Two-component adhesive composition

Abstract

Provided herein are novel monomers for making polymers, particularly adhesives, and adhesives made with said novel monomers.

Description

[Technical Field]

[0001] The present invention relates to the field of thermally conductive two-part adhesive compositions. [Background technology]

[0002] The automotive industry has seen a trend towards lighter vehicles over the past decade. This trend has been driven primarily by regulations to reduce CO2 emissions from vehicle fleets. In recent years, lightweight construction strategies have been further fuelled by the increasing number of electrified vehicles.

[0003] To provide long driving range, batteries with high energy density are required. Several battery strategies are currently being developed with various detailed concepts, but what all long-range endurance battery concepts have in common is the need for thermal management to deal with the heat generated during charging and discharging of the battery.

[0004] Thermal interface materials and / or thermally conductive adhesives are required to thermally connect battery cells or modules to the cooling system. To avoid loss of efficiency and the initiation of dangerous thermal runaway reactions, cells must be kept within their optimal operating temperature range (preferably 25-40°C). Active cooling is increasingly being used, for example, by pumping a chilled water-glycol mixture through channels that cool a metal base plate on which the battery cells / modules are placed. Cells or arrays of cells can be directly bonded to the cooling plate with thermally conductive adhesives. This provides not only good mechanical fixation of the cells but also thermal connectivity. TIMs and thermally conductive adhesives typically have their good thermal properties due to a high loading of thermally conductive fillers, such as aluminum trihydroxide (ATH).

[0005] The common method for assembling large batteries has been to arrange battery cells into modules and then place the modules into a battery pack. A thermal interface material (TIM) is placed between the module and the cold plate. Because the TIM primarily provides thermal conductivity and very little structural support, the modules are typically fastened with screws or other mechanical methods. One way to increase energy density is to eliminate the module level and bond the cells directly onto the cold plate, in what is known as a cell-to-pack (CTP) approach. Because individual cells cannot be fastened manually, the TIM now must fulfill both structural and thermal roles. This has led to what are known as structural TIMs or thermally conductive adhesives.

[0006] The requirements for a thermally conductive adhesive are varied, but a thermal conductivity of 1.5 W / mK or greater and a lap shear strength of more than 4 MPa are most important. The cold plate, and often the cell as well, is made from aluminium, meaning that good adhesion to the aluminium is crucial.

[0007] Polyurethanes have been used as thermally conductive adhesives, but they suffer from poor adhesion to untreated aluminum and impaired shelf life in the presence of high loadings of thermally conductive fillers, especially ATH.

[0008] It is known to produce polyurethane analogs by replacing the terminal NCO groups in conventional polyurethane prepolymers with moieties derived from reacting the terminal NCO groups with molecules such as ethyl 2-oxocyclopentane-1-carboxylate (CPEE). While such prepolymers avoid the use of NCO-terminated compounds by end users, they often suffer from reduced strength after cure, especially when used in thermally conductive adhesives where high filler loadings are used. Summary of the Invention [Problem to be solved by the invention]

[0009] There is a continuing need for alternative polyurethane systems that exhibit excellent cure strength even with high filler loadings. [Means for solving the problem]

[0010] In a first aspect, the present invention provides a two-part thermally conductive adhesive comprising: (A) The following: (a1) General formula I:

[0011] [ka]

[0012] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 is a divalent C4-8 alkylene group having 2 to 5 C1-3 alkyl substituents on the alkylene chain. at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; The second part (Part B) includes Includes; wherein at least one of Part A and Part B contains a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or more, and at least one of Part A and Part B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and Part A and Part B are designed to be stored isolated from each other and mixed together to form the adhesive mixture before use. Provide an adhesive.

[0013] In a second aspect, the present invention provides a kit for forming a two-part thermally conductive adhesive, comprising: (A) The following: (a1) General formula I:

[0014] [ka]

[0015] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; A second part (Part B) containing Includes; wherein at least one of Part A and Part B contains a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or more, and at least one of Part A and Part B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and Part A and Part B are designed to be stored isolated from each other and mixed together to form the adhesive mixture before use. Provide a kit.

[0016] In a third aspect, the present invention provides a method for bonding a first substrate and a second substrate, comprising: (1)(A) and (B): (A) The following: (a1) General formula I:

[0017] [ka]

[0018] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 -divalent C with alkyl substituents 4~8 alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; A second part (Part B) containing providing a two-part thermally conductive adhesive comprising: wherein at least one of Part A and Part B contains a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or more, and at least one of Part A and Part B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and Part A and Part B are designed to be stored isolated from each other and mixed together to form the adhesive mixture before use; (2) mixing Part A and Part B to create an adhesive mixture; (3) applying the adhesive mixture to a first substrate; (4) bringing a second substrate into adhesive contact with the first substrate; (5) curing the adhesive mixture; The present invention provides a method comprising:

[0019] In a fourth aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: (1) a first substrate; (2) a second substrate; (3)(A) and (B): (A) The following: (a1) General formula I:

[0020] [ka]

[0021] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 -divalent C with alkyl substituents 4~8 -alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; The second part (Part B) includes A mixture of wherein at least one of Part A and Part B comprises a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or greater, and at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I. A thermally conductive adhesive composition resulting from curing 1. An adhesive assembly comprising: a first and second substrate in adhesive contact with the adhesive composition sandwiched therebetween; An adhesive assembly is provided. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present inventors have discovered novel monomers of general formula I for forming polymers, particularly adhesives, upon reaction with polyamines containing two or more primary or secondary amine groups.

[0023] Definitions and Abbreviations MDI Methylenebis(phenylisocyanate) HDI Hexamethylene Diisocyanate IPDI Isophorone Diisocyanate PU Polyurethane SEC size exclusion chromatography RH Relative Humidity PDI polydispersity index TMDI 2,4,4-trimethylhexamethylene diisocyanate CPEE Ethyl 2-oxocyclopentane-1-carboxylate RH Relative Humidity

[0024] Molecular weights of polymers as reported herein are reported in Daltons (Da) as number or weight average molecular weights as measured by gel permeation chromatography (GPC).

[0025] Compounds of general formula I In a first aspect, the present invention provides compounds of general formula I:

[0026] [ka]

[0027] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 -divalent C with alkyl substituents 4~8 alkylene group) The present invention provides a compound of the formula:

[0028] In a preferred embodiment, R 1 and R 2 are independently selected from H and C1-C4 alkyl, more preferably H and C1-C2 alkyl, and particularly preferably R 1 and R 2 is H.

[0029] In a preferred embodiment, n is 1.

[0030] In a preferred embodiment, R 3 is C1-C4 alkyl, more preferably R 3 is C1-C2 alkyl, and particularly preferably R 3 is ethyl.

[0031] In a preferred embodiment, R 4 is a divalent C6 alkylene group having 2 to 5 methyl substituents on the alkylene chain. 4 is a C6 alkylene group with three methyl substituents on the alkylene chain.

[0032] In a particularly preferred embodiment, the compound of general formula I has the formula I'':

[0033] [ka]

[0034] It is of the type.

[0035] Compounds of general formula I may be represented by formula III:

[0036] [ka]

[0037] (In the formula, R 4 is as defined above, including preferred embodiments), with at least two equivalents of a diisocyanate of formula IV:

[0038] [ka]

[0039] (In the formula, R 1 , R 2 , R 3 and n are defined as above, including preferred embodiments, with a compound of formula IV in the presence of a catalyst capable of catalyzing the reaction between an NCO group and a molecule of formula IV. The catalyst is preferably selected from bismuth and / or zinc catalysts. In a preferred embodiment, it is selected from bismuth and / or zinc carboxylates. In a particularly preferred embodiment, the catalyst is a mixture of bismuth and zinc carboxylates.

[0040] In an exemplary synthesis, 2,4,4-trimethylhexamethylene diisocyanate is reacted with at least two equivalents of a molecule of formula IV in the presence of a bismuth and / or zinc catalyst, particularly a mixture of bismuth and / or zinc catalysts:

[0041] At least one liquid epoxy resin Part A of the adhesive of the present invention comprises at least one liquid epoxy resin, which means an epoxy resin that is liquid at 23° C. Preferably, the liquid epoxy resin has a viscosity of 0.1 to 20 s -1 The viscosity at 23°C is measured on a Kinexus (Bohlin) apparatus using a cone-plate 20 mm diameter geometry (4° cone) at 23°C according to a shear rate rise / fall curve of 50 Pas or less, more preferably 25 Pas or less, and more particularly preferably 15 Pas or less.

[0042] The liquid epoxy resin is preferably non-rubber modified.

[0043] If only a single epoxy resin is present, it is a liquid at 23°C. If two or more epoxy resins are present, the individual epoxy resins in the mixture may themselves be solid at 23°C, but the mixture is a liquid at 23°C.

[0044] A wide variety of epoxy resins can be used, such as those described in U.S. Pat. No. 4,734,332, column 2, line 66 to column 4, line 24, which is incorporated herein by reference. The epoxy resin should have an average of at least 1.8, and preferably at least 2.0, epoxide groups per molecule. The epoxy equivalent weight can be, for example, 75 to 350, preferably 140 to 250, and in some embodiments, 150 to 225. When a mixture of non-rubber-modified epoxy resins is present, the mixture should have an average epoxy functionality of at least 1.8, preferably at least 2.0, and an epoxy equivalent weight as in the preceding sentence; more preferably, each epoxy resin in the mixture has such an epoxy functionality and epoxy equivalent weight.

[0045] Suitable epoxy resins include diglycidyl ethers of polyhydric phenolic compounds such as resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, and tetramethylbiphenol; diglycidyl ethers of aliphatic glycols such as diglycidyl ethers of C2-24 alkylene glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins (epoxy novolac resins), alkyl-substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenolic resins, and dicyclopentadiene-substituted phenolic resins; and any combination of any two or more thereof.

[0046] Suitable epoxy resins include diglycidyl ethers of bisphenol A resins, such as those sold by Olin Corporation under the designations DER® 330, DER® 331, DER® 332, DER® 383, DER661, and DER® 662 resins.

[0047] In a preferred embodiment, the at least one epoxy resin comprises or consists of a reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent weight (according to ASTM D-1652) of 176 to 185 g / eq, an epoxide percentage (according to ASTM D-1652) of 23.2 to 24.4%, an epoxide group content (according to ASTM D-1652) of 5,400 to 5,680 mmol / kg, and a viscosity at 25°C (according to ASTM D-445) of 7,000 to 10,000 MPas.

[0048] Epoxy novolac resins can be used, such as those commercially available from Olin Corporation as DEN® 354, DEN® 431, DEN® 438, and DEN® 439.

[0049] Other suitable epoxy resins are cycloaliphatic epoxides, which have the following structure V:

[0050] [ka]

[0051] (wherein R is an aliphatic, alicyclic and / or aromatic group, and n is a number from 1 to 10, preferably from 2 to 4). The alicyclic epoxy resins include saturated carbocyclic rings with epoxy oxygens bonded to two adjacent atoms in the carbocyclic ring, as exemplified by: When n is 1, the alicyclic epoxide is a monoepoxide. When n is 2 or greater, a diepoxide or polyepoxide is formed. Mixtures of monoepoxides, diepoxides, and / or polyepoxides can be used. Cycloaliphatic epoxy resins such as those described in U.S. Pat. No. 3,686,359, incorporated herein by reference, can be used in the present invention. Cycloaliphatic epoxy resins of particular interest are (3,4-epoxycyclohexyl-methyl)-3,4-epoxy-cyclohexanecarboxylate, bis-(3,4-epoxycyclohexyl)adipate, vinylcyclohexene monoxide, and mixtures thereof.

[0052] Other suitable epoxy resins include oxazolidone-containing compounds such as those described in U.S. Patent No. 5,112,932. Additionally, chain-extended epoxy-isocyanate copolymers such as those commercially sold as DER592 and DER6508 (Olin Corporation) can be used.

[0053] The liquid epoxy resin is preferably present in an amount of 2 to 20% by weight, more preferably 2 to 10% by weight, and especially preferably 4 to 8% by weight, based on the total weight of Part A.

[0054] The liquid epoxy resin is preferably present at 12 to 50% by weight, more preferably 15 to 35% by weight, and most especially preferably 20 to 30% by weight, based on the total organic content of Part A.

[0055] In a preferred embodiment, the at least one liquid epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent weight (according to ASTM D-1652) of 176 to 185 g / eq, an epoxide percentage (according to ASTM D-1652) of 23.2 to 24.4%, an epoxide group content (according to ASTM D-1652) of 5,400 to 5,680 mmol / kg, and a viscosity at 25°C (according to ASTM D-445) of 7,000 to 10,000 MPas, and is present in Part A in an amount of 2 to 20% by weight, more preferably 2 to 10% by weight, and particularly preferably 4 to 8% by weight, based on the total weight of Part A.

[0056] In another preferred embodiment, the at least one liquid epoxy resin comprises the liquid reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight (according to ASTM D-1652) of 176 to 185 g / eq, an epoxide percentage (according to ASTM D-1652) of 23.2 to 24.4%, an epoxide group content (according to ASTM D-1652) of 5,400 to 5,680 mmol / kg, a viscosity at 25°C (according to ASTM D-445) of 7,000 to 10,000 MPas, and is present in Part A in an amount of 12 to 50 wt.-%, more preferably 15 to 35 wt.-%, and more particularly preferably 20 to 30 wt.-%, based on the total organic content of Part A.

[0057] Thermally conductive filler Part A and / or Part B includes a thermally conductive filler.

[0058] The thermally conductive filler is not particularly limited. Suitable thermally conductive fillers have a thermal conductivity coefficient of more than 5 W / m°K, more preferably more than 10 W / m°K, or particularly preferably more than 15 W / m°K. Examples of thermally conductive fillers include alumina, alumina trihydrate or aluminum trihydroxide (ATH), silicon carbide, boron nitride, diamond, and graphite, as well as mixtures thereof. Aluminum trihydroxide (ATH) and aluminum oxide are particularly preferred, and ATH is most preferred. The thermally conductive filler may or may not be surface-treated.

[0059] In a preferred embodiment, the thermally conductive filler has a D of 3 or greater or about 3 or greater. 90 / D 50 Particularly preferably, the thermally conductive filler has a broad particle size distribution characterized by a D ratio of 3 or greater or about 3 or greater. 90 / D 50 ATH or aluminum oxide having a broad particle size distribution characterized by the ratio, most preferably ATH.

[0060] Also preferred are thermally conductive fillers having a bimodal particle size distribution. 90 / D 50 This is the case when the ratio is 3 or more or about 3 or more, more preferably 5 or more or about 5 or more, and most preferably 9 or more or about 9 or more. For example, D of 5 to 20 microns 50 and D of 70 to 90 microns 90 , especially D of 7 to 9 microns 50 and D of 78 to 82 microns 90 Particles having a D of 3 or more, more preferably 5 or more, and most preferably 9 or more. 90 / D 50 It is an ATH that has the following.

[0061] In a preferred embodiment, the thermally conductive filler has the following particle size distribution (preferably at 1 g / l by laser diffraction in deionized water containing a dispersing aid, such as NaPOx10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 A bimodal distribution of aluminum trihydroxide (ATH) having

[0062] The thermally conductive filler is preferably present in the final adhesive resulting from mixing Part A and Part B at a concentration of 30 to 85% by weight, more preferably 40 to 85% by weight, and most preferably 60 to 85% by weight, based on the total weight of the adhesive.

[0063] In a preferred embodiment, the thermally conductive filler is aluminum trihydroxide (ATH), used at a concentration of 30 to 85% by weight, more preferably 40 to 85% by weight, and most particularly preferably 60 to 85% by weight, based on the total weight of the adhesive.

[0064] In another preferred embodiment, the thermally conductive filler is bimodal aluminum trihydroxide (ATH) used in a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and more particularly preferably 60 to 85 wt. %, based on the total weight of the adhesive.

[0065] In another preferred embodiment, the thermally conductive filler has the following particle size distribution (preferably at 1 g / l by laser diffraction in deionized water containing a dispersing aid, such as NaPOx10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 and Aluminum trihydroxide (ATH) is used in a concentration of 30 to 85% by weight, more preferably 40 to 85% by weight, and more particularly preferably 60 to 85% by weight, based on the total weight of the adhesive.

[0066] The concentration of the thermally conductive filler in Part A is preferably 30 to 85% by weight, more preferably 40 to 85% by weight, and most preferably 60 to 85% by weight, based on the total weight of Part A.

[0067] The concentration of the thermally conductive filler in Part B is preferably 30 to 85% by weight, more preferably 40 to 85% by weight, and most preferably 60 to 85% by weight, based on the total weight of Part B.

[0068] In a preferred embodiment, the thermally conductive filler is aluminum trihydroxide (ATH), which is used in Part A and / or Part B at a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and most preferably 60 to 85 wt. %, based on the total weight of Part A or Part B.

[0069] In another preferred embodiment, the thermally conductive filler is an ATH with a bimodal pore size used in Part A and / or Part B at a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and even more preferably 60 to 85 wt. %, based on the total weight of Part A or Part B.

[0070] In a preferred embodiment, the thermally conductive filler has the following particle size distribution (preferably at 1 g / l by laser diffraction in deionized water containing a dispersing aid such as NaPOx10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 and Aluminum trihydroxide (ATH) is used in a concentration of 30 to 85% by weight, more preferably 40 to 85% by weight, and most preferably 60 to 85% by weight, based on the total weight of Part A or Part B.

[0071] at least one polyamine Component B comprises at least one polyamine having two or more primary or secondary amine groups.

[0072] In a preferred embodiment, the at least one polyamine comprises a triamine.

[0073] Preferably, the at least one polyamine comprises a polyamine having a molecular weight of at least 400 Da, more preferably at least 1,000 Da, and even more preferably at least 2,000 Da. In a preferred embodiment, the at least one polyamine comprises a polyamine having a molecular weight of 2,000 to 4,000 Da, more preferably about 3,000 Da.

[0074] In another preferred embodiment, the at least one polyamine comprises a polyamine having a molecular weight of at least 300 Da, more preferably at least 350 Da, and even more preferably at least 400 Da. In a preferred embodiment, the at least one polyamine comprises a polyamine having a molecular weight of 300 to 500 Da, more preferably about 400 to 440 Da.

[0075] In another preferred embodiment, the polyamine is a triamine having primary amine groups and having a molecular weight of 2,000 to 4,000 Da, more preferably 3,000 Da.

[0076] Examples of suitable compounds having primary and / or secondary amino groups include polyoxyalkylene polyamines having two or more amine groups per polyamine, two to four amine groups per polyamine, or two to three amine groups per polyamine. Polyether amines having three amine groups are particularly preferred.

[0077] The polyoxyalkylene polyamine may have a weight average molecular weight of at least 400 Da, more preferably at least 1,000 Da, and even more preferably at least 2,000 Da. In a preferred embodiment, the polyoxyalkylene polyamine has a molecular weight of 2,000 to 4,000 Da, more preferably about 3,000 Da. The polyoxyalkylene polyamine may have a weight average molecular weight of about 5,000 or less, or about 3,000 or less.

[0078] Exemplary polyoxyalkylene polyamines include the following: 1. Polyamines based on a propylene oxide polyether backbone. Examples include: A trifunctional primary amine having an average molecular weight of approximately 440 is included, the amine group of which is located on a secondary carbon atom at the end of an aliphatic polyether chain:

[0079] [ka]

[0080] ; Polypropylene oxide diamine with a molecular weight of about 400:

[0081] [ka]

[0082] ; A difunctional, primary amine having an average molecular weight of about 2000. The primary amine group is located on the terminal secondary carbon atom of an aliphatic polyether chain:

[0083] [ka]

[0084] formula:

[0085] [ka]

[0086] of approximately 3000 molecular weight triamine formula:

[0087] [ka]

[0088] of approximately 5,000 g / mol of triamine.

[0089] 2. Polyamines based primarily on a polyethylene oxide polyether backbone. Examples include those of the general formula:

[0090] [ka]

[0091] It is of the type. For example, a polyamine with a molecular weight of 600 g / mol (y ≈ 9, (x + z) ≈ 3.6); polyamine with a molecular weight of 900 g / mol (y ≈ 12.5, (x + z) ≈ 6); Polyamines with a molecular weight of 2,000 g / mol (y ≈ 39, (x + z) ≈ 6), etc.;

[0092] In a particularly preferred embodiment, the at least one polyamine has the formula:

[0093] [ka]

[0094] The compound comprises or consists of a triamine of approximately 3000 molecular weight.

[0095] In another preferred embodiment, the at least one polyamine has the following general structure:

[0096] [ka]

[0097] The present invention comprises or consists of a polyetheramine polyamine of approximately 440 molecular weight.

[0098] Other suitable polyamines include polyamidoamines, which contain repeating branched subunits of amide and amine functional groups. For example, suitable polyamidoamines can be initiated with ammonia or ethylenediamine and reacted by Michael addition with an acrylate ester (e.g., methyl acrylate), followed by reaction of the ester functional group with a diamine (e.g., ethylenediamine). This results in a primary amine-terminated polyamine, which can be reacted again by Michael addition, followed by reaction with a diamine again. The first "cycle" is represented diagrammatically below using ethylenediamine and methyl acrylate:

[0099] [ka]

[0100] Other suitable polyamines include phenalkamines prepared by the Mannich reaction between cardanol, formaldehyde, and at least one polyamine.

[0101] In a preferred embodiment, the at least one polyamine has the formula:

[0102] [ka]

[0103] a triamine of approximately 3000 molecular weight, The general structure is:

[0104] [ka]

[0105] with a polyetheramine triamine of approximately 440 molecular weight.

[0106] The at least one polyamine is preferably present in part B in an amount of 8 to 30% by weight, more preferably 10 to 20% by weight, and more particularly preferably 12 to 16% by weight, based on the total weight of part B.

[0107] The at least one polyamine is preferably present in part B in an amount of 80 to 99% by weight, more preferably 85 to 95% by weight, especially preferably 87 to 92% by weight, based on the organic content of part B.

[0108] In a preferred embodiment, the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines, which are used in part B in an amount of 8 to 30% by weight, more preferably 10 to 20% by weight, and more particularly preferably 12 to 16% by weight, based on the total weight of part B.

[0109] In another preferred embodiment, the at least one polyamine comprises or consists of a mixture of a polyethertriamine of approximately 3,000 Da and a polyethertriamine of approximately 440 Da, used in Part B in an amount of 8 to 30% by weight, more preferably 10 to 20% by weight, and more particularly preferably 12 to 16% by weight, based on the total weight of Part B.

[0110] In a preferred embodiment, the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines used in part B in an amount of 80 to 99% by weight, more preferably 85 to 95% by weight, particularly preferably 87 to 92% by weight, based on the organic content of part B.

[0111] In another preferred embodiment, the at least one polyamine comprises or consists of a mixture of approximately 3,000 Da polyethertriamine and approximately 440 Da polyethertriamine, used in Part B in an amount of 80 to 99% by weight, more preferably 85 to 95% by weight, and particularly preferably 87 to 92% by weight, based on the organic content of Part B.

[0112] At least one catalyst At least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I.

[0113] The catalyst is preferably selected from tertiary amine catalysts.

[0114] Examples of suitable tertiary amines include 2,4,6-tris-(dimethylaminomethyl)phenol, tetramethylguanidine, heptamethylisobiguanide, N,N-dimethylbenzylamine, and 1,4-diazabicyclo[2.2.2]octane.

[0115] In a preferred embodiment, the catalyst is 2,4,6-tris-(dimethylaminomethyl)phenol.

[0116] In another preferred embodiment, the catalyst is 1,4-diazabicyclo[2.2.4]octane.

[0117] In a preferred embodiment, the catalyst is a mixture of 2,4,6-tris-(dimethylaminomethyl)phenol and 1,4-diazabicyclo[2.2.4]octane.

[0118] The catalyst may be present in Part A and / or Part B. In a preferred embodiment, it is present in Part B.

[0119] The catalyst is preferably used in an amount of 0.05 to 0.75% by weight, more preferably 0.1 to 0.6% by weight, and most particularly preferably 0.45 to 0.55% by weight, based on the total weight of part B.

[0120] In a preferred embodiment, the catalyst comprises or consists of 2,4,6-tris-(dimethylaminomethyl)phenol, used in an amount of 0.2 to 0.8 wt. %, more preferably 0.3 to 0.5 wt. %, based on the total weight of Part B.

[0121] In another preferred embodiment, the catalyst comprises or consists of 1,4-diazabicyclo[2.2.2]octane, used in an amount of 0.02 to 0.35 wt. %, more preferably 0.05 to 0.15 wt. %, based on the total weight of Part A.

[0122] In a particularly preferred embodiment, the catalyst comprises or consists of a mixture of 2,4,6-tris-(dimethylaminomethyl)phenol and 1,4-diazabicyclo[2.2.2]octane, comprising 0.2 to 0.8 wt. %, more preferably 0.3 to 0.5 wt. %, of 2,4,6-tris-(dimethylaminomethyl)phenol and 0.02 to 0.35 wt. %, more preferably 0.05 to 0.15 wt. %, of 1,4-diazabicyclo[2.2.2]octane, based on the total weight of Part B.

[0123] Optional Ingredients The adhesive composition of the present invention may optionally contain a plasticizer, which may be present in part A or B or both. Examples of plasticizers are esters, particularly diesters and triesters, especially those with a viscosity of 10 at 23°C. -4 Those having a vapor pressure of less than 1000 kJ / cm 3 hPa. Examples include dialkyl phthalate esters, alkyl esters of fatty acids, and phosphate esters (e.g., trioctyl phosphate). Diisononyl phthalate is particularly preferred. When used, plasticizers are typically present in an amount of 10 to 20 wt. %, preferably 12 to 18 wt. %, based on the total weight of the adhesive composition. In a particularly preferred embodiment, diisononyl phthalate is used in an amount of 12 to 18 wt. %, more preferably 16 to 17 wt. %, based on the total weight of the adhesive composition.

[0124] The adhesive composition of the present invention may optionally contain fillers such as carbon black, clays, carbonates (e.g., calcium carbonate), metal hydrates, and fumed silica, which may be present in part A or B or both, in addition to any thermally conductive filler. Fillers are preferably used in an amount of 0 to 10% by weight, preferably 1 to 6% by weight, more preferably 2 to 5% by weight, based on the total weight of the relevant part.

[0125] In a preferred embodiment, the adhesive of the present invention contains carbon black as a filler. The carbon black is not particularly limited. Preferred carbon black has a viscosity of at least 80, preferably at least 90, more preferably at least 95 cm3 per 100 g of carbon black, as measured according to ASTM D-2414-09. 3 In addition, the carbon black desirably has an iodine number of at least 80, as measured in accordance with ASTM D1510-11.

[0126] When used, carbon black is used in an amount of 5 to 30 wt %, more preferably 15 to 25 wt %, based on the total weight of the adhesive composition. In a particularly preferred embodiment, carbon black is used in an amount of 15 to 25 wt %, preferably 22 to 23 wt %, based on the total weight of the adhesive composition.

[0127] The adhesive composition of the present invention may optionally contain calcium carbonate in part A and / or part B in an amount of 0 to 5% by weight, more preferably 1 to 3% by weight, particularly preferably 1.5 to 2.5% by weight, based on the total weight of the relevant part. The calcium carbonate particles may be untreated or surface modified by treatment with chemical agents, such as organic acids or esters of organic acids.

[0128] The adhesive composition of the present invention may optionally contain fumed silica at 0 to 1.5 wt %, more preferably 0.5 to 1 wt %, based on the total weight of the adhesive.

[0129] When fumed silica is used, the particles may be untreated or may be surface modified by treatment with chemical agents such as chlorosilanes, dichlorosilanes, alkyltrialkoxysilanes, or polydimethylsiloxanes.

[0130] The adhesive composition of the present invention may optionally contain talc, which may be present in Component A or B, or both. In a preferred embodiment, talc is used in Component B at 25 to 40 wt %, more preferably 30 to 35 wt %, based on the total weight of Component B.

[0131] The adhesive compositions of the present invention may optionally include an adhesion promoter, which may be present in either Component A or B, or both. Suitable adhesion promoters include silanes, such as gamma-glycidoxypropyltrimethoxysilane. In a preferred embodiment, gamma-glycidoxypropyltrimethoxysilane is used in Part A at 0.1 to 1 wt %, preferably 0.3 to 0.6 wt %, based on the total weight of Part A.

[0132] The adhesive composition of the present invention may optionally include a flame retardant and a synergist. Examples of suitable flame retardants and synergists include: 1. Aluminum, zinc and titanium salts of diethylphosphinic acid, in particular aluminum diethylphosphinate; 2. Nitrogen and / or phosphorus-containing molecules, such as melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, etc.; 3. Aluminum and / or zinc phosphite Examples include:

[0133] A preferred flame retardant / synergist combination is aluminum diethylphosphinate plus melamine polyphosphate.

[0134] The adhesive compositions of the present invention may optionally include one or more additional stabilizers, such as heat, visible light, and UV stabilizers.

[0135] Examples of heat stabilizers include alkyl-substituted phenols, phosphites, sebacates, and cinnamates. When present, a preferred heat stabilizer is an organic phosphite, more specifically, trisnonylphenyl phosphite, as disclosed in U.S. Pat. No. 6,512,033, incorporated herein by reference. The heat stabilizer may comprise at least 0.01 or at least 0.3 weight percent, and at most 5 weight percent, 2 weight percent, or 1.0 weight percent, based on the total weight of the adhesive composition. The adhesive composition may avoid such heat stabilizers.

[0136] As for UV light stabilizers, they include benzophenones and benzotriazoles.Specific UV light absorbers include those manufactured by BASF, such as TINUVIN® P, TINUVIN® 326, TINUVIN® 213, TINUVIN® 327, TINUVIN® 571, and TINUVIN® 328, and those manufactured by Cytec, such as CYASORB® UV-9, CYASORB® UV-24, CYASORB® UV-1164, CYASORB® UV-2337, CYASORB® UV-2908, CYASORB® UV-5337, CYASORB® UV-531, and CYASORB® UV-3638.Among these, TINUVIN® 571 is preferred. The one or more UV light absorbers may comprise at least 0.1 weight percent, at least 0.2 weight percent, or at least 0.3 weight parts of the adhesive composition weight, and may comprise no more than 3 weight percent, no more than 2 weight percent, or no more than 1 weight percent thereof.

[0137] The adhesive composition of the present invention may further comprise one or more visible light stabilizers. Preferred visible light stabilizers include hindered amine visible light stabilizers such as TINUVIN™ 144, TINUVIN™ 622, TINUVIN™ 77, TINUVIN™ 123, TINUVIN™ 765, and CHIMASSORB™ 944, available from Cytec; and CYASORB™ UV-500, CYASORB™ UV-3581, and CYASORB™ UV-3346, all available from Ciba-Geigy. Of these, TINUVIN™ 765 is a preferred choice. The visible light stabilizer may comprise at least 0.1 weight percent, at least 0.2 weight percent, or at least 0.3 weight percent of the adhesive composition, and may comprise no more than 3 weight percent, no more than 2 weight percent, or no more than 1.5 weight percent.

[0138] Method for producing adhesive composition Part A and Part B are preferably prepared by mixing the ingredients in a planetary mixer or a double asymmetric centrifuge. In the first stage, the liquid phase is mixed, and then the solid materials are added to the formulation. The formulation is mixed under vacuum for about 30 minutes and then filled into cartridges, pails, or drums. The two parts are stored separately until use, at which point they are mixed.

[0139] How to use The present invention provides a method for bonding two substrates, comprising: (1)(A) and (B): (A) The following: (a1) General formula I:

[0140] [ka]

[0141] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; A second part (Part B) containing providing a two-part thermally conductive adhesive comprising: wherein at least one of Part A and Part B contains a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or more, and at least one of Part A and Part B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and Part A and Part B are designed to be stored isolated from each other and mixed together to form the adhesive mixture before use; (2) mixing Part A and Part B to create an adhesive mixture; (3) applying the adhesive mixture to a first substrate; (4) bringing a second substrate into adhesive contact with the first substrate; (5) curing the adhesive mixture; The present invention provides a method comprising:

[0142] As noted above, a preferred method of providing the adhesive of the present invention is in an airtight container, such as an airtight sealed tube. The container is opened immediately prior to use and the two parts are mixed.

[0143] Part A and Part B can be mixed in any ratio. In a preferred embodiment, the ratio of Part A to Part B is 0.5:1 to 1:0.5 (v:v), more preferably 1:1.5 to 1.5:1 (v:v), and particularly preferably 1:1 (v:v).

[0144] The adhesive composition of the present invention can be applied by any application method, for example, by spreading, applying through a nozzle, or the like, either manually or with a robotic device.

[0145] In a preferred embodiment, one or both of the first and second substrates is selected from aluminum, glass, steel, particularly aluminum, more particularly untreated aluminum, e-coated metal (Al, steel), powder coated metal, other coated metal, passivated aluminum, or plastic coated metal, plastic such as poly(ethylene terephthalate), polyethylene, polypropylene, polyamide, polyimide, polycarbonate, and particularly preferably aluminum.

[0146] Curing is accomplished by leaving the bonded assembly at room temperature. Full cure is typically observed after 1-2 days, although a 7-day cure period is often used.

[0147] Particularly preferred embodiments The following are particularly preferred embodiments of the adhesive composition of the present invention:

[0148] 1. A two-component thermally conductive adhesive, (A) The following: (a1) General formula I: [ka] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents4~8 alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; The second part (Part B) includes Including, wherein at least one of Part A and Part B contains a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or more, and at least one of Part A and Part B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and Part A and Part B are designed to be stored isolated from each other and mixed together to form the adhesive mixture before use. glue.

[0149] 2. A kit for forming a two-component thermally conductive adhesive, comprising: (A) The following: (a1) General formula I: [ka] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; The second part (Part B) includes Including, wherein at least one of Part A and Part B contains a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or more, and at least one of Part A and Part B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and Part A and Part B are designed to be stored isolated from each other and mixed together to form the adhesive mixture before use. kit.

[0150] 3. A method for bonding a first substrate to a second substrate, comprising: (1)(A) and (B): (A) The following: (a1) General formula I: [ka] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; The second part (Part B) includes providing a two-part thermally conductive adhesive comprising: wherein at least one of Part A and Part B comprises a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or greater, and at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I; (2) mixing Part A and Part B to create an adhesive mixture; (3) applying the adhesive mixture to a first substrate; (4) bringing a second substrate into adhesive contact with the first substrate; (5) curing the adhesive mixture; A method comprising:

[0151] 4. (1) a first substrate; (2) a second substrate; (3)(A) and (B): (A) The following: (a1) General formula I: [ka] (In the formula, R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene group) at least one compound of (a2) at least one liquid epoxy resin The first part (Part A) includes: (B) The following: (b1) at least one polyamine having two or more primary or secondary amine functional groups; A second part (Part B) containing A mixture of wherein at least one of Part A and Part B comprises a thermally conductive filler such that when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or greater, and at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I. A thermally conductive adhesive composition resulting from curing 1. An adhesive assembly comprising: a first and second substrate in adhesive contact with the adhesive composition sandwiched therebetween; Adhesive assembly.

[0152] 5.R 1 and R 2 are independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl, and R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 Any one of embodiments 1 to 4, wherein the alkylene group.

[0153] 6.R 1 and R 2 are independently selected from H and C1-C4 alkyl, more preferably H and C1-C2 alkyl, and particularly preferably R 1 and R 2 Any one of embodiments 1 to 5, wherein is H.

[0154] 7. Any one of embodiments 1-6, wherein n is 1.

[0155] 8.R 3 is C1-C4 alkyl, more preferably R 3 is C1-C2 alkyl, and particularly preferably R 3 Any one of embodiments 1-7, wherein is ethyl.

[0156] 9.R 4Any one of embodiments 1 to 8, wherein is a divalent C6 alkylene group having 2 to 5 methyl substituents on the alkylene chain.

[0157] 10.R 4 Any one of embodiments 1-9, wherein is a C6 alkylene group having three methyl substituents on the alkylene chain.

[0158] 11. Compounds of general formula I have the formula I'': [ka] Any one of embodiments 1 to 10,

[0159] 12. Any one of embodiments 1-11, wherein the at least one liquid epoxy resin is chosen from epoxy resins that are liquid at 23°C.

[0160] 13. Any one of embodiments 1-12, wherein the liquid epoxy resin has a viscosity at 23°C of 50 Pas or less, more preferably 25 Pas or less, and particularly preferably 15 Pas or less.

[0161] 14. Any one of embodiments 1-13, wherein if only a single epoxy resin is present, it is liquid at 23°C.

[0162] 15. Any one of embodiments 1-14, wherein when two or more epoxy resins are present, the individual epoxy resins within the mixture may themselves be solid at 23°C, but the mixture thereof is liquid at 23°C.

[0163] 16. Any one of embodiments 1-15, wherein the at least one liquid epoxy resin has an average of at least 1.8, preferably at least 2.0, epoxide groups per molecule.

[0164] 17. Any one of embodiments 1-16, wherein the at least one liquid epoxy resin comprises an epoxy resin having an epoxy equivalent weight of 75 to 350 g / eq, preferably 140 to 250 g / eq, and more preferably 150 to 225 g / eq.

[0165] 18. Any one of embodiments 1-17, wherein the epoxy resin is selected from diglycidyl ethers of polyhydric phenolic compounds, such as resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, and tetramethylbiphenol; diglycidyl ethers of aliphatic glycols, such as diglycidyl ethers of C2-24 alkylene glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins (epoxy novolac resins), alkyl-substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenolic resins, and dicyclopentadiene-substituted phenolic resins; and any combination of any two or more thereof.

[0166] 19. Any one of embodiments 1-18, wherein the at least one epoxy resin comprises or consists of a reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent weight (according to ASTM D-1652) of 176 to 185 g / eq, an epoxide percentage (according to ASTM D-1652) of 23.2 to 24.4%, an epoxide group content (according to ASTM D-1652) of 5,400 to 5,680 mmol / kg, and a viscosity at 25°C (according to ASTM D-445) of 7,000 to 10,000 MPas.

[0167] 20. Any one of embodiments 1-19, wherein the liquid epoxy resin is present in an amount of 2 to 20 wt. %, more preferably 2 to 10 wt. %, and especially preferably 4 to 8 wt. %, based on the total weight of Part A.

[0168] 21. Any one of embodiments 1-20, wherein the liquid epoxy resin is present at 12-50 wt.%, more preferably 15-35 wt.%, and more particularly preferably 20-30 wt.%, based on the total organic content of Part A.

[0169] 22. Any one of embodiments 1 to 21, wherein the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent weight (according to ASTM D-1652) of 176 to 185 g / eq, an epoxide percentage (according to ASTM D-1652) of 23.2 to 24.4%, an epoxide group content (according to ASTM D-1652) of 5,400 to 5,680 mmol / kg, and a viscosity (according to ASTM D-445) of 7,000 to 10,000 MPas, and is present in Part A at 2 to 20 wt. %, more preferably 2 to 10 wt. %, and particularly preferably 4 to 8 wt. %, based on the total weight of Part A.

[0170] 23. Any one of embodiments 1-22, wherein the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent weight (according to ASTM D-1652) of 176 to 185 g / eq, an epoxide percentage (according to ASTM D-1652) of 23.2 to 24.4%, an epoxide group content (according to ASTM D-1652) of 5,400 to 5,680 mmol / kg, and a viscosity at 25°C (according to ASTM D-445) of 7,000 to 10,000 MPas, and is present in Part A at 12 to 50 wt%, more preferably 15 to 35 wt%, and more particularly preferably 20 to 30 wt%, based on the total weight of Part A.

[0171] 24. Any one of embodiments 1-23, wherein both part A and / or part B comprise a thermally conductive filler.

[0172] 25. Any one of embodiments 1-24, wherein Part A and / or Part B comprises a thermally conductive filler selected from those having a thermal conductivity coefficient greater than 5 W / m°K, more preferably greater than 10 W / m°K, or particularly preferably greater than 15 W / m°K.

[0173] 26. Any one of embodiments 1-25, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is selected from alumina, alumina trihydrate or aluminum trihydroxide (ATH), silicon carbide, boron nitride, diamond, and graphite, and mixtures thereof.

[0174] 27. Any one of embodiments 1-26, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is selected from aluminum trihydroxide (ATH) and aluminum oxide, with ATH being most preferred.

[0175] 28. Part A and / or Part B contain a thermally conductive filler, and the thermally conductive filler has a D of 3 or greater or about 3 or greater. 90 / D 50 Any one of the preceding embodiments, having a broad particle size distribution characterized by the ratio:

[0176] 29. Part A and / or Part B includes a thermally conductive filler, and the thermally conductive filler has a D of 3 or greater or about 3 or greater. 90 / D 50 Any one of embodiments 1-28, wherein the aluminum oxide is ATH or aluminum oxide, most preferably ATH, having a broad particle size distribution characterized by the ratio

[0177] 30. Any one of embodiments 1-29, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler has a bimodal particle size distribution.

[0178] 31. Part A and / or Part B comprises a thermally conductive filler, the thermally conductive filler having a ratio D of 3 or more or about 3 or more, more preferably 5 or more or about 5 or more, and more particularly preferably 9 or more or about 9 or more. 90 / D 50 Any one of embodiments 1 to 30, comprising:

[0179] 32. Part A and / or Part B comprises a thermally conductive filler, the thermally conductive filler having the following particle size distribution (preferably at 1 g / l by laser diffraction in deionized water containing a dispersing aid, such as Na4P2O7×10H2O): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 Any one of embodiments 1-31, wherein the ATH is a bimodal distribution aluminum trihydroxide (ATH) having:

[0180] 33. Any one of embodiments 1 to 32, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is present in the final adhesive resulting from mixing Part A and Part B in a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and even more preferably 60 to 85 wt. %, based on the total weight of the adhesive.

[0181] 34. Any one of embodiments 1-33, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is aluminum trihydroxide (ATH), used at a concentration of 30-85 wt. %, more preferably 40-85 wt. %, and more particularly preferably 60-85 wt. %, based on the total weight of the adhesive.

[0182] 35. Any one of embodiments 1-34, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is bimodal aluminum trihydroxide (ATH) used in a concentration of 30-85 wt. %, more preferably 40-85 wt. %, and even more preferably 60-85 wt. %, based on the total weight of the adhesive. 36. Part A and / or Part B comprises a thermally conductive filler, the thermally conductive filler having the following particle size distribution (preferably at 1 g / l by laser diffraction in deionized water containing a dispersing aid, such as Na4P2O7×10H2OO): D 10 (microns) 0.5 D 50(microns) 8 D 90 (microns) 80 and Any one of embodiments 1 to 35, wherein the aluminum trihydroxide (ATH) is used at a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and more particularly preferably 60 to 85 wt. %, based on the total weight of the adhesive.

[0183] 37. Any one of embodiments 1 to 36, wherein Part A and / or Part B comprises a thermally conductive filler, and the concentration of the thermally conductive filler in Part A is 30 to 85 wt. %, more preferably 40 to 85 wt. %, and more particularly preferably 60 to 85 wt. %, based on the total weight of Part A.

[0184] 38. Any one of embodiments 1 to 37, wherein Part A and / or Part B comprises a thermally conductive filler, and the concentration of the thermally conductive filler in Part B is 30 to 85 wt. %, more preferably 40 to 85 wt. %, and more particularly preferably 60 to 85 wt. %, based on the total weight of Part B.

[0185] 39. Any one of embodiments 1-38, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is aluminum trihydroxide (ATH), used in Part A and / or Part B at a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and more particularly preferably 60 to 85 wt. %, based on the total weight of Part A or Part B.

[0186] 40. Any one of embodiments 1-39, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is an ATH having a bimodal particle size, used in Part A and / or Part B at a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and more particularly preferably 60 to 85 wt. %, based on the total weight of Part A or Part B.

[0187] 41. Part A and / or Part B comprises a thermally conductive filler, the thermally conductive filler having the following particle size distribution (preferably at 1 g / l by laser diffraction in deionized water containing a dispersing aid, such as Na4P2O7×10H2O): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 and Any one of embodiments 1-40, wherein aluminum trihydroxide (ATH) is used in Part A and / or Part B at a concentration of 30 to 85 wt. %, more preferably 40 to 85 wt. %, and more particularly preferably 60 to 85 wt. %, based on the total weight of Part A or Part B.

[0188] 42. Any one of embodiments 1-41, wherein the at least one polyamine comprises a polyamine having a molecular weight of at least 400 Da, more preferably at least 1,000 Da, and more particularly preferably at least 2,000 Da.

[0189] 43. Any one of embodiments 1-42, wherein the at least one polyamine comprises a polyamine having a molecular weight of 2,000 to 4,000 Da, more preferably about 3,000 Da.

[0190] 44. Any one of embodiments 1-43, wherein the at least one polyamine comprises a polyamine having a molecular weight of at least 300 Da, more preferably at least 350 Da, and more particularly preferably at least 400 Da.

[0191] 45. Any one of embodiments 1-44, wherein the at least one polyamine comprises a polyamine having a molecular weight of 300-500 Da, more preferably about 400-440 Da.

[0192] 46. ​​Any one of embodiments 1-45, wherein the polyamine comprises a triamine having primary amine groups and having a molecular weight of 2,000 to 4,000 Da, more preferably 3,000 Da.

[0193] 47. Any one of embodiments 1-46, wherein the polyamine comprises a polyoxyalkylene polyamine having two or more amine groups per polyamine, two to four amine groups per polyamine, or two to three amine groups per polyamine.

[0194] 48. Any one of embodiments 1-47, wherein the polyamine comprises a polyetheramine having three amine groups.

[0195] 49. Any one of embodiments 1-48, wherein the polyamine comprises a polyamine based on a propylene oxide polyether backbone.

[0196] 50. Any one of embodiments 1-49, wherein the polyamine comprises a trifunctional primary amine having an average molecular weight of approximately 440.

[0197] 51. A polyamine has the following structure: [ka] Any one of embodiments 1-50, comprising a polyetheramine having

[0198] 52. Polyamines have the formula: [ka] Any one of embodiments 1-51, comprising a triamine of approximately 3000 molecular weight.

[0199] 53. At least one polyamine has the formula: [ka] a triamine of approximately 3000 molecular weight, The general structure is: [ka] Any one of the preceding embodiments, comprising or consisting of a mixture of a polyether triamine of approximately 440 molecular weight and a hydroxypropyl methylcellulose of 1,2-dimethyl-2,3-dimethyl-1,3-dimethyl-2,4-dimethyl-1,4 ...

[0200] 54. Any one of embodiments 1 to 53, wherein the at least one polyamine is present in Part B in an amount of 8 to 30% by weight, more preferably 10 to 20% by weight, and more particularly preferably 12 to 16% by weight, based on the total weight of Part B.

[0201] 55. Any one of embodiments 1 to 54, wherein the at least one polyamine is present in Part B in an amount of 80 to 99 wt. %, more preferably 85 to 95 wt. %, and particularly preferably 87 to 92 wt. %, based on the organic content of Part B.

[0202] 56. Any one of embodiments 1 to 55, wherein the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines used in Part B in an amount of 8 to 30% by weight, more preferably 10 to 20% by weight, and more particularly preferably 12 to 16% by weight, based on the total weight of Part B.

[0203] 57. Any one of embodiments 1-56, wherein the at least one polyamine comprises or consists of a mixture of approximately 3,000 Da polyethertriamine and approximately 440 Da polyethertriamine, used in Part B in an amount of 8 to 30 wt. %, more preferably 10 to 20 wt. %, and more particularly preferably 12 to 16 wt. %, based on the total weight of Part B.

[0204] 58. Any one of embodiments 1 to 57, wherein the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines used in Part B in an amount of 80 to 99 wt. %, more preferably 85 to 95 wt. %, and particularly preferably 87 to 92 wt. %, based on the organic content of Part B.

[0205] 59. Any one of embodiments 1 to 58, wherein the at least one polyamine comprises or consists of a mixture of approximately 3,000 Da polyethertriamine and approximately 440 Da polyethertriamine, used in Part B in an amount of 80 to 99 wt. %, more preferably 85 to 95 wt. %, and particularly preferably 87 to 92 wt. %, based on the organic content of Part B.

[0206] 60. Any one of embodiments 1-59, wherein the catalyst is selected from tertiary amine catalysts.

[0207] 61. Any one of embodiments 1-60, wherein the catalyst is selected from 2,4,6-tris-(dimethylaminomethyl)phenol, tetramethylguanidine, heptamethylisobiguanide, N,N-dimethylbenzylamine, 1,4-diazabicyclo[2.2.2]octane, and mixtures thereof.

[0208] 62. Any one of embodiments 1-61, wherein the catalyst comprises or consists of 2,4,6-tris-(dimethylaminomethyl)phenol.

[0209] 63. Any one of embodiments 1-62, wherein the catalyst comprises or consists of 1,4-diazabicyclo[2.2.2]octane.

[0210] 64. Any one of embodiments 1-63, wherein the catalyst is a mixture of 2,4,6-tris-(dimethylaminomethyl)phenol and 1,4-diazabicyclo[2.2.2]octane.

[0211] 65. Any one of embodiments 1-63, wherein the catalyst is present in part A and / or part B.

[0212] 66. Any one of embodiments 1-65, wherein the catalyst is present in Part B.

[0213] 67. Any one of embodiments 1 to 66, wherein the catalyst is used in an amount of 0.05 to 0.75 wt. %, more preferably 0.1 to 0.6 wt. %, and more particularly preferably 0.45 to 0.55 wt. %, based on the total weight of Part B.

[0214] 68. Any one of embodiments 1-67, wherein the catalyst comprises or consists of 2,4,6-tris-(dimethylaminomethyl)phenol, used in an amount of 0.2 to 0.8 wt. %, more preferably 0.3 to 0.5 wt. %, based on the total weight of Part B.

[0215] 69. Any one of embodiments 1-68, wherein the catalyst comprises or consists of 1,4-diazabicyclo[2.2.2]octane, used in an amount of 0.02 to 0.35 wt. %, more preferably 0.05 to 0.15 wt. %, based on the total weight of Part A.

[0216] 70. Any one of embodiments 1-69, wherein the catalyst comprises or consists of a mixture of 2,4,6-tris-(dimethylaminomethyl)phenol and 1,4-diazabicyclo[2.2.2]octane, comprising 0.2 to 0.8 wt. %, more preferably 0.3 to 0.5 wt. % of 2,4,6-tris-(dimethylaminomethyl)phenol and 0.02 to 0.35 wt. %, more preferably 0.05 to 0.15 wt. % of 1,4-diazabicyclo[2.2.4]octane, based on the total weight of Part B.

[0217] 71. Any one of embodiments 1-70, wherein Part A and / or Part B comprises a plasticizer.

[0218] 72. Any one of embodiments 1-71, wherein Part A and / or Part B comprises a filler in addition to any thermally conductive filler.

[0219] 73. Any one of embodiments 1-72, wherein Part A and / or Part B comprises a filler selected from carbon black, clay, carbonates (e.g., calcium carbonate), metal hydrates, fumed silica, and mixtures thereof.

[0220] 74. Any one of embodiments 1-73, wherein Part A and / or Part B comprises a filler used in an amount of 0-10 wt.%, preferably 1-6 wt.%, more preferably 2-5 wt.%, based on the total weight of the relevant part.

[0221] 75. Any one of embodiments 1-74, wherein part A and / or part B comprises 0-5 wt.-%, more preferably 1-3 wt.-%, and particularly preferably 1.5-2.5 wt.-% calcium carbonate, based on the total weight of the relevant part.

[0222] 76. Any one of embodiments 1-75, wherein Part A and / or Part B comprises one or more adhesion promoters.

[0223] 77. Any one of embodiments 1-76, wherein Part A and / or Part B comprises one or more adhesion promoters in the form of one or more silanes.

[0224] 78. Any one of embodiments 1-77, wherein Part A and / or Part B comprises one or more adhesion promoters in the form of one or more aminosilanes, mercaptosilanes, and epoxysilanes.

[0225] 79. Any one of embodiments 1-78, wherein Part A and / or Part B comprises gamma-glycidoxypropyltrimethoxysilane.

[0226] 80. Any one of embodiments 1-79, wherein Part A comprises 0.1 to 1 wt. %, preferably 0.3 to 0.6 wt. %, of gamma-glycidoxypropyltrimethoxysilane, based on the total weight of Part A. [Example]

[0227] [Table 1]

[0228] [Table 2]

[0229] [Table 3]

[0230] GF210 and GF213 Prepolymer Preparation (Conventional and CPEE-Capped Prepolymers) The following procedure was carried out using the amounts listed in Table 3: Voranol 1010 was added to a laboratory reactor and heated to 130°C under stirring and vacuum. Once this temperature was reached, the mixture was cooled to 70°C with stirring. The vacuum was broken and HDI was added. The mixture was stirred under nitrogen for 2 minutes, and the bismuth catalyst (TiB 718) was added. The mixture was allowed to react at an 85°C bath temperature under stirring and nitrogen for 45 minutes. The mixture was then cooled to 60°C under stirring and nitrogen. CPEE was added, and the mixture was allowed to react at an 85°C bath temperature under stirring and nitrogen for 45 minutes. The isocyanate content was checked, and if 0, the mixture was stirred at 85°C under vacuum for an additional 20 minutes. The prepolymer was stored under an inert atmosphere until use.

[0231] Preparation of CPEE-functionalized diisocyanates (GF216, GF217, GF 218, GF219) The following procedure was carried out using the amounts listed in Table 2: The diisocyanate and bismuth catalyst (TiB 718) were added to a laboratory reactor and mixed under nitrogen at 23°C. The CPEE was added in small portions, taking care not to allow the temperature to exceed 60°C. After all the CPEE was added, the mixture was stirred under vacuum at a bath temperature of 70°C for 45 minutes. The CPEE-functionalized diisocyanate was stored under an inert atmosphere until use.

[0232] [Table 4]

[0233] Considerations for CPEE-functionalized molecules When MDI is functionalized with CPEE (GF216), the resulting product is solid at room temperature, which is undesirable for an adhesive monomer. The same is true when HDI is functionalized with CPEE (GF217).

[0234] When IPDI is functionalized with CPEE (GF218), the result is a liquid, but the viscosity at 23° C. is high (310 Pa.s), making it unsuitable for use as an adhesive monomer.

[0235] When 2,4,4-trimethylhexamethylene diisocyanate is functionalized with CPEE, the result is an easy-to-manage liquid with a viscosity suitable for use as a monomer for adhesives.

[0236] adhesive formulation Using the ingredients listed in Table 3, formulations were mixed in a planetary mixer or a dual asymmetric centrifuge. In the first stage, the liquid phase was mixed, and then the solid materials were added to the formulation. The formulations were mixed under vacuum for approximately 30 minutes and then filled into cartridges, pails, or drums.

[0237] [Table 5]

[0238] [Table 6]

[0239] [Table 7]

[0240] Test Method viscosity Rheological measurements were performed on an Anton Paar MC 302 rheometer in parallel plate geometry. 25 mm diameter plates were used, with a gap fixed at 0.5 mm. The material was placed between the two plates, and shear rate tests were then performed at 0.001 to 20 1 / s. -1 The viscosity at is reported.

[0241] Press-fitting The press-in force is measured with a tensiometer (Zwick). The material is placed on a metal surface. A 40 mm diameter aluminum piston is placed on top and compresses the material to 5 mm (initial position). The material is then compressed to 0.3 mm at a speed of 1 mm / s and the force-displacement curve is recorded. The force (N) at a thickness of 0.5 mm is considered as the press-in force and is reported in Table 3.

[0242] thermal conductivity Thermal conductivity is measured according to ASTM 5470-12 on a Thermal Interface Materials Tester manufactured by ZFW Stuttgart. Testing is performed in Spaltplus mode at thicknesses of 1.8-1.2 mm. The material is considered a Type I (viscous liquid) as described in ASTM 5470-12. The upper contact is heated to approximately 40°C and the lower contact to approximately 10°C, resulting in a sample temperature of approximately 25°C. The A and B components are mixed in a static mixer when applied from a manual cartridge system.

[0243] GPC The molecular weight data of the polyurethane prepolymers were determined by gel permeation chromatography (GPC) on a Malvern Viscothek GPC max instrument using EMSURE-THF (ACS, Reag. Ph EUR analytical grade) as the eluent, PL GEL MIXED D (Agilent, 300 × 7.5 mm, 5 μm) as the column, and a Malvern Viscotek TDA as the detector.

[0244] Lap shear strength Aluminum substrates (Novelis, AA6061 T6 1.92 mm MF noPT no lub) (140 × 25 mm, 1.9 mm thick) were used. The substrates were cleaned with isopropanol before use. The adhesive was applied to one substrate, and the second substrate was bonded within 5 minutes. The thickness was adjusted to 1.0 mm, and the overlap area was 25 mm × 25 mm. The material was cured and stored at 23 °C and 50% relative humidity for 7 days before lap shear testing. The lap shear specimens were then mounted on a tensile meter and subjected to lap shear testing using a pulling rate of 10 mm / min. Force-deflection curves were recorded, and the strength at break was reported as the lap shear strength.

[0245] NCO content NCO measurements were performed according to ASTM D2572-97 (Reapproved 2010) (GEX081). This test method is applicable to isocyanate-containing fluids, including monomers (e.g., methylene diphenyl diisocyanate (MDI)), prepolymers, and adhesive formulations. The isocyanate (NCO) sample was reacted with excess dibutylamine to form the corresponding urea. The NCO content was determined from the amount of dibutylamine consumed in the reaction. Results are reported as percent NCO (weight percent).

[0246] result As noted above, the results in Table 2 show that of the diisocyanates tested, only the branched aliphatic diisocyanate, TMDI, resulted in a reaction product with CPEE that was a liquid with a viscosity suitable for use as a "prepolymer."

[0247] The data in Table 3 show that the highest lap shear strength was obtained when the molecule of general formula I (TMDI-CPEE) was used in Part A (IE1) in combination with a liquid epoxy resin (DER 330). In contrast, conventional polyurethane prepolymers (see Desmodur E21, CE1 and CE2) gave significantly lower lap shear strengths both with (CE2) and without (CE1) the epoxy.

[0248] Inventive Example 1 also exhibits good thermal conductivity of 1.8, demonstrating that it is possible to have high loadings of thermally conductive fillers while not compromising lap shear strength.

Claims

1. A two-component thermal conductive adhesive, (A) See below: (a1) General formula I: 【Chemistry 1】 (wherein, R 1 and R 2 are each independently selected from hydrogen and C 1 - C 6 alkyl, n is an integer of 1 - 2, R 3 is C 1 - C 6 alkyl, R 4 is a divalent C 1~3 alkylene group having 2 - 5 C 4~8 alkyl substituents on the alkylene chain) At least one compound of; (a2) at least one liquid epoxy resin The first part (Part A) includes; (B) See below: (b1) At least one polyamine having two or more primary or secondary amine functional groups The second part (Part B) includes Includes, Here, when Part A and Part B are mixed to form an adhesive mixture, the concentration of the thermally conductive filler in the adhesive mixture is 70% by weight or more based on the total weight of the adhesive mixture, such that at least one of Part A and Part B contains a thermally conductive filler, and at least one of Part A and Part B contains a catalyst capable of catalyzing the reaction between an amine and a compound of general formula I, and Part A and Part B are designed to be stored isolated from each other and mixed together before use to form an adhesive mixture. glue.

2. R 1 and R 2 These are, independently, hydrogen and C 1 ~C 6 Selected from alkyl groups, where n is an integer between 1 and 2, R 3 is C 1 ~C 6 It is alkyl, R 4 There are 2 to 5 C atoms on the Achillene chain. 1~3 Divalent C having alkyl substituents 4~8 The adhesive according to claim 1, wherein the group is an alkylene group.

3. R 1 and R 2 The adhesive according to claim 2, wherein is independently selected from H and C1-C4 alkyl.

4. The adhesive according to claim 2, wherein n is 1.

5. R 3 is C 1 ~C 4 The adhesive according to claim 2, wherein it is alkyl.

6. R 4 This is a divalent C having 2 to 5 methyl substituents on the alkylene chain. 6 The adhesive according to claim 2, wherein the adhesive is an alkylene group.

7. R 4 This is a C with three methyl substituents on the alkylene chain. 6 The adhesive according to claim 2, wherein the adhesive is an alkylene group.

8. The compound of general formula I is formula I'': 【Chemistry 2】 The adhesive according to claim 1.

9. The adhesive according to claim 1, wherein the at least one liquid epoxy resin has an average of at least 1.8 epoxide groups per molecule.

10. The adhesive according to claim 1, wherein the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A.

11. The adhesive according to claim 1, wherein the liquid epoxy resin is present in an amount of 2 to 20% by weight based on the total weight of part A.

12. The adhesive according to claim 1, wherein part A and / or part B comprises a thermally conductive filler, the thermally conductive filler being selected from aluminum trihydrate (ATH) and aluminum oxide.

13. The adhesive according to claim 1, wherein part A and / or part B comprises a thermally conductive filler, the thermally conductive filler having a bimodal particle size distribution.

14. The adhesive according to claim 13, wherein part A and / or part B comprises a thermally conductive filler, wherein the thermally conductive filler is a bimodal aluminum trihydrate (ATH) used at a concentration of 30 to 85% by weight, based on the total weight of the adhesive.

15. The adhesive according to claim 1, wherein the at least one polyamine comprises a polyamine having a molecular weight of at least 400 Da.

16. The adhesive according to claim 15, wherein the at least one polyamine comprises a polyamine having a molecular weight of 2,000 to 4,000 Da.

17. The adhesive according to claim 1, wherein the at least one polyamine comprises a mixture of a triamine having a molecular weight of 400 to 450 Da and a triamine having a molecular weight of approximately 3,000 Da.

18. The adhesive according to claim 1, wherein the catalyst is selected from tertiary amine catalysts.

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