Two-component adhesive composition

Abstract

Provided herein are novel monomers for producing polymers, particularly adhesives, and adhesives produced using the novel monomers.

Description

[Technical Field]

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

[0002] Two-part polyurethane and epoxy adhesives are well known in the art and offer a wide variety of adhesives with a wide range of properties making them suitable for many different applications.

[0003] Two-part polyurethane adhesives typically contain an isocyanate component, which contains molecules with isocyanate (NCO) functionality, and a polyol component, which contains molecules with multiple OH functional groups. The two components are stored separately until use and are then mixed. Curing is initiated by the reaction of the NCO functional groups of the isocyanate component with the OH functional groups of the polyol component to form urethane bonds, resulting in the formation of a cured three-dimensional matrix.

[0004] The isocyanate component is often in the form of a prepolymer formed by reaction of excess NCO groups with a polyol or polyols, resulting in a medium to high molecular weight polymer terminated with NCO groups, which react with the OH functional groups of the polyol component to form a cured network after mixing at the time of use.

[0005] While NCO-terminated prepolymers are useful in many situations, there are some concerns regarding their health and safety performance. Because monomeric diisocyanates are inherently toxic, the adhesives are often classified as carcinogens. Therefore, there is a need for alternative two-component solutions that exhibit similar final properties upon curing but are subject to less stringent labeling requirements.

[0006] It is known to modify NCO-terminated polyurethane prepolymers by reacting the terminal NCO functional groups of the prepolymer with molecules such as ethyl 2-oxocyclopentane-1-carboxylate (CPEE). This technique offers several advantages, including the elimination of toxic NCO groups, the same terminal cure characteristics as NCO-terminated polyurethanes, and fast cure rates. However, CPEE-terminated prepolymers typically suffer from a decrease in lap shear strength upon curing. Summary of the Invention [Means for solving the problem]

[0007] In a first aspect, the present invention provides compounds of general formula I:

[0008] [ka]

[0009] (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 radical) to provide.

[0010] In a second aspect, the present invention provides compounds of 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 R4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene radical) as a monomer in a polymer.

[0013] In a third aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: (A) (a1) at least one compound of 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 radical) A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: A two-component adhesive comprising: Provided is a two-part adhesive, wherein at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are designed to be mixed together to form an adhesive mixture prior to use.

[0016] In a fourth aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: (A) (a1) at least one compound of 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 radical) A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: 1. A kit for forming an adhesive comprising: The kit is provided in which at least one of parts A and B contains a catalyst capable of catalyzing the reaction between an amine and a compound of general formula I, and parts A and B are stored separately from each other and are designed to be mixed together before use to form an adhesive mixture.

[0019] In a fifth aspect, the present invention provides a method for producing a pharmaceutical composition comprising: (1) (A) a step of preparing a two-component adhesive, the two-component adhesive comprising: (a1) at least one compound of 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 radical) A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: Including, at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are designed to be mixed together to form an adhesive mixture prior to use; (2) mixing Part A and Part B to form an adhesive mixture; (3) applying the adhesive mixture to a first substrate; (4) bringing a second substrate into adhesive contact with the first substrate; and (5) curing the adhesive mixture; The present invention provides a method for bonding a first substrate to a second substrate, comprising:

[0022] In a sixth aspect, the present invention provides a method for producing a pharmaceutical composition comprising: (1) a first substrate; (2) a second substrate; (3) An adhesive composition, (A) (a1) at least one compound of general formula I:

[0023] [ka]

[0024] (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 radical) A first liquid (liquid A) containing (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; A second liquid (liquid B) containing an adhesive composition obtained by curing the mixture; A bonded assembly comprising: At least one of parts A and B includes a catalyst capable of catalyzing the reaction between an amine and a compound of general formula I, and a bonded assembly is provided in which first and second substrates are in adhesive contact with the adhesive composition sandwiched therebetween.

[0025] In a seventh aspect, the present invention provides a process for preparing a compound of general formula I, comprising reacting a molecule of formula III with at least two equivalents of a molecule of formula IV in the presence of a catalyst:

[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 radical). DETAILED DESCRIPTION OF THE INVENTION

[0028] We 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.

[0029] 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

[0030] Polymer molecular weights reported herein are reported in Daltons (Da) as number average molecular weight or weight average molecular weight as determined by gel permeation chromatography (GPC).

[0031] Compounds of general formula I In a first aspect, the present invention provides compounds of general formula I:

[0032] [ka]

[0033] (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 radical) to provide.

[0034] 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.

[0035] In a preferred embodiment, n is 1.

[0036] In a preferred embodiment, R 3 is C1-C4 alkyl, more preferably R3 is C1-C2 alkyl, and particularly preferably R 3 is ethyl.

[0037] In a preferred embodiment, R 4 is a divalent C6 alkylene radical having 2 to 5 methyl substituents on the alkylene chain. In a more preferred embodiment, R 4 is a C6 alkylene radical with three methyl substituents on the alkylene chain.

[0038] In a particularly preferred embodiment, the compound of general formula I is a compound of formula I″:

[0039] [ka]

[0040] is.

[0041] The compound of general formula I can be reacted with a diisocyanate of formula III: in the presence of a catalyst capable of catalyzing the reaction of NCO groups with a molecule of general formula IV:

[0042] [ka]

[0043] (In the formula, R 4 are as defined above, including preferred embodiments) with at least two equivalents of a compound of formula IV:

[0044] [ka]

[0045] (In the formula, R 1 , R 2 , R 3 and n is as defined above, including preferred embodiments. 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.

[0046] In one example of synthesis, 2,4,4-trimethylhexamethylene diisocyanate (II) 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:

[0047] [ka]

[0048] In another preferred embodiment of the synthesis, 2,4,4-trimethylhexamethylene diisocyanate (II) is reacted with at least two equivalents of ethyl 2-oxocyclopentane-1-carboxylate in the presence of a bismuth and / or zinc catalyst, in particular a mixture of bismuth and / or zinc catalysts:

[0049] [ka]

[0050] At least one liquid epoxy resin Part A of the adhesive of the present invention optionally contains at least one liquid epoxy resin, and liquid epoxy resin here means an epoxy resin that is liquid at 23°C. Preferably, the liquid epoxy resin has a viscosity of 50 Pas or less, more preferably 25 Pas or less, and particularly preferably 15 Pas or less at 23°C, which can be measured using a Kinexus (Bohlin) apparatus with a 20 mm diameter cone-plate geometry (4° cone) at a viscosity of 0.1 to 20 Pas. -1 The shear rate is measured at 23°C over a shear rate up / down curve.

[0051] The liquid epoxy resin is preferably not rubber-modified.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] Suitable epoxy resins include diglycidyl ethers of bisphenol A resins, such as those sold by Olin Corporation as DER® 330, DER® 331, DER® 332, DER® 383, DER661, and DER® 662 resins.

[0056] 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 proportion (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.

[0057] Epoxy novolac resins may be used, such as those commercially available from Olin Corporation as DEN® 354, DEN® 431, DEN® 438, and DEN® 439.

[0058] Other suitable epoxy resins are cycloaliphatic epoxides, which have the following structure V:

[0059] [ka]

[0060] (wherein R is an aliphatic, alicyclic, and / or aromatic group, and n is a number from 1 to 10, preferably 2 to 4), the alicyclic epoxide comprises a saturated carbocyclic ring with epoxy oxygens bonded to two adjacent atoms in the carbocyclic ring. 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.

[0061] 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.

[0062] The liquid epoxy resin is present in an amount of preferably 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 Liquid A.

[0063] The liquid epoxy resin is present in an amount of preferably 12 to 50% by weight, more preferably 15 to 35% by weight, and particularly preferably 20 to 30% by weight, based on the total organic content of Liquid A.

[0064] In a preferred embodiment, the at least one epoxy resin comprises the liquid reaction product of epichlorohydrin and bisphenol A, has an epoxide equivalent weight (per ASTM D-1652) of 176-185 g / eq, an epoxide fraction (per ASTM D-1652) of 23.2-24.4%, an epoxide group content (per ASTM D-1652) of 5,400-5,680 mmol / kg, and a viscosity (per ASTM D-445) of 7,000-10,000 MPas at 25°C, and is present in Part A at 2-20 wt%, more preferably 2-10 wt%, and most preferably 4-8 wt%, based on the total weight of Part A.

[0065] In another preferred embodiment, the at least one liquid epoxy resin comprises the liquid reaction product of epichlorohydrin and bisphenol A, has an epoxide equivalent weight (per ASTM D-1652) of 176-185 g / eq, an epoxide fraction (per ASTM D-1652) of 23.2-24.4%, an epoxide group content (per ASTM D-1652) of 5,400-5,680 mmol / kg, and a viscosity (per ASTM D-445) of 7,000-10,000 MPas at 25°C, and is present in Part A in an amount of 12-50 wt. %, more preferably 15-35 wt. %, and especially preferably 20-30 wt. %, based on the total organic content of Part A.

[0066] Thermally conductive filler In certain preferred embodiments, where it is desired that the cured adhesive have a thermal conductivity of preferably 1.5 W / mK or greater, Part A and / or Part B may contain a thermally conductive filler.

[0067] The thermally conductive filler is not particularly limited. Suitable thermally conductive fillers have a thermal conductivity of more than 5 W / m°K, more preferably more than 10 W / m°K, and 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.

[0068] In a preferred embodiment, the thermally conductive filler has a D of 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 about 3 or greater. 90 / D 50 ATH or aluminum oxide having a wide particle size distribution characterized by the ratio, most preferably ATH.

[0069] Also preferred are thermally conductive fillers having a bimodal particle size distribution. 90 / D 50 The ratio is about 3 or more, more preferably about 5 or more, and particularly preferably 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 The particle size can be determined using laser diffraction. For ATH, a suitable solvent is deionized water containing a dispersing aid such as Na4P2O7x10H2O, preferably at 1 g / l. Preferred are aluminum oxide and ATH with a bimodal distribution, especially ATH. In a preferred embodiment, the thermally conductive filler has a D of about 3 or more, more preferably about 5 or more, and especially about 9 or more. 90 / D 50 It is an ATH that has the following.

[0070] In a preferred embodiment, the thermally conductive filler is a bimodal aluminum trihydroxide (ATH) having the following particle size distribution (by laser diffraction, preferably in deionized water containing a dispersing aid such as 1 g / l NaPO×10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 It has.

[0071] The thermally conductive filler is preferably present in the final adhesive obtained by mixing Part A and Part B at a concentration of 30 to 85 wt %, more preferably 40 to 85 wt %, and particularly preferably 60 to 85 wt %, based on the total weight of the adhesive.

[0072] In a preferred embodiment, the thermally conductive filler is aluminum trihydroxide (ATH) and is used at a concentration of 30 to 85 wt %, more preferably 40 to 85 wt %, and particularly preferably 60 to 85 wt %, based on the total weight of the adhesive.

[0073] In another preferred embodiment, the thermally conductive filler is bimodal aluminum trihydroxide (ATH) used in a concentration of 30-85 wt. %, more preferably 40-85 wt. %, and especially preferably 60-85 wt. %, based on the total weight of the adhesive.

[0074] In another preferred embodiment, the thermally conductive filler is aluminum trihydroxide (ATH) and has the following particle size distribution (preferably by laser diffraction in deionized water containing a dispersing aid such as 1 g / l NaPO×10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 and It is used at a concentration of 30 to 85% by weight, more preferably 40 to 85% by weight, and particularly preferably 60 to 85% by weight, based on the total weight of the adhesive.

[0075] The concentration of the thermally conductive filler in Liquid A is preferably 30 to 85% by weight, more preferably 40 to 85% by weight, and particularly preferably 60 to 85% by weight, based on the total weight of Liquid A.

[0076] The concentration of the thermally conductive filler in the liquid B is 30 to 85% by weight, more preferably 40 to 85% by weight, and particularly preferably 60 to 85% by weight, based on the total weight of the liquid B.

[0077] 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 particularly preferably 60 to 85 wt %, based on the total weight of Part A or Part B.

[0078] In another preferred embodiment, the thermally conductive filler is an ATH having a bimodal particle size, and is used in Part A and / or Part B at a concentration of 30 to 85 wt %, more preferably 40 to 85 wt %, and particularly preferably 60 to 85 wt %, based on the total weight of Part A or Part B.

[0079] In a preferred embodiment, the thermally conductive filler is aluminum trihydroxide (ATH) having the following particle size distribution (by laser diffraction, preferably in deionized water containing a dispersing aid such as 1 g / l NaPO×10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 and It is used in solution A and / or solution B at a concentration of 30 to 85% by weight, more preferably 40 to 85% by weight, and particularly preferably 60 to 85% by weight, based on the total weight of solution A or B.

[0080] at least one polyamine Component B comprises at least one polyamine having two or more primary or secondary amine groups.

[0081] In a preferred embodiment, the at least one polyamine comprises a triamine.

[0082] 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 particularly 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.

[0083] 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 particularly 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.

[0084] In another preferred embodiment, the polyamine is a triamine having primary amine groups and a molecular weight of 2,000 to 4,000 Da, more preferably 3,000 Da.

[0085] 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.

[0086] The polyoxyalkylene polyamine may have a weight average molecular weight of at least 400 Da, more preferably at least 1,000 Da, and particularly 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.

[0087] 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 about 440, the amine group of which is located on a secondary carbon atom at the end of an aliphatic polyether chain:

[0088] [ka]

[0089] Polypropylene oxide diamine with a molecular weight of about 400:

[0090] [ka]

[0091] A difunctional primary amine having an average molecular weight of about 2000, the primary amine group of which is located on a secondary carbon atom at the end of an aliphatic polyether chain:

[0092] [ka]

[0093] A triamine of the formula:

[0094] [ka]

[0095] Approximately 5,000 g / mol of triamine of the formula:

[0096] [ka]

[0097] 2. Polyamines based primarily on a polyethylene oxide polyether backbone. Examples include those of the general formula:

[0098] [ka]

[0099] It is of For example, a polyamine with a molecular weight of 600 g / mol, where y ≈ 9 and (x + z) ≈ 3.6; polyamine with y ≈ 12.5, (x + z) ≈ 6 and a molecular weight of 900 g / mol; It is a polyamine with a molecular weight of 2,000 g / mol, where y≒39 and (x+z)≒6.

[0100] In a particularly preferred embodiment, the at least one polyamine has the formula:

[0101] [ka]

[0102] The compound comprises or consists of a triamine of about 3000 molecular weight.

[0103] In another preferred embodiment, the at least one polyamine has the following general structure:

[0104] [ka]

[0105] The composition comprises or consists of a polyether triamine of about 440 molecular weight.

[0106] 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, reacted by Michael addition with an acrylate ester (e.g., methyl acrylate), and then reacted with a diamine (e.g., ethylenediamine) through the ester functional group. This results in a primary amine-terminated polyamine, which can be again subjected to a Michael addition reaction and then reacted again with a diamine. The first "cycle" is represented diagrammatically below using ethylenediamine and methyl acrylate:

[0107] [ka]

[0108] Other suitable polyamines include phenalkamines prepared by the Mannich reaction between cardanol, formaldehyde, and at least one polyamine.

[0109] In a preferred embodiment, the at least one polyamine has the formula:

[0110] [ka]

[0111] and a triamine of approximately 3,000 molecular weight having the following general structure:

[0112] [ka]

[0113] and a mixture of about 440 molecular weight polyetheramine triamine.

[0114] The at least one polyamine is preferably present in Solution B in an amount of 8 to 30% by weight, more preferably 10 to 20% by weight, and particularly preferably 12 to 16% by weight, based on the total weight of Solution B.

[0115] The at least one polyamine is preferably present in the liquid 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 the liquid B.

[0116] In a preferred embodiment, the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines and is used in Part B in an amount of 8 to 30 wt %, more preferably 10 to 20 wt %, and particularly preferably 12 to 16 wt %, based on the total weight of Part B.

[0117] In another preferred embodiment, the at least one polyamine comprises or consists of a mixture of about 3,000 Da polyethertriamine and about 440 Da polyethertriamine, and is used in Part B at 8 to 30 wt %, more preferably 10 to 20 wt %, and particularly preferably 12 to 16 wt %, based on the total weight of Part B.

[0118] In a preferred embodiment, the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines and is 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.

[0119] In another preferred embodiment, the at least one polyamine comprises or consists of a mixture of about 3,000 Da polyethertriamine and about 440 Da polyethertriamine, and is used in Part B at 80 to 99 wt %, more preferably 85 to 95 wt %, and especially preferably 87 to 92 wt %, based on the organic content of Part B.

[0120] At least one catalyst At least one of Part A and Part B contains a catalyst capable of catalyzing the reaction of the compound of general formula I with an amine.

[0121] The catalyst is preferably selected from tertiary amine catalysts.

[0122] 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.

[0123] In a preferred embodiment, the catalyst is 2,4,6-tris(dimethylaminomethyl)phenol.

[0124] In another preferred embodiment, the catalyst is 1,4-diazabicyclo[2.2.2]octane.

[0125] In a preferred embodiment, the catalyst is a mixture of 2,4,6-tris(dimethylaminomethyl)phenol and 1,4-diazabicyclo[2.2.2]octane.

[0126] The catalyst may be present in Part A and / or Part B. In a preferred embodiment, the catalyst is present in Part B.

[0127] 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 particularly preferably 0.45 to 0.55% by weight, based on the total weight of Solution B.

[0128] In a preferred embodiment, the catalyst comprises or consists of 2,4,6-tris(dimethylaminomethyl)phenol and is 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 Solution B.

[0129] In another preferred embodiment, the catalyst comprises or consists of 1,4-diazabicyclo[2.2.2]octane and is used in an amount of 0.02 to 0.35% by weight, more preferably 0.05 to 0.15% by weight, based on the total weight of Solution A.

[0130] 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, and contains 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 Solution B.

[0131] Optional Ingredients The adhesive composition of the present invention may optionally contain a plasticizer, which may be present in Part A or Part B, or both. Examples of plasticizers are esters, particularly diesters and triesters, and particularly those having a viscosity of 10 at 23°C. -4 Those having a vapor pressure of less than 1000 kJ / cm 3 hPa. Examples include dialkyl phthalates, alkyl esters of fatty acids, and phosphate esters (e.g., trioctyl phosphate). Diisononyl phthalate is particularly preferred. When used, the plasticizer is 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.

[0132] In addition to the thermally conductive filler, the adhesive composition of the present invention may optionally contain fillers, such as carbon black, clay, carbonates (e.g., calcium carbonate), metal hydrates, and fumed silica, which may be present in Part A or Part B, or both. Fillers are preferably used in amounts of 0 to 10 wt. %, preferably 1 to 6 wt. %, and more preferably 2 to 5 wt. %, based on the total weight of the relevant parts.

[0133] 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 exhibits an oil absorption of dibutyl phthalate of at least 80, preferably at least 90, and more preferably at least 95 cm³ per 100 g of carbon black, as measured in accordance with ASTM D-2414-09. Furthermore, the carbon black desirably has an iodine number of at least 80, as measured in accordance with ASTM D1510-11.

[0134] 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.

[0135] The adhesive composition of the present invention may optionally contain calcium carbonate in parts A and / or B in an amount of 0 to 5 wt. %, more preferably 1 to 3 wt. %, and especially preferably 1.5 to 2.5 wt. %, based on the total weight of the relevant parts. The calcium carbonate particles may be untreated or may be surface-modified by treatment with chemicals, such as organic acids or esters of organic acids.

[0136] 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.

[0137] When fumed silica is used, the particles may be untreated or surface modified with chemicals such as chlorosilanes, dichlorosilanes, alkyltrialkoxysilanes, or polydimethylsiloxanes.

[0138] The adhesive composition of the present invention may optionally include 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.

[0139] 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.

[0140] 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-containing and / or phosphorus-containing molecules, such as melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, etc.; 3. Aluminum phosphite and / or zinc phosphite Examples include:

[0141] A preferred flame retardant / synergist combination is aluminum diethylphosphinate plus melamine polyphosphate.

[0142] The adhesive compositions of the present invention may optionally include one or more additional stabilizers, such as heat, visible light, and UV stabilizers.

[0143] 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 wt. % or at least 0.3 wt. %, up to at most 5 wt. %, up to 2 wt. %, or up to 1.0 wt. %, based on the total weight of the adhesive composition. The adhesive composition may not contain such a heat stabilizer.

[0144] 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 absorbers may comprise at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt%, and may comprise up to 3 wt%, up to 2 wt%, or up to 1 wt%, of the weight of the adhesive composition.

[0145] 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%, at least 0.2%, or at least 0.3% by weight of the adhesive composition, and may comprise up to 3%, up to 2%, or up to 1.5% by weight of the adhesive composition.

[0146] Method for producing adhesive composition Parts A and B are produced by mixing the ingredients, preferably in a planetary mixer or dual asymmetric centrifuge. In the first stage, the liquid phases are mixed before the solid materials are added to the formulation. The formulation is mixed under vacuum for approximately 30 minutes and then filled into cartridges, pails, or drums. The two parts are stored separately until use, at which point they are mixed.

[0147] How to use The present invention provides (1) A step of preparing a two-component adhesive, the two-component adhesive comprising: (A) (a1) at least one compound of general formula I:

[0148] [ka]

[0149] (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 R4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene radical) A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: Including, at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are designed to be mixed together to form an adhesive mixture prior to use; (2) mixing Part A and Part B to form an adhesive mixture; (3) applying the adhesive mixture to a first substrate; (4) bringing a second substrate into adhesive contact with the first substrate; and (5) curing the adhesive mixture; The present invention provides a method for bonding two substrates, comprising:

[0150] Preferred embodiments of the method use preferred embodiments of the adhesives described herein.

[0151] As noted above, a preferred method of providing the adhesive of the present invention is in an airtight container, such as a hermetically sealed container, which is opened immediately prior to use and the two parts are mixed.

[0152] Solutions A and B can be mixed in any ratio. In a preferred embodiment, the ratio of solution A to solution 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).

[0153] The adhesive composition of the present invention can be applied by any application method, such as by spreading, applying through a nozzle, or the like, either manually or using robotic equipment.

[0154] In preferred embodiments, one or both of the first and second substrates are selected from aluminum, glass, steel, electrocoated metal, powder coated metal, coated metal, and plastic substrates such as polyethylene terephthalate, polyethylene, polypropylene, polyamide, polyimide, polycarbonate, with aluminum being particularly preferred.

[0155] Curing is accomplished by leaving the bonded assembly at room temperature. Complete cure is typically observed after 1-2 days, although a 7-day cure period is often used.

[0156] Particularly preferred embodiments The following are particularly preferred embodiments of the adhesive composition of the present invention. 1. Compounds of 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 radical). 2. Compounds of 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 radical) of as a monomer in polymers. 3. A two-component adhesive, (A) (a1) at least one compound of 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 4~8 Divalent C with alkyl substituents 1~3 alkylene radical) A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: A two-component adhesive comprising: 1. A two-part adhesive, wherein at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are designed to be mixed together to form an adhesive mixture prior to use. 4. A kit for making an adhesive mixture, comprising: (A) (a1) at least one compound of 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, R 4 has 2 to 5 C on the alkylene chain 1~3 Divalent C with alkyl substituents 4~8 alkylene radical) A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: 1. A kit for forming an adhesive comprising: 1. A kit, wherein at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are stored separately from each other and are designed to be mixed together prior to use to form an adhesive mixture. 5. A method for bonding a first substrate to a second substrate, comprising: (1) A step of preparing a two-component adhesive, the two-component adhesive comprising: (A) (a1) at least one compound of 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 radical) A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: Including, at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are designed to be mixed together to form an adhesive mixture prior to use; (2) mixing Part A and Part B to form an adhesive mixture; (3) applying the adhesive mixture to a first substrate; (4) bringing a second substrate into adhesive contact with the first substrate; and (5) curing the adhesive mixture; 1. A method for bonding a first substrate to a second substrate, comprising: 6. (1) a first substrate; (2) a second substrate; (3) An adhesive composition, (A) (a1) at least one compound of 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 radical) A first liquid (liquid A) containing (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; A second liquid (liquid B) containing an adhesive composition obtained by curing the mixture; A bonded assembly comprising: 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 first and second substrate in adhesive contact with the adhesive composition sandwiched therebetween; Glued assembly. 7. A two-component adhesive, (A) (a1) at least one compound of 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 an alkylene radical), (a2) at least one liquid epoxy resin; A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: A two-component adhesive comprising: A two-part adhesive, wherein at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are designed to be mixed together to form the adhesive mixture prior to use. 8. A kit for making an adhesive mixture, comprising: (A) (a1) at least one compound of 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 an alkylene radical), (a2) at least one liquid epoxy resin; A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: 1. A kit for forming an adhesive comprising: 1. A kit, wherein at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are stored separately from each other and are designed to be mixed together prior to use to form an adhesive mixture. 9. A method for bonding a first substrate to a second substrate, comprising: (1) A step of preparing a two-component adhesive, the two-component adhesive comprising: (A) (a1) at least one compound of 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 an alkylene radical), (a2) at least one liquid epoxy resin; A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; and a second liquid (liquid B) containing: Including, at least one of parts A and B contains a catalyst capable of catalyzing the reaction of an amine with a compound of general formula I, and parts A and B are designed to be mixed together to form an adhesive mixture prior to use; (2) mixing Part A and Part B to form an adhesive mixture; (3) applying the adhesive mixture to a first substrate; (4) bringing a second substrate into adhesive contact with the first substrate; and (5) curing the adhesive mixture; 1. A method for bonding a first substrate to a second substrate, comprising: 10. (1) a first substrate; (2) a second substrate; (3) An adhesive composition, (A) (a1) at least one compound of 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 radical) (a2) at least one liquid epoxy resin; A first liquid (liquid A) containing: (B) (b1) at least one polyamine having two or more primary or secondary amine functional groups; A second liquid (liquid B) containing an adhesive composition obtained by curing the mixture; A bonded assembly comprising: 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 first and second substrate in adhesive contact with the adhesive composition sandwiched therebetween; Glued assembly. 11. A method for preparing a compound of general formula I, comprising reacting a molecule of formula III with at least two equivalents of a molecule of formula IV in the presence of a catalyst: [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 radical). 12.R 1 and R 2is 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 However, there are 2 to 5 C groups on the alkylene chain. 1~3 Divalent C with alkyl substituents 4~8 Any one of the preceding embodiments, wherein the radical is an alkylene radical. 13.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 the preceding embodiments, wherein is H. 14. Any one of the preceding embodiments, wherein n is 1. 15.R 3 is C1-C4 alkyl, more preferably R 3 is C1-C2 alkyl, and particularly preferably R 3 Any one of the preceding embodiments, wherein is ethyl. 16.R 4 Any one of the preceding embodiments, wherein is a divalent C6 alkylene radical having 2 to 5 methyl substituents on the alkylene chain. 17.R 4 Any one of the preceding embodiments, wherein is a C6 alkylene radical having three methyl substituents on the alkylene chain. 18. The compound of general formula I is a compound of formula I″: [ka] Any one of the preceding embodiments, 19. Any one of the preceding embodiments, wherein the at least one liquid epoxy resin is selected from epoxy resins that are liquid at 23°C. 20. Any one of the preceding embodiments, wherein the liquid epoxy resin has a viscosity at 23°C of 50 Pas or less, more preferably 25 Pas or less, and especially preferably 15 Pas or less. 21. Any one of the preceding embodiments, wherein if only a single epoxy resin is present, it is a liquid at 23°C. 22. Any one of the preceding embodiments, 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 is liquid at 23°C. 23. Any one of the preceding embodiments, 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. 24. Any one of the previous embodiments, 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. 25. Any one of the preceding embodiments, 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-hydroxylphenyl)-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. 26. Any one of the preceding embodiments, wherein the at least one epoxy resin comprises or consists of a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight (per ASTM D-1652) of 176 to 185 g / eq, an epoxide percentage (per ASTM D-1652) of 23.2 to 24.4%, an epoxide group content (per ASTM D-1652) of 5,400 to 5,680 mmol / kg, and a viscosity at 25°C (per ASTM D-445) of 7,000 to 10,000 MPas. 27. Any one of the preceding embodiments, 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. 28. Any one of the preceding embodiments, wherein the liquid epoxy resin is present at 12-50 wt. %, more preferably 15-35 wt. %, and especially preferably 20-30 wt. %, based on the total organic content of Part A. 29. Any one of the preceding embodiments, wherein the at least one epoxy resin has an epoxide equivalent weight (per ASTM D-1652) of 176-185 g / eq, an epoxide fraction (per ASTM D-1652) of 23.2-24.4%, an epoxide group content (per ASTM D-1652) of 5,400-5,680 mmol / kg, and a viscosity at 25°C (per ASTM D-445) of 7,000-10,000 MPas, and is present in Part A at 2-20 wt%, more preferably 2-10 wt%, and especially preferably 4-8 wt%, based on the total weight of Part A. 30. Any one of the preceding embodiments, wherein the at least one liquid epoxy resin comprises the liquid reaction product of epichlorohydrin and bisphenol A, and has an epoxide equivalent weight (per ASTM D-1652) of 176-185 g / eq, an epoxide fraction (per ASTM D-1652) of 23.2-24.4%, an epoxide group content (per ASTM D-1652) of 5,400-5,680 mmol / kg, and a viscosity (per ASTM D-445) of 7,000-10,000 MPas at 25°C, and is present in Part A at 12-50 wt%, more preferably 15-35 wt%, and especially preferably 20-30 wt%, based on the total organic content of Part A. 31. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler. 32. Any one of the previous embodiments, wherein Part A and / or Part B comprises a thermally conductive filler selected from those having a thermal conductivity of greater than 5 W / m°K, more preferably greater than 10 W / m°K, and especially preferably greater than 15 W / m°K. 33. Any one of the preceding embodiments, 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. 34. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler, the thermally conductive filler being selected from aluminum trihydroxide (ATH) and aluminum oxide, with ATH being most preferred. 35. Solution A and / or solution B contain a thermally conductive filler, and the thermally conductive filler is about 3 or more D 90 / D 50 Any one of the preceding embodiments, having a broad particle size distribution characterized by the ratio: 36. Solution A and / or solution B contain a thermally conductive filler, and the thermally conductive filler has a D of about 3 or more. 90 / D 50 Any one of the preceding embodiments, wherein the aluminum oxide is ATH or aluminum oxide, most preferably ATH, having a broad particle size distribution characterized by the ratio: 37. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler has a bimodal particle size distribution. 38. Liquid A and / or liquid B contains a thermally conductive filler, and the thermally conductive filler has a ratio D of 3 or more, more preferably 5 or more, particularly preferably 9 or more. 90 / D 50 Any one of the preceding embodiments, 39. Part A and / or Part B contain a thermally conductive filler, wherein the thermally conductive filler is aluminum trihydroxide (ATH) with a bimodal distribution and has the following particle size distribution (preferably by laser diffraction in deionized water containing a dispersing aid such as 1 g / l NaPO x 10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 Any one of the preceding embodiments, 40. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is present in the final adhesive obtained by mixing Part A and Part B at a concentration of 30 to 85 wt %, more preferably 40 to 85 wt %, and especially preferably 60 to 85 wt %, based on the total weight of the adhesive. 41. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is aluminum trihydroxide (ATH) and is used at a concentration of 30-85 wt %, more preferably 40-85 wt %, and especially preferably 60-85 wt %, based on the total weight of the adhesive. 42. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is bimodal aluminum trihydroxide (ATH) used at a concentration of 30-85 wt %, more preferably 40-85 wt %, and especially preferably 60-85 wt %, based on the total weight of the adhesive. 43. Part A and / or Part B contain a thermally conductive filler, the thermally conductive filler being aluminum trihydroxide (ATH), and have the following particle size distribution (preferably by laser diffraction in deionized water containing 1 g / l of a dispersing aid such as NaPO x 10HO): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 and Any one of the preceding embodiments, wherein the adhesive is used at a concentration of 30-85 wt %, more preferably 40-85 wt %, and especially preferably 60-85 wt %, based on the total weight of the adhesive. 44. Any one of the preceding embodiments, 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 particularly preferably 60 to 85 wt %, based on the total weight of Part A. 45. Any one of the preceding embodiments, wherein Liquid A and / or Liquid B comprises a thermally conductive filler, and the concentration of the thermally conductive filler in Liquid B is 30 to 85 wt %, more preferably 40 to 85 wt %, and particularly preferably 60 to 85 wt %, based on the total weight of Liquid B. 46. ​​Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler, and the thermally conductive filler is aluminum trihydroxide (ATH) and is used in Part A and / or Part B at a concentration of 30 to 85 wt %, more preferably 40 to 85 wt %, and especially preferably 60 to 85 wt %, based on the total weight of Part A or B. 47. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a thermally conductive filler, wherein the thermally conductive filler is an ATH having a bimodal particle size and is used in Part A and / or Part B at a concentration of 30 to 85 wt %, more preferably 40 to 85 wt %, and especially preferably 60 to 85 wt %, based on the total weight of Part A or Part B. 48. Part A and / or Part B contain a thermally conductive filler, the thermally conductive filler being aluminum trihydroxide (ATH), and have the following particle size distribution (preferably by laser diffraction in deionized water containing 1 g / l of a dispersing aid such as Na4P2O7×10H2O): D 10 (microns) 0.5 D 50 (microns) 8 D 90 (microns) 80 and Any one of the preceding embodiments, wherein the compound is used in Part A and / or Part B at a concentration of 30 to 85 wt %, more preferably 40 to 85 wt %, and especially preferably 60 to 85 wt %, based on the total weight of Part A or Part B. 49. Any one of the previous embodiments, 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 especially preferably at least 2,000 Da. 50. Any one of the preceding embodiments, 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. 51. Any one of the previous embodiments, 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 especially preferably at least 400 Da. 52. Any one of the previous embodiments, wherein the at least one polyamine comprises a polyamine having a molecular weight of 300-500 Da, more preferably about 400-440 Da. 53. Any one of the previous embodiments, 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. 54. Any one of the preceding embodiments, wherein the polyamine comprises a polyoxyalkylene polyamine having two or more amine groups per polyamine, two to four amine groups per polyamine, or two or three amine groups per polyamine. 55. Any one of the preceding embodiments, wherein the polyamine comprises a polyetheramine having three amine groups. 56. Any one of the preceding embodiments, wherein the polyamine comprises a polyamine based on a propylene oxide polyether backbone. 57. Any one of the preceding embodiments, wherein the polyamine comprises a trifunctional primary amine having an average molecular weight of about 440. 58. A polyamine having the following structure: [ka] Any one of the preceding embodiments, comprising a polyetheramine having: 59. A polyamine having the formula: [ka] Any one of the preceding embodiments, comprising a triamine of about 3000 molecular weight. 60. At least one polyamine has the formula: [ka] a triamine of about 3000 molecular weight, The general structure: [ka] Any one of the preceding embodiments, comprising or consisting of a mixture of about 440 molecular weight polyether triamine and about 440 molecular weight polyether triamine. 61. Any one of the preceding embodiments, wherein the at least one polyamine is present in Part B at 8 to 30 wt %, more preferably 10 to 20 wt %, and especially preferably 12 to 16 wt %, based on the total weight of Part B. 62. Any one of the preceding embodiments, wherein the at least one polyamine is present in Part B at 80 to 99 wt. %, more preferably 85 to 95 wt. %, and especially preferably 87 to 92 wt. %, based on the organic content of Part B. 63. Any one of the preceding embodiments, wherein the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines and is used in Part B at 8 to 30 wt %, more preferably 10 to 20 wt %, and especially preferably 12 to 16 wt %, based on the total weight of Part B. 64. Any one of the preceding embodiments, wherein the at least one polyamine comprises or consists of a mixture of about 3,000 Da polyethertriamine and about 440 Da polyethertriamine, and is used in Part B at 8-30 wt %, more preferably 10-20 wt %, and especially preferably 12-16 wt %, based on the total weight of Part B. 65. Any one of the preceding embodiments, wherein the at least one polyamine comprises or consists of a polyethertriamine or a mixture of polyethertriamines and is used in Part B at 80 to 99 wt. %, more preferably 85 to 95 wt. %, and especially preferably 87 to 92 wt. %, based on the organic content of Part B. 66. Any one of the preceding embodiments, wherein the at least one polyamine comprises or consists of a mixture of about 3,000 Da polyethertriamine and about 440 Da polyethertriamine, and is used in Part B at 80-99 wt. %, more preferably 85-95 wt. %, and especially preferably 87-92 wt. %, based on the organic content of Part B. 67. Any one of the preceding embodiments, wherein the catalyst is selected from a tertiary amine catalyst. 68. Any one of the preceding embodiments, 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. 69. Any one of the preceding embodiments, wherein the catalyst comprises or consists of 2,4,6-tris-(dimethylaminomethyl)phenol. 70. Any one of the preceding embodiments, wherein the catalyst comprises or consists of 1,4-diazabicyclo[2.2.2]octane. 71. Any one of the preceding embodiments, wherein the catalyst is a mixture of 2,4,6-tris-(dimethylaminomethyl)phenol and 1,4-diazabicyclo[2.2.2]octane. 72. Any one of the preceding embodiments, wherein a catalyst is present in Part A and / or Part B. 73. Any one of the preceding embodiments, wherein the catalyst is present in Solution B. 74. Any one of the preceding embodiments, wherein the catalyst is used in an amount of 0.05 to 0.75 wt. %, more preferably 0.1 to 0.6 wt. %, and especially preferably 0.45 to 0.55 wt. %, based on the total weight of Part B. 75. Any one of the preceding embodiments, wherein the catalyst comprises or consists of 2,4,6-tris(dimethylaminomethyl)phenol and is 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. 76. Any one of the preceding embodiments, wherein the catalyst comprises or consists of 1,4-diazabicyclo[2.2.2]octane and is used at 0.02 to 0.35 wt %, more preferably 0.05 to 0.15 wt %, based on the total weight of Part A. 77. Any one of the preceding embodiments, wherein the catalyst comprises or consists of a mixture of 2,4,6-tris(dimethylaminomethyl)phenol and 1,4-diazabicyclo[2.2.2]octane, and comprises 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. 78. Any one of the preceding embodiments, wherein Part A and / or Part B comprises a plasticizer. 79. Any one of the preceding embodiments, wherein Part A and / or Part B includes a filler in addition to the thermally conductive filler. 80. Any one of the preceding embodiments, 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. 81. Any one of the preceding embodiments, 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. 82. Any one of the preceding embodiments, wherein Part A and / or Part B comprises 0-5 wt. %, more preferably 1-3 wt. %, and especially preferably 1.5-2.5 wt. % calcium carbonate, based on the total weight of the relevant part. 83. Any one of the preceding embodiments, wherein Part A and / or Part B comprises one or more adhesion promoters. 84. Any one of the preceding embodiments, wherein Part A and / or Part B comprises one or more adhesion promoters in the form of one or more silanes. 85. Any one of the preceding embodiments, wherein Part A and / or Part B comprises one or more adhesion promoters in the form of one or more aminosilanes, mercaptosilanes, and epoxysilanes. 86. Any one of the preceding embodiments, wherein Part A and / or Part B comprises gamma-glycidoxypropyltrimethoxysilane. 87. Any one of the preceding embodiments, wherein Part A comprises 0.1 to 1 wt. % gamma-glycidoxypropyltrimethoxysilane, preferably 0.3 to 0.6 wt. %, based on the total weight of Part A. [Example]

[0157] [Table 1]

[0158] [Table 2]

[0159] [Table 3]

[0160] Preparation of GF210 and GF213 Prepolymers (Conventional CPEE-Capped Prepolymers) The following procedure was carried out using the amounts listed in Table 3.

[0161] Voranol 1010 was placed in a laboratory reactor and heated to 130°C under vacuum with stirring. Upon reaching that temperature, 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 then bismuth catalyst (TiB718) was added. The mixture was allowed to react for 45 minutes at an 85°C bath temperature with stirring under nitrogen. The mixture was then cooled to 60°C with stirring under nitrogen. CPEE was added, and the mixture was allowed to react for 45 minutes at an 85°C bath temperature with stirring under nitrogen. The isocyanate content was checked, and if it was zero, the mixture was stirred for an additional 20 minutes at 85°C under vacuum. The prepolymer was stored under an inert atmosphere until use.

[0162] Preparation of CPEE-functionalized diisocyanates (GF216, GF217, GF218, GF219) The following procedure was carried out using the amounts listed in Table 2.

[0163] The diisocyanate and bismuth catalyst (TiB 718) were placed in 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 reacted under vacuum at a bath temperature of 70°C for 45 minutes. The CPEE-functionalized diisocyanate was stored under an inert atmosphere until use.

[0164] [Table 4]

[0165] A look at CPEE-functionalized diisocyanates. When MDI is functionalized with CPEE (GF216), the resulting product is solid at room temperature, which is undesirable as a monomer for adhesives. The same is true when HDI is functionalized with CPEE (GF217).

[0166] 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 a monomer for adhesives.

[0167] Functionalization of 2,4,4-trimethylhexamethylene diisocyanate with CPEE results in a manageable liquid with a viscosity suitable for use as a monomer in adhesives.

[0168] adhesive formulation The formulations were mixed in a planetary mixer or dual asymmetric centrifuge using the ingredients listed in Table 3. 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 before being filled into cartridges, pails, or drums.

[0169] [Table 5]

[0170] [Table 6]

[0171] [Table 7]

[0172] Test Method viscosity Rheological measurements were performed on an Anton Paar MC302 rheometer in parallel plate geometry. Plates with a diameter of 25 mm were used, with a gap fixed at 0.5 mm. The material was placed between the two plates, after which shear rate tests were performed at 0.001–20 1 / s. -1 The viscosity at is reported.

[0173] Press-fitting The press-in force is measured with a tensiometer (Zwick). The material is placed on a metal surface. An aluminum piston with a diameter of 40 mm is placed on top of it 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.

[0174] thermal conductivity Thermal conductivity is measured according to ASTM 5470-12 on a ZFW Stuttgart Thermal Interface Materials Tester. Tests are performed in Spaltplus mode at thicknesses of 1.8-1.2 mm. The material is considered to be Type I (viscous liquid) as described in ASTM 5470-12. The upper contact is heated to approximately 40°C and the lower contact is heated to approximately 10°C, resulting in a sample temperature of approximately 25°C. When dispensed from a manual cartridge system, components A and B are mixed in a static mixer.

[0175] GPC The molecular weight data of the polyurethane prepolymers were determined by gel permeation chromatography (GPC) using a Malvern Viscothek GPC max instrument, 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.

[0176] Lap shear strength Aluminum substrates (AA6061 T6 1.92mm MF noPT no lub, 140 x 25mm, 1.9mm thick, from Novelis) were used. The substrates were cleaned with isopropanol before use. After the adhesive was applied to one substrate, the second substrate was bonded within 5 minutes. The thickness was adjusted to 1.0mm, and the overlap area was 25mm x 25mm. The material was cured and left at 23°C and 50% relative humidity for 7 days before undergoing lap shear testing. The lap shear specimens were then mounted on a tensile tester and subjected to lap shear testing using a tension speed of 10mm / min. The force-deflection curve was recorded, and the strength at break was reported as the lap shear strength.

[0177] 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 (wt%).

[0178] result As noted above, the results in Table 2 show that of the diisocyanates tested, only the branched aliphatic diisocyanate TMDI reacted with CPEE to produce a reaction product that was a liquid with a viscosity suitable for use as a prepolymer.

[0179] The data in Table 3 show that the highest lap shear strength was achieved when molecules of general formula I (TMDI-CPEE) were used in part A and combined with a liquid epoxy resin (DER330). In contrast, conventional polyurethane prepolymers (see Desmodur E21, CE1, and CE2) showed a significant decrease in lap shear strength, both with (CE2) and without (CE1) epoxy.

Claims

1. It is a two-part adhesive, (A) (a1) At least one compound of general formula I: 【Chemistry 1】 (wherein, R 1 and R 2 are independently selected from hydrogen and C 1 - C 6 alkyl, n is an integer of 1 to 2, R 3 is C 1 - C 6 alkyl, R 4 is a divalent C 1~3 alkylene radical having 2 to 5 C 4~8 alkyl substituents on the alkylene chain) The first solution (Solution A) contains; (B) (b1) At least one polyamine having two or more primary or secondary amine functional groups The second solution (solution B) contains; A two-part adhesive containing, A two-component adhesive in which at least one of solution A and solution B contains a catalyst capable of catalyzing the reaction between an amine and a compound of general formula I, and solution A and solution B are designed to be mixed together before use to form an adhesive mixture.

2. The adhesive according to claim 1, wherein the compound of general formula I is produced by reacting a molecule of formula III with at least two equivalents of a molecule of formula IV in the presence of a catalyst: 【Chemistry 2】 (In the formula, 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 carbon atoms on the alkylene chain. 1~3 divalent carbon having alkyl substituents 4~8 (It is an alkylene radical.)

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

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

5. The adhesive according to claim 1, wherein n is 1.

6. The adhesive according to claim 1, wherein R3 is a C1-C4 alkyl group.

7. R 4 However, divalent carbon has 2 to 5 methyl substituents on the alkylene chain. 6 The adhesive according to claim 1, wherein the adhesive is an alkylene radical.

8. R 4 However, C has three methyl substituents on the alkylene chain. 6 The adhesive according to claim 7, wherein the adhesive is an alkylene radical.

9. The compound of general formula I mentioned above is a compound of formula I'': 【Transformation 3】 The adhesive according to claim 1.

10. The adhesive according to claim 1, wherein liquid A further comprises at least one liquid epoxy resin (a2).

11. The adhesive according to claim 10, wherein the at least one liquid epoxy resin is selected from epoxy resins that are liquid at 23°C.

12. The adhesive according to claim 11, wherein the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A.

13. The adhesive according to claim 10, wherein the liquid epoxy resin is present in an amount of 12 to 50% by weight based on the total organic matter content of liquid A.

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

15. The adhesive according to claim 1, wherein the at least one polyamine comprises a mixture of a triamine having a molecular weight of 2,000 to 4,000 Da and a polyamine having a molecular weight of 300 to 500 Da.

16. The adhesive according to claim 1, wherein at least one polyamine is present in solution B at an amount of 80 to 99% by weight, based on the organic matter content of solution B.

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

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