by weight, more preferably 12 to 20% by weight, particularly preferably 14 to 16% by weight, of the at least one epoxy resin, based on the total weight of Part B, the adhesive or method according to any one of claims 1 to 59.

61. The oxidizing agent (bi) is selected from organic peroxides, the adhesive or method according to any one of claims 1 to 60.

62. The oxidizing agent (bi) is selected from diacyl peroxides, hydroperoxides, peresters, and ketone hydroperoxides, the adhesive or method according to any one of claims 1 to 61.

63. The oxidizing agent (bi) is selected from benzoyl peroxide, cumene hydroperoxide, β-butyl peroxybenzoate, and methyl ethyl ketone hydroperoxide, the adhesive or method according to any one of claims 1 to 62.

64. The oxidizing agent (bi) is benzoyl peroxide, the adhesive or method according to any one of claims 1 to 63.

65. The oxidizing agent (bi) is present in Part B at 1.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total weight of Part B, the adhesive or method according to any one of claims 1 to 64.

66. Part B contains 1.5 to 5% by weight, more preferably 2 to 4% by weight, of benzoyl peroxide, based on the total weight of Part B, the adhesive or method according to any one of claims 1 to 65.

67. The heat conductive filler contains, consists essentially of, or consists entirely of one or more heat conductive fillers having a thermal conductivity of about 3 W / mK to about 80 W / mK, the adhesive or method according to any one of claims 1 to 66.

68. The heat conductive filler is selected from aluminum hydroxide, aluminum oxide, aluminum powder, zinc oxide, boron nitride, and mixtures thereof, the adhesive or method according to any one of claims 1 to 67.

69. The heat conductive filler is aluminum hydroxide, the adhesive or method according to any one of claims 1 to 68.

70. The adhesive mixture formed by mixing part A and part B contains a sufficient amount of heat conductive filler such that the thermal conductivity of the adhesive mixture is at least about 0.9 W / mK or more, preferably about 1.0 W / mK or more after curing, the adhesive or method according to any one of claims 1 to 69.

71. The heat conductive filler is ATH having a multimodal particle size distribution, the adhesive or method according to any one of claims 1 to 70.

72. The heat conductive filler is ATH having a bimodal particle size distribution, the adhesive or method according to any one of claims 1 to 71.

73. The heat conductive filler has the following particle size distribution: D １０ = 0.5 μm D ５０ = 8 μm D ９０ = 80 μm is aluminum trihydroxide having, the adhesive or method according to any one of claims 1 to 72.

74. The heat conductive filler is in part A and / or part B such that when the two components are mixed (preferably in a volume ratio of 2:1 to 10:1, more preferably 4:1) to form an adhesive mixture, the concentration of the heat conductive filler in the adhesive mixture is at least 40% by weight based on the total weight of the adhesive mixture, the adhesive or method according to any one of claims 1 to 73.

75. The heat conductive filler is in part A and / or part B such that when the two components are mixed (preferably in a volume ratio of 2:1 to 10:1, more preferably 4:1) to form an adhesive mixture, the concentration of the heat conductive filler in the adhesive mixture is 55 - 65% by weight based on the total weight of the adhesive mixture, the adhesive or method according to any one of claims 1 to 74.

76. The thermally conductive filler is present in part A, part B, or both, of the adhesive or method according to any one of claims 1 to 75. **Claim 77** The adhesive or method according to any one of claims 1 to 76, wherein both part A and part B contain a thermally conductive filler. **Claim 78** The concentration of the thermally conductive filler in part A is 40 to 90% by weight, more preferably 55 to 62% by weight, and particularly preferably 44 to 57% by weight, based on the total weight of part A, of the adhesive or method according to any one of claims 1 to 77. **Claim 79** The concentration of the thermally conductive filler in part B is 55 to 90% by weight, more preferably 60 to 70% by weight, and particularly preferably 44 to 57% by weight, based on the total weight of part B, of the adhesive or method according to any one of claims 1 to 78. **Claim 80** The concentration of the thermally conductive filler in part A is 40 to 90% by weight, more preferably 55 to 62% by weight, and particularly preferably 44 to 57% by weight, based on the total weight of part A, and the concentration of the thermally conductive filler in part B is 55 to 90% by weight, more preferably 60 to 70% by weight, and particularly preferably 44 to 57% by weight, based on the total weight of part B, of the adhesive or method according to any one of claims 1 to 79. **Claim 81** The adhesive of the present invention has a lap shear strength on cold rolled steel of 10 MPa or more, using the following test method: test specimens are prepared and tested according to SAE J1523 [2012 02 01], a 25.4 mm × 101.6 mm test specimen is mated with a 12.7 mm overlap and a 0.10 mm bond line thickness, then cured at room temperature, and the test specimen is tested at a rate of 12.7 mm / min, of the adhesive or method according to any one of claims 1 to 80. **Claim 82** The adhesive of the present invention has a lap shear strength on nickel-plated steel of 10 MPa or more, using the following test method: test specimens are prepared and tested according to SAE J1523 [2012 02 01], a 25.4 mm × 101.6 mm test specimen is mated with a 12.7 mm overlap and a 0.10 mm bond line thickness, then cured at room temperature, and the test specimen is tested at a rate of 12.7 mm / min, of the adhesive or method according to any one of claims 1 to 81. **Claim 83** The adhesive or method according to any one of claims 1 to 82, wherein when tested as described above for lap shear strength, the adhesive exhibits a cohesive failure mode of at least 90%, more preferably at least 95%, on cold rolled steel.

84. The adhesive or method according to any one of claims 1 to 83, wherein when tested as described above for lap shear strength, the adhesive exhibits a cohesive failure mode of at least 50%, more preferably at least 80%, on nickel plated steel.

85. The adhesive or method according to any one of claims 1 to 84, wherein the adhesive exhibits good storage stability as demonstrated by no gelation of part A after heat aging at 54°C for 2 weeks.

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