Two-part polyurethane adhesive

Abstract

To provide a thermally conductive adhesive that can maintain its structural properties after aging. [Solution] A two-component flame-retardant polyurethane adhesive compound comprising: (A) a first liquid containing a polyurethane prepolymer made from at least one polyol, at least one polyisocyanate, and an aminosilane, which is partially terminated at a silane moiety and has a reactive NCO moiety; and (B) a second liquid containing one or more polyether polyols; and (b2) one or more catalysts that can promote the reaction between the NCO moiety of (a1) and (b1), wherein liquid A and / or liquid B contain aluminum hydroxide.

Description

[Technical Field]

[0001] This invention relates to adhesives, particularly two-component polyurethane adhesives. [Background technology]

[0002] The ongoing pursuit of weight reduction has led to increased use of aluminum alloys in the building blocks of vehicle body design. In particular, in electric vehicles (EVs), batteries significantly increase the overall vehicle weight. Batteries themselves utilize many aluminum alloys in various structures and components. For example, the battery pack housing is typically made of aluminum, and the side and edge panels of the battery module are also made of aluminum alloy. Bonding aluminum alloys to other battery components becomes crucial. Adhesive bonding, along with other bonding methods such as welding and riveting, is currently a common method for joining aluminum in the automotive industry. The typical bonding strength required for joining structural components needs to be greater than 5 MPa, preferably 10 MPa or more.

[0003] The most commonly used adhesives for joining aluminum alloys are based on epoxy and acrylic chemistry. However, epoxy adhesives have a relatively slow curing speed and can become brittle in the cured state. This hinders their use in structural bonding of aluminum alloys within battery pack applications. Acrylic adhesives often have an unpleasant odor and are not very user-friendly.

[0004] Polyurethane (PU) adhesives are typically used to bond painted substrates to plastic components in automotive applications. However, PU adhesives typically do not provide strong and durable bonds to aluminum alloys, and their adhesion to aluminum, in particular, deteriorates significantly when exposed to harsh weathering conditions such as high temperatures and humidity. In addition, in battery applications, adhesives used inside battery packs must be fire-resistant or flame-retardant. Flame-retardant additives typically used in the polyurethane industry are halogen-containing or phosphorus-based. Unfortunately, these additives dramatically reduce the adhesive or bonding performance of the adhesive, often resulting in damage to the structural properties of the bonded system.

[0005] In the industry, there is a growing trend to bond battery cells with thermally conductive adhesives that offer a dual function, providing not only thermal conductivity but also structural bonding. Achieving a thermal conductivity of over 1 W / mK with thermally conductive adhesives typically requires a high amount of thermally conductive filler (>50% by weight), which makes it difficult to maintain structural properties, especially adhesive strength to aluminum, particularly after aging. [Overview of the project] [Means for solving the problem]

[0006] In the first aspect, the present invention is (A) (a1) A polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, wherein the polyurethane prepolymer is partially terminated at a silane moiety and has a reactive NCO moiety; The first liquid contains, (B) (b1) One or more polyether polyols; (b2) One or more catalysts capable of promoting the reaction between the NCO moiety of (a1) and (b1); The second liquid contains A two-component flame-retardant polyurethane adhesive compound containing, Liquid A and / or Liquid B contain aluminum hydroxide such that when Liquid A and Liquid B are mixed together to form an adhesive mixture (preferably in a volume ratio of 1:1), the concentration of aluminum hydroxide is at least 50% by weight. A two-component flame-retardant polyurethane adhesive formulation is provided.

[0007] A method for bonding two or more substrates, (1) (A) (a1) A polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, wherein the polyurethane prepolymer is partially terminated at a silane moiety and has a reactive NCO moiety; The first liquid contains, (B) (b1) One or more polyether polyols; (b2) One or more catalysts capable of promoting the reaction between the NCO moiety of (a1) and (b1); The second liquid contains A step of preparing a two-component flame-retardant polyurethane adhesive compound containing, A step in which liquid A and / or liquid B contain aluminum hydroxide such that when liquid A and liquid B are mixed together to form an adhesive mixture (preferably in a volume ratio of 1:1), the aluminum hydroxide concentration is at least 50% by weight; (2) A step of mixing liquid A and liquid B to obtain an uncured adhesive; (3) A step of applying an uncured adhesive to at least one substrate; (4) A step of bringing the uncured adhesive into adhesive contact with the second substrate; (5) The process of curing the uncured adhesive; A method that includes this.

[0008] (1) First substrate; (2) Second substrate; A bonded assembly comprising a first substrate and a second substrate, bonded to each other by a cured adhesive obtained by mixing liquid A and liquid B together, Solution A, (A) (a1) A polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, which is terminated partially at silane sites and has reactive NCO sites; A first liquid containing the same; The B liquid is (B) (b1) One or more polyether polyols; (b2) One or more catalysts capable of promoting the reaction between the NCO sites of (a1) and (b1); A second liquid containing the same; The A liquid and / or the B liquid contains aluminum hydroxide such that when the A liquid and the B liquid are mixed together to form an adhesive mixture (preferably at a volume ratio of 1:1), the concentration of aluminum hydroxide becomes at least 50% by weight, and the mixture is cured, adhered assembly.

Mode for Carrying Out the Invention

[0009] The inventors have found that by blending a thermally conductive flame retardant adhesive with polyurethane, i) lap shear strength exceeding 7.5 MPa for aluminum, ii) a flame retardant grade of V0, and iii) excellent retention of lap shear strength after long-term exposure to harsh conditions can be obtained.

[0010] Definitions and Abbreviations DSC Differential Scanning Calorimetry MDI 4,4'-Methylenebis(phenyl isocyanate) HDI Hexamethylene diisocyanate IPDI Isophorone diisocyanate PU Polyurethane SEC Size Exclusion Chromatography RH Relative Humidity ATH Aluminum trihydroxide, aluminum hydroxide

[0011] Equivalent weight and molecular weight were measured by gel permeation chromatography (GPC) using a Malvern Viscothek GPC max instrument. Tetrahydrofuran (THF) was used as the eluent, PL GEL MIXED D (Agilent, 300*7.5 mm, 5 μm) was used as the column, and MALVERN Viscotek TDA (integrated refractive index viscometer and light scattering) was used as the detector.

[0012] The adhesive of the present invention is a two-component polyurethane adhesive comprising liquid A and liquid B. Liquids A and B can be packaged together as a kit. Liquids A and B are mixed together in an appropriate ratio, preferably 1:1 by volume, before use, and then applied to one or more substrates as quickly as possible.

[0013] Solutions A and B will be disclosed in more detail below.

[0014] Solution A (isocyanate) Solution A comprises a polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, wherein the prepolymer is partially terminated at a silane moiety and has a reactive NCO moiety.

[0015] The polyisocyanates used to produce the prepolymer may be aliphatic, aromatic, or a mixture, with aromatic polyisocyanates being preferred. Examples of aromatic polyisocyanates include methylenediphenyl diisocyanate (MDI), polycarbodiimide-modified MDI, toluene diisocyanate (TDI), p-phenylenediisocyanate (PPDI), and naphthalene diisocyanate (NDI). MDI and / or polycarbodiimide-modified MDI are particularly preferred. In some embodiments, a mixture of MDI and polycarbodiimide-modified MDI is used.

[0016] The polyisocyanate used in the production of the prepolymer is preferably used in an amount of 15-40% by weight, more preferably 17-35% by weight, and particularly preferably 20-32% by weight, based on the total weight of component A.

[0017] In a particularly preferred embodiment, the prepolymer is prepared using 15-40% by weight, more preferably 17-35% by weight, and especially preferably 20-32% by weight of MDI and / or polycarbodiimide-modified MDI based on the total weight of component A.

[0018] The polyol used in the production of the prepolymer is preferably a polyether polyol. The polyol may have two or more OH groups. An example of a polyether polyol is a poly(alkylene oxide)diol, in which the alkylene group is C2-C6, and particularly preferably C2-C4. Examples of suitable polyols include poly(ethylene oxide) polyol, poly(propylene oxide) polyol, and poly(tetramethylene oxide) polyol. Poly(propylene oxide) polyol, particularly poly(propylene glycol), is especially preferred. In a preferred embodiment, the polyether polyol is a polyether polyol based on propylene glycol. In a particularly preferred embodiment, this is a polyether polyol based on ethylene oxide-capped propylene glycol having a molecular weight of about 2,000 Da and a functional value of 2.

[0019] The polyether polyol used in the production of the prepolymer is preferably used in an amount of 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight, based on the total weight of component A.

[0020] In preferred embodiments, the polyol used in the production of the prepolymer is a polyether polyol based on propylene glycol, and is used in an amount of 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight, based on the total weight of component A.

[0021] Polyisocyanate is used in excess relative to the polyether polyol so that the prepolymer is terminated with isocyanate groups. The final prepolymer has an NCO% by weight preferably in the range of 5 to 30% by weight, more preferably in the range of 10 to 25% by weight.

[0022] The aminosilane in component A preferably has general formula I or general formula II:

[0023] [ka]

[0024] (In the formula, R 1 R is independently selected from C1-C6 alkyl groups, 2 (These are independently selected from C2-C6 alkylenes).

[0025] In a preferred embodiment, the aminosilane of component A is of general formula I, and R 1 R2 is a C1-C2 alkyl group, and R2 is a C2-C4 alkylene group. In a more preferred embodiment, the aminosilane is of general formula I, and R 1 R1 is methyl, and R2 is propylene.

[0026] In another preferred embodiment, the aminosilane in component A is of general formula II, and R 1 R2 is a C1-C2 alkyl group, and R2 is a C2-C4 alkylene group. In a more preferred embodiment, the aminosilane is of general formula II, and R 1 R1 is methyl, and R2 is propylene.

[0027] In a particularly preferred embodiment, the aminosilane in component A is bis(trimethoxysilylpropyl)amine.

[0028] The aminosilane in component A is preferably used in an amount of 0.5 to 4% by weight, more preferably 1 to 3% by weight, and particularly preferably 1.5 to 2.5% by weight, based on the total weight of component A.

[0029] In preferred embodiments, the aminosilane in component A is bis(trimethoxysilylpropyl)amine, and is used in an amount of 0.5 to 4% by weight, more preferably 1 to 3% by weight, and particularly preferably 1.5 to 2.5% by weight, based on the total weight of component A.

[0030] In a preferred embodiment, the prepolymer in component A is manufactured using the following: • 15-40% by weight, more preferably 17-35% by weight, and especially preferably 20-32% by weight of polyisocyanate based on the total weight of component A; • 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight of polyether polyols based on the total weight of component A; and • 0.5 to 4% by weight, more preferably 1 to 3% by weight, and especially preferably 1.5 to 2.5% by weight of aminosilane based on the total weight of component A.

[0031] In a more preferred embodiment, the prepolymer in component A is manufactured using the following: • 15-40% by weight, more preferably 17-35% by weight, and especially preferably 20-32% by weight of MDI and / or polycarbodiimide-modified MDI, or a mixture of MDI and polycarbodiimide-modified MDI, based on the total weight of component A; • A polyether polyol based on propylene glycol, preferably having an OH value (mgKOH / g) of 109 to 115, in an amount of 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight, based on the total weight of component A; Based on the total weight of component A, 0.5 to 4% by weight, more preferably 1 to 3% by weight, and particularly preferably 1.5 to 2.5% by weight of an aminosilane of general formula II (where R in the formula is R) 1 R2 is a C1-C2 alkyl group, R2 is a C2-C4 alkylene group, and R 1 (R2 is methyl, and R2 is propylene).

[0032] In a particularly preferred embodiment, the prepolymer in component A is manufactured using the following: A mixture of MDI and polycarbodiimide-modified MDI in an amount of 20-32% by weight, based on the total weight of component A; • A polyether polyol based on propylene glycol having an OH number (mgKOH / g) of 10⁹ to 11⁵, in an amount of 9 to 12% by weight relative to the total weight of component A; and • 0.5 to 4% by weight, more preferably 1 to 3% by weight, and especially preferably 1.5 to 2.5% by weight of bis-(trimethoxysilylpropyl)amine, based on the total weight of component A.

[0033] The prepolymer is prepared by mixing the components, preferably in a dry and / or inert atmosphere, for a sufficient time for substantially all of the OH groups of the polyol and the amino groups of the aminosilane to react with the polyisocyanate. In preferred embodiments, the mixing is carried out for 1 to 2 hours. The ratio is selected so that the prepolymer is terminated with isocyanate groups and partially with silane groups.

[0034] Solution B (Polyol) Solution B is One or more polyether polyols; and One or more catalysts capable of promoting the reaction between the NCO moiety of the prepolymer and the polyol of component B; Includes.

[0035] The polyol used in component B is a polyether polyol. The polyol may have two or more OH groups. An example of a polyether polyol is poly(alkylene oxide)diol, in which the alkylene group is C2 to C6, and particularly preferably C2 to C4. Examples of suitable polyols include poly(ethylene oxide) polyol, poly(propylene oxide) polyol, and poly(tetramethylene oxide) polyol. Poly(propylene oxide) polyol is particularly preferred.

[0036] In a preferred embodiment, the polyether polyol of component B is a diol.

[0037] In another preferred embodiment, the polyether polyol of component B is a mixture of polyols having a functional value of 2 to 6. In a particularly preferred embodiment, the polyether polyol of component B is a mixture of at least one diol, at least one triol, and at least one polyol having a functional value greater than 3.

[0038] In a preferred embodiment, the polyether polyol of component B comprises or is a mixture thereof of a diol, a triol, and a polyol having a nominal functional value of 5 to 6.

[0039] In a preferred embodiment, the polyether polyol of component B is a poly(propylene oxide) polyol having a functional value of 2.

[0040] In a preferred embodiment, the polyether polyol of component B is a mixture of poly(propylene oxide) polyols having a functional value of 2 to 6. In a particularly preferred embodiment, the polyether polyol of component B is a mixture comprising, or consisting of, at least one poly(propylene oxide) diol, at least one poly(propylene oxide) triol, and at least one poly(propylene oxide) polyol having a functional value greater than 3.

[0041] In a preferred embodiment, the polyether polyol of component B comprises or is a mixture thereof of a poly(propylene oxide)diol, a poly(propylene oxide)triol, and a poly(propylene oxide)polyol having a nominal functional value of 5 to 6.

[0042] In another preferred embodiment, the polyether polyol of component B consists of a poly(propylene oxide)diol.

[0043] In another preferred embodiment, the polyether polyol of component B comprises, based on the total weight of the polyether polyols in component B, 0 to 45% by weight of a polyether triol, 0 to 30% by weight of a polyether polyol having a functional value greater than 3, and 25 to 100% by weight of a polyether diol.

[0044] In another preferred embodiment, the polyether polyol of component B comprises, based on the total weight of the polyether polyols in component B, 5 to 45% by weight of a polyether triol, 10 to 35% by weight of a polyether polyol having a functional value greater than 3, and 30 to 80% by weight of a polyether diol.

[0045] In another preferred embodiment, the polyether polyol of component B comprises, based on the total weight of the polyether polyols in component B, 0 to 45% by weight of poly(propylene oxide)triol, 0 to 30% by weight of poly(propylene oxide)polyol having a functional value greater than 3, and 25 to 100% by weight of poly(propylene oxide)diol.

[0046] The polyether polyol in component B, when combined, is preferably present in an amount of 15-50% by weight, more preferably 16-45% by weight, and particularly preferably 18-42% by weight, based on the total weight of component B.

[0047] In a preferred embodiment, component B comprises a mixture of polyether polyols comprising, or consisting thereof, in an amount of 15 to 50% by weight, more preferably 16 to 45% by weight, and particularly preferably 18 to 42% by weight, based on the total weight of component B: (1) Based on the total weight of polyether polyols in component B, 30-45% by weight of polyether triol, 19-30% by weight of polyether polyol having a functional value greater than 3, and 27-40% by weight of polyether diol; or (2) Based on the total weight of polyether polyols in component B, 5 to 15% by weight of polyether triol, 10 to 25% by weight of polyether polyol having a functional value greater than 3, and 70 to 80% by weight of polyether diol; or (3) 100% by weight of polyetherdiol based on the total weight of polyether polyols in component B; or (4) Based on the total weight of the polyether polyols in component B, 30-45% by weight of poly(propylene oxide) triol, 19-30% by weight of poly(propylene oxide) polyol having a functional value greater than 3, and 27-40% by weight of poly(propylene oxide) diol; or (5) Based on the total weight of the polyether polyols in component B, 5 to 15% by weight of poly(propylene oxide) triol, 10 to 25% by weight of poly(propylene oxide) polyol having a functional value greater than 3, and 70 to 80% by weight of poly(propylene oxide) diol.

[0048] Component B may optionally include diols and / or triols having a molecular weight of less than 200 Da, more preferably less than 150 Da. Examples of diols include propylene glycol and butanediol, with butanediol (e.g., 1,4-butanediol) being particularly preferred. Examples of triols include glycerin and trimethylolpropane, with glycerin being particularly preferred.

[0049] If present, diols or triols with a molecular weight of less than 200 Da are preferably used in an amount of 2 to 8% by weight, more preferably 2.5 to 5% by weight, based on the total weight of component B.

[0050] In a preferred embodiment, component B comprises 2 to 8% by weight, more preferably 2.5 to 5% by weight, of butanediol (e.g., 1,4-butanediol) based on the total weight of component B.

[0051] In another preferred embodiment, component B comprises 2 to 8% by weight, more preferably 2.5 to 5% by weight, of glycerin based on the total weight of component B.

[0052] Component B comprises one or more catalysts capable of promoting the reaction between the NCO moiety of the prepolymer of component A and one or more polyether polyols of component B.

[0053] The catalyst is preferably selected from Lewis bases and Lewis acids. Tertiary amines such as diazabicyclo[2.2.2]octane, tris-2,4,6-((dimethylamino)methyl)phenol, DMDEE (2,2'-dimorpholinodiethyl ether), imidazole (e.g., 4-methylimidazole), triethanolamine, and polyethyleneimine are preferred, with diazabicyclo[2.2.2]octane being particularly preferred.

[0054] Furthermore, organotin compounds, such as dioctyltindineodecanoate, dibutyltindi(acetate), and di-n-octyltinbis(isooctylmercaptoacetate), are also suitable. Di-n-octyltinbis(isooctylmercaptoacetate) is particularly preferred.

[0055] The catalyst is preferably used in an amount of 0.005 to 0.02% by weight, more preferably 0.0075 to 0.015% by weight, and particularly preferably 0.01% by weight, based on the total weight of component B.

[0056] In preferred embodiments, the catalyst is di-n-octyl tinbis(isooctyl mercaptoacetate), used in an amount of 0.005 to 0.02% by weight, more preferably 0.0075 to 0.015% by weight, and particularly preferably 0.01% by weight, based on the total weight of component B.

[0057] Aluminum hydroxide Solution A and / or Solution B contains aluminum hydroxide. When Solution A and Solution B are mixed together to form an adhesive mixture (preferably in a volume ratio of 1:1), the aluminum hydroxide concentration is at least 50% by weight based on the total weight of the adhesive mixture.

[0058] Preferably, the aluminum hydroxide concentration in the adhesive mixture is 50 - 70% by weight, more preferably 55 - 68% by weight, based on the total weight of the mixture.

[0059] In a preferred embodiment, aluminum hydroxide is present in Component A at 50 - 70% by weight, more preferably 55 - 68% by weight, based on the total weight of Component A.

[0060] [[ID=I2]]In another preferred embodiment, aluminum hydroxide is present in Component B at 50 - 70% by weight, more preferably 55 - 68% by weight, based on the total weight of Component B.

[0061] In a preferred embodiment, aluminum hydroxide is present in both Component A and Component B.

[0062] In another preferred embodiment, aluminum hydroxide is present in both Component A and Component B at 50 - 70% by weight, more preferably 55 - 68% by weight, based on the total weight of each component.

[0063] In a preferred embodiment, aluminum hydroxide has a D of about 20 microns 50 and.

[0064] Preferably, the adhesive mixture (preferably in a volume ratio of 1:1) obtained by mixing Component A and Component B contains aluminum hydroxide having a D of about 20 microns at 50 - 70% by weight, more preferably 55 - 68% by weight, based on the total weight of the mixture. 50 and.

[0065] In another preferred embodiment, Component A has a D of about 20 microns 50The material contains aluminum hydroxide having the property shown in the image, in an amount of 50-70% by weight, more preferably 55-68% by weight, based on the total weight of component A.

[0066] In another preferred embodiment, component B is approximately 20 microns of D 50 The material contains aluminum hydroxide having the property shown in the image, in an amount of 50-70% by weight, more preferably 55-68% by weight, based on the total weight of component B.

[0067] In another preferred embodiment, both component A and component B are D approximately 20 microns in size. 50 The material contains aluminum hydroxide having the following properties in an amount of 50-70% by weight, more preferably 55-68% by weight, based on the total weight of each component.

[0068] Selective raw materials of components A and B Components A and / or B may additionally contain other raw materials such as talc, molecular sieves, silica (especially amorphous silica), and carbon black.

[0069] Application to the substrate Liquid (A) and liquid (B) are mixed and can be applied to the substrate using known methods such as a manual application system or an automated method using a pump system with a 20-liter pail, a 200-liter drum, or any other preferred container.

[0070] Preferred substrates include aluminum, electrodeposited aluminum, electrodeposited steel, laser-treated aluminum, or passivated aluminum.

[0071] Features The cured adhesive composition obtained by mixing components A and B preferably has a thermal conductivity of at least 0.75 W / mK, more preferably at least 0.8 W / mK, after curing for 7 days at 23°C and 50% relative humidity and then being left to stand, as measured according to ASTM D5470.

[0072] The cured adhesive composition obtained by mixing components A and B preferably has a lap shear strength of 7.5 MPa or more, more preferably 8 MPa or more, on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity and then standing, as measured according to the method shown in the examples.

[0073] The cured adhesive composition obtained by mixing components A and B preferably has a lap shear strength of 6 MPa or more, more preferably 8 MPa or more, and particularly preferably 9 MPa or more on an aluminum substrate, after being cured for 7 days at 23°C and 50% relative humidity, followed by cataplasm treatment for 7 days, as measured according to the method shown in the examples.

[0074] The cured adhesive composition obtained by mixing components A and B preferably has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, on an aluminum substrate after being cured for 7 days at 23°C and 50% relative humidity, followed by being left to stand at 85°C and 85% relative humidity for 168 hours, as measured according to the method shown in the examples.

[0075] The cured adhesive composition obtained by mixing components A and B preferably has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, and particularly preferably 10 MPa or more on an aluminum substrate, after being cured for 7 days at 23°C and 50% relative humidity, followed by being left to stand for 1,000 hours at 85°C and 85% relative humidity, as measured according to the method shown in the examples.

[0076] The cured adhesive composition obtained by mixing components A and B preferably has a V0 rating according to UL94 after curing for 7 days at 23°C and 50% relative humidity.

[0077] In a preferred embodiment, the cured adhesive composition obtained by mixing components A and B (for 7 days at 23°C and 50% relative humidity) has a lap shear strength of 7.5 MPa or more, more preferably 8 MPa or more, on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity and then standing, as measured according to the method shown in the examples, and has a UL94 V0 grade after curing for 7 days at 23°C and 50% relative humidity.

[0078] In another preferred embodiment, the cured adhesive (at 23°C and 50% relative humidity for 7 days) has a lap shear strength of 6 MPa or more, more preferably 8 MPa or more, and particularly preferably 9 MPa or more on an aluminum substrate after 7 days of cataplasm treatment, as measured according to the method shown in the examples, and has a UL94 V0 grade after curing at 23°C and 50% relative humidity for 7 days.

[0079] In another preferred embodiment, the cured adhesive (at 23°C and 50% relative humidity for 7 days) has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, on an aluminum substrate after being left at 85°C and 85% relative humidity for 168 hours, as measured according to the method shown in the examples, and has a UL94 V0 grade after curing at 23°C and 50% relative humidity for 7 days.

[0080] In another preferred embodiment, a cured adhesive composition obtained by mixing components A and B (for 7 days at 23°C and 50% relative humidity) has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, and particularly preferably 10 MPa or more on an aluminum substrate after 1,000 hours at 85°C and 85% relative humidity, as measured according to the method shown in the examples, and has a UL94 V0 grade after curing for 7 days at 23°C and 50% relative humidity.

[0081] In another preferred embodiment, the cured adhesive composition obtained by mixing components A and B has a lap shear strength of 7.5 MPa or more, more preferably 8 MPa or more, on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity and then standing, as measured according to the method shown in the examples, and has a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, as measured according to ASTM D5470.

[0082] In another preferred embodiment, the cured adhesive composition obtained by mixing components A and B has, when measured according to the method shown in the examples, a lap shear strength of 6 MPa or more, more preferably 8 MPa or more, particularly preferably 9 MPa or more on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity, followed by cataplasm treatment for 7 days, and a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, when measured according to ASTM D5470.

[0083] In another preferred embodiment, the cured adhesive composition obtained by mixing components A and B has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, on an aluminum substrate after being cured for 7 days at 23°C and 50% relative humidity, followed by being left to stand at 85°C and 85% relative humidity for 168 hours, as measured according to the method shown in the examples, and has a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, as measured according to ASTM D5470.

[0084] In another preferred embodiment, the cured adhesive composition obtained by mixing components A and B has, when measured according to the method shown in the examples, a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, and particularly preferably 10 MPa or more on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity, followed by standing at 85°C and 85% relative humidity for 1,000 hours, and a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, when measured according to ASTM D5470.

[0085] Particularly Preferred Embodiment The following are particularly preferred embodiments of the present invention: 1. (A) (a1) A polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, wherein the polyurethane prepolymer is partially terminated at a silane moiety and has a reactive NCO moiety; The first liquid contains, (B) (b1) One or more polyether polyols; (b2) One or more catalysts capable of promoting the reaction between the NCO moiety of (a1) and (b1); The second liquid contains A two-component flame-retardant polyurethane adhesive compound containing, Liquid A and / or Liquid B contain aluminum hydroxide such that when Liquid A and Liquid B are mixed together to form an adhesive mixture (preferably in a volume ratio of 1:1), the aluminum hydroxide concentration is at least 50% by weight. A two-component flame-retardant polyurethane adhesive compound. 2. A method for bonding two or more substrates, (1) (A) (a1) A polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, wherein the polyurethane prepolymer is partially terminated at a silane moiety and has a reactive NCO moiety; The first liquid contains, (B) (b1) One or more polyether polyols; (b2) One or more catalysts capable of promoting the reaction between the NCO moiety of (a1) and (b1); The second liquid contains A step of preparing a two-component flame-retardant polyurethane adhesive compound containing, A step in which liquid A and / or liquid B contain aluminum hydroxide such that when liquid A and liquid B are mixed together to form an adhesive mixture (preferably in a volume ratio of 1:1), the aluminum hydroxide concentration is at least 50% by weight; (2) A step of mixing liquid A and liquid B to obtain an uncured adhesive; (3) A step of applying an uncured adhesive to at least one substrate; (4) A step of bringing the uncured adhesive into adhesive contact with the second substrate; (5) The process of curing the uncured adhesive; A method that includes this. 3. (1) First substrate; (2) Second substrate; A bonded assembly comprising a first substrate and a second substrate, bonded together by a cured adhesive obtained by mixing liquid A and liquid B together, Solution A, (A) (a1) A polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, wherein the polyurethane prepolymer is partially terminated at a silane moiety and has a reactive NCO moiety; It is the first liquid containing; Solution B, (B) (b1) One or more polyether polyols; (b2) One or more catalysts capable of promoting the reaction between the NCO moiety of (a1) and (b1); It is a second liquid containing; A bonded assembly in which liquid A and / or liquid B contain aluminum hydroxide to such a concentration as at least 50% by weight when liquid A and liquid B are mixed together to form an adhesive mixture (preferably in a volume ratio of 1:1), and the mixture is cured. 4. Any one of the preceding embodiments wherein the polyisocyanate used in the production of the prepolymer is selected from aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof. 5. Any one of the preceding embodiments, wherein the polyisocyanate used in the production of the prepolymer is selected from aromatic polyisocyanates. 6. Any one of the preceding embodiments wherein the polyisocyanate used in the production of the prepolymer is selected from methylenediphenyl diisocyanate (MDI), polycarbodiimide-modified MDI, toluene diisocyanate (TDI), p-phenylenediisocyanate (PPDI), and naphthalene diisocyanate (NDI). 7. Any one of the preceding embodiments, wherein the polyisocyanate used in the production of the prepolymer is MDI and / or polycarbodiimide-modified MDI. 8. Any one of the preceding embodiments, wherein the polyisocyanate used in the production of the prepolymer is used in an amount of 15-40% by weight, more preferably 17-35% by weight, and particularly preferably 20-32% by weight, based on the total weight of component A. 9. Any one of the preceding embodiments, in which the prepolymer is prepared using 15-40% by weight, more preferably 17-35% by weight, and particularly preferably 20-32% by weight of MDI and / or polycarbodiimide-modified MDI based on the total weight of component A. 10. Any one of the preceding embodiments, wherein the polyol used in the manufacture of the prepolymer is a polyether polyol. 11. Any one of the preceding embodiments, wherein the polyol used in the production of the prepolymer comprises polyols selected from poly(alkylene oxide)diols (where the alkylene group is C2-C6, and particularly preferably C2-C4), and mixtures thereof. 12. Any one of the preceding embodiments wherein the polyol used in the production of the prepolymer comprises a polyol selected from poly(ethylene oxide) polyol, poly(propylene oxide) polyol, poly(tetramethylene oxide) polyol, and mixtures thereof. 13. Any one of the preceding embodiments, wherein the polyol used in the production of the prepolymer comprises a polyol selected from poly(propylene oxide) polyols. 14. Any one of the preceding embodiments wherein the polyol used in the production of the prepolymer comprises a polyether polyol based on ethylene oxide-capped propylene glycol having a molecular weight of about 2,000 Da and a functional value of 2. 15. Any one of the preceding embodiments, wherein the polyether polyol used in the production of the prepolymer is used in an amount of 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight, based on the total weight of component A. 16. Any one of the preceding embodiments, wherein the polyol used in the production of the prepolymer is a polyether polyol based on propylene glycol, and is used in an amount of 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight, based on the total weight of component A. 17. Any one of the preceding embodiments wherein the final prepolymer has NCO% by weight in the range of 5 to 30% by weight, more preferably 10 to 25% by weight. 18. Any one of the preceding embodiments in which the aminosilane in component A preferably has general formula I or general formula II:

[0086] [ka]

[0087] (In the formula, R 1 R is independently selected from C1-C6 alkyl groups, 2 (These are independently selected from C2-C6 alkylenes). 19. The aminosilane in component A is of general formula I, and R 1 In any one of the preceding embodiments, R is a C1-C2 alkyl and R2 is a C2-C4 alkylene. In a more preferred embodiment, the aminosilane is of general formula I, and R 1 R1 is methyl, and R2 is propylene. 20. The aminosilane in component A is of general formula II, and R 1 One of the preceding embodiments, wherein R2 is a C1-C2 alkyl group and R2 is a C2-C4 alkylene group. 21. The aminosilane is of general formula II, and R 1 Any one of the preceding embodiments, wherein R2 is methyl and R2 is propylene. 22. Any one of the preceding embodiments wherein the aminosilane of component A is bis(trimethoxysilylpropyl)amine. 23. Any one of the preceding embodiments, wherein the aminosilane in component A is used in an amount preferably 0.5 to 4% by weight, more preferably 1 to 3% by weight, and particularly preferably 1.5 to 2.5% by weight, based on the total weight of component A. 24. Any one of the preceding embodiments, wherein the aminosilane in component A is bis(trimethoxysilylpropyl)amine, and is used in an amount of 0.5 to 4% by weight, more preferably 1 to 3% by weight, and particularly preferably 1.5 to 2.5% by weight, based on the total weight of component A. 25. The prepolymer in component A is • 15-40% by weight, more preferably 17-35% by weight, and especially preferably 20-32% by weight of polyisocyanate based on the total weight of component A; • 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight of polyether polyols based on the total weight of component A; and • 0.5 to 4% by weight, more preferably 1 to 3% by weight, and especially preferably 1.5 to 2.5% by weight of aminosilane based on the total weight of component A; One of the preceding embodiments manufactured using 26. The prepolymer in component A is • 15-40% by weight, more preferably 17-35% by weight, and especially preferably 20-32% by weight of MDI and / or polycarbodiimide-modified MDI, or a mixture of MDI and polycarbodiimide-modified MDI, based on the total weight of component A; • A polyether polyol based on propylene glycol, preferably having an OH value (mgKOH / g) of 109 to 115, in an amount of 5 to 20% by weight, more preferably 8 to 15% by weight, and particularly preferably 9 to 12% by weight, based on the total weight of component A; Based on the total weight of component A, 0.5 to 4% by weight, more preferably 1 to 3% by weight, and particularly preferably 1.5 to 2.5% by weight of an aminosilane of general formula II (where R in the formula is R) 1 R2 is a C1-C2 alkyl group, R2 is a C2-C4 alkylene group, and R 1 (R2 is methyl, and R2 is propylene.) One of the preceding embodiments manufactured using 27. The prepolymer in component A is A mixture of MDI and polycarbodiimide-modified MDI in an amount of 20-32% by weight, based on the total weight of component A; • A polyether polyol based on propylene glycol having an OH number (mgKOH / g) of 10⁹ to 11⁵, in an amount of 9 to 12% by weight relative to the total weight of component A; and • 0.5 to 4% by weight, more preferably 1 to 3% by weight, and especially preferably 1.5 to 2.5% by weight of bis-(trimethoxysilylpropyl)amine based on the total weight of component A. One of the preceding embodiments manufactured using 28. Any one of the preceding embodiments, wherein the polyol used in component B is a polyether polyol. 29. Any one of the preceding embodiments, wherein the polyol used in component B has two or more OH groups. 30. Any one of the preceding embodiments, wherein the polyol used in component B is selected from poly(alkylene oxide)diols, and the alkylene group is C2 to C6, and particularly preferably C2 to C4. 31. Any one of the preceding embodiments, wherein the polyol used in component B is selected from poly(ethylene oxide) polyol, poly(propylene oxide) polyol, and poly(tetramethylene oxide) polyol. 32. Any one of the preceding embodiments, wherein the polyol used in component B is selected from poly(propylene oxide) polyols. 33. Any one of the preceding embodiments, wherein the polyol used in component B comprises a polyol selected from polyetherdiols. 34. Any one of the preceding embodiments, wherein the polyether polyol of component B is a mixture of polyols having a functional value of 2 to 6. 35. Any one of the preceding embodiments, wherein the polyether polyol of component B is a mixture of at least one diol, at least one triol, and at least one polyol having a functional value greater than 3. 36. Any one of the preceding embodiments, wherein the polyether polyol of component B comprises or is a mixture of a diol, a triol, and a polyol having a nominal functional value of 5 to 6. 37. Any one of the preceding embodiments, wherein the polyether polyol of component B comprises a poly(propylene oxide) polyol having a functional value of 2. 38. Any one of the preceding embodiments, wherein the polyether polyol of component B is a mixture of poly(propylene oxide) polyols having a functional value of 2 to 6. 39. Any one of the preceding embodiments, wherein the polyether polyol of component B comprises or is a mixture of at least one poly(propylene oxide)diol, at least one poly(propylene oxide)triol, and at least one poly(propylene oxide)polyol having a functional value greater than 3. 40. Any one of the preceding embodiments, wherein the polyether polyol of component B comprises or is a mixture of a poly(propylene oxide) diol, a poly(propylene oxide) triol, and a poly(propylene oxide) polyol having a nominal functional value of 5 to 6. 41. Any one of the preceding embodiments, wherein the polyether polyol of component B comprises 0 to 45% by weight of a polyether triol, 0 to 30% by weight of a polyether polyol having a functional value greater than 3, and 25 to 100% by weight of a polyether diol, based on the total weight of the polyether polyols in component B. 42. Any one of the preceding embodiments, wherein the polyether polyol of component B comprises, based on the total weight of the polyether polyols in component B, 5 to 45% by weight of a polyether triol, 10 to 35% by weight of a polyether polyol having a functional value greater than 3, and 30 to 80% by weight of a polyether diol. 43. Any one of the preceding embodiments, wherein the polyether polyol of component B comprises 0 to 45% by weight of poly(propylene oxide) triol, 0 to 30% by weight of poly(propylene oxide) polyol having a functional value greater than 3, and 25 to 100% by weight of poly(propylene oxide) diol, based on the total weight of polyether polyol in component B. 44. Any one of the preceding embodiments, wherein the polyether polyol, combined from all components of component B, is present in an amount of 15-50% by weight, more preferably 16-45% by weight, and particularly preferably 18-42% by weight, based on the total weight of component B. 45. Any one of the preceding embodiments wherein component B comprises a mixture of polyether polyols comprising or consisting of the following, in an amount of 15 to 50% by weight, more preferably 16 to 45% by weight, and particularly preferably 18 to 42% by weight, based on the total weight of component B: (1) Based on the total weight of polyether polyols in component B, 30-45% by weight of polyether triol, 19-30% by weight of polyether polyol having a functional value greater than 3, and 27-40% by weight of polyether diol; or (2) Based on the total weight of polyether polyols in component B, 5 to 15% by weight of polyether triol, 10 to 25% by weight of polyether polyol having a functional value greater than 3, and 70 to 80% by weight of polyether diol; or (3) 100% by weight of polyetherdiol based on the total weight of polyether polyols in component B; or (4) Based on the total weight of the polyether polyols in component B, 30-45% by weight of poly(propylene oxide) triol, 19-30% by weight of poly(propylene oxide) polyol having a functional value greater than 3, and 27-40% by weight of poly(propylene oxide) diol; or (5) Based on the total weight of the polyether polyols in component B, 5 to 15% by weight of poly(propylene oxide) triol, 10 to 25% by weight of poly(propylene oxide) polyol having a functional value greater than 3, and 70 to 80% by weight of poly(propylene oxide) diol. 46. ​​Any one of the preceding embodiments, wherein component B comprises a diol and / or triol having a molecular weight of less than 200 Da, more preferably less than 150 Da. 47. Any one of the preceding embodiments, wherein component B comprises butanediol (e.g., 1,4-butanediol). 48. Any one of the preceding embodiments wherein component B contains glycerin. 49. Any one of the preceding embodiments, wherein component B contains 2 to 8% by weight, more preferably 2.5 to 5% by weight, of a diol or triol having a molecular weight of less than 200 Da, based on the total weight of component B. 50. Any one of the preceding embodiments, wherein component B contains butanediol (e.g., 1,4-butanediol) in an amount of 2 to 8% by weight, more preferably 2.5 to 5% by weight, based on the total weight of component B. 51. Any one of the preceding embodiments, wherein component B contains glycerin in an amount of 2 to 8% by weight, more preferably 2.5 to 5% by weight, based on the total weight of component B. 52. Any one of the preceding embodiments, wherein the catalyst is selected from Lewis bases and Lewis acids. 53. Any one of the preceding embodiments wherein the catalyst is selected from tertiary amines, organotin compounds, and combinations thereof. 54. Any one of the preceding embodiments wherein the catalyst comprises diazabicyclo[2.2.2]octane. 55. Any one of the preceding embodiments wherein the catalyst comprises an organotin compound. 56. Any one of the preceding embodiments wherein the catalyst comprises di-n-octyl tungbis(isooctyl mercaptoacetate). 57. Any one of the preceding embodiments, wherein the catalyst is used in an amount of 0.005 to 0.02% by weight, more preferably 0.0075 to 0.015% by weight, and particularly preferably 0.01% by weight, based on the total weight of component B. 58. Any one of the preceding embodiments, wherein the catalyst is di-n-octyl tungbis(isooctyl mercaptoacetate) and is used in an amount of 0.005 to 0.02% by weight, more preferably 0.0075 to 0.015% by weight, and particularly preferably 0.01% by weight, based on the total weight of component B. 59. Any one of the preceding embodiments, wherein the concentration of aluminum hydroxide in the adhesive mixture obtained by mixing components A and B is 50 to 70% by weight, more preferably 55 to 68% by weight, based on the total weight of the mixture. 60. Any one of the preceding embodiments, wherein aluminum hydroxide is present in component A at a concentration of 50-70% by weight, more preferably 55-68% by weight, based on the total weight of component A. 61. Any one of the preceding embodiments, wherein aluminum hydroxide is present in component B at a concentration of 50-70% by weight, more preferably 55-68% by weight, based on the total weight of component B. 62. Any one of the preceding embodiments, wherein aluminum hydroxide is present in both component A and component B. 63. Any one of the preceding embodiments, wherein aluminum hydroxide is present in both component A and component B in an amount of 50-70% by weight, more preferably 55-68% by weight, based on the total weight of each component. 64. Aluminum hydroxide is approximately 20 microns in size D 50 A prior embodiment having the following: 65. The adhesive mixture obtained by mixing component A and component B (preferably in a volume ratio of 1:1) has a diameter of approximately 20 microns. 50 Any one of the preceding embodiments, comprising 50 to 70% by weight, more preferably 55 to 68% by weight, of aluminum hydroxide having the property of the total weight of the mixture. 66. Component A is approximately 20 microns of D50 Any one of the preceding embodiments, comprising 50 to 70% by weight, more preferably 55 to 68% by weight, of aluminum hydroxide having the property, based on the total weight of component A. 67. Component B is approximately 20 microns of D 50 Any one of the preceding embodiments, comprising 50 to 70% by weight, more preferably 55 to 68% by weight, of aluminum hydroxide having the property, based on the total weight of component B. 68. Both component A and component B are approximately 20 microns of D 50 Any one of the preceding embodiments, comprising 50 to 70% by weight, more preferably 55 to 68% by weight, of aluminum hydroxide having the same property, based on the total weight of each component. 69. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has a thermal conductivity of at least 0.75 W / mK, more preferably at least 0.8 W / mK, after curing for 7 days at 23°C and 50% relative humidity and then being left to stand, as measured according to ASTM D5470. 70. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has a lap shear strength of 7.5 MPa or more, more preferably 8 MPa or more, on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity and then standing, as measured according to the method shown in the Examples. 71. Any one of the preceding embodiments wherein a cured adhesive composition obtained by mixing components A and B has a lap shear strength of 6 MPa or more, more preferably 8 MPa or more, and particularly preferably 9 MPa or more on an aluminum substrate, after being cured for 7 days at 23°C and 50% relative humidity, then left to stand, and subsequently treated with cataplasma for 7 days, as measured according to the method shown in the Examples. 72. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, on an aluminum substrate after being cured for 7 days at 23°C and 50% relative humidity, followed by being left to stand, and then left at 85°C and 85% relative humidity for 168 hours, as measured according to the method shown in the Examples. 73. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, and particularly preferably 10 MPa or more on an aluminum substrate, after being cured for 7 days at 23°C and 50% relative humidity, then left to stand, and subsequently left to stand for 1,000 hours at 85°C and 85% relative humidity, as measured according to the method shown in the Examples. 74. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has a V0 rating according to UL94 after curing at 23°C and 50% relative humidity for 7 days. 75. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B (at 23°C and 50% relative humidity for 7 days) has a lap shear strength of 7.5 MPa or more, more preferably 8 MPa or more, on an aluminum substrate after curing at 23°C and 50% relative humidity for 7 days and then being left to stand, and has a V0 rating in UL94 after curing at 23°C and 50% relative humidity for 7 days. 76. Any one of the preceding embodiments, wherein the cured adhesive (at 23°C and 50% relative humidity for 7 days) has a lap shear strength of 6 MPa or more, more preferably 8 MPa or more, and particularly preferably 9 MPa or more on an aluminum substrate after 7 days of cataplasm treatment, as measured according to the method shown in the examples, and has a UL94 V0 grade after curing at 23°C and 50% relative humidity for 7 days. 77. Any one of the preceding embodiments wherein the cured adhesive (at 23°C and 50% relative humidity for 7 days) has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, on an aluminum substrate after 168 hours at 85°C and 85% relative humidity, as measured according to the method shown in the Examples, and has a UL94 V0 rating after curing for 7 days at 23°C and 50% relative humidity. 78. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B (at 23°C and 50% relative humidity for 7 days) has a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, and particularly preferably 10 MPa or more on an aluminum substrate after 1,000 hours at 85°C and 85% relative humidity, as measured according to the method shown in the Examples, and has a UL94 V0 rating after curing for 7 days at 23°C and 50% relative humidity. 79. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has a lap shear strength of 7.5 MPa or more, more preferably 8 MPa or more, on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity and then standing, as measured according to the method shown in the Examples, and has a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, as measured according to ASTM D5470. 80. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has, when measured according to the method shown in the Examples, a lap shear strength of 6 MPa or more, more preferably 8 MPa or more, particularly preferably 9 MPa or more on an aluminum substrate after curing at 23°C and 50% relative humidity for 7 days, followed by cataplasm treatment for 7 days, and a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, when measured according to ASTM D5470. 81. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has, when measured according to the method shown in the Examples, a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity, followed by standing at 85°C and 85% relative humidity for 168 hours, and a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, when measured according to ASTM D5470. 82. Any one of the preceding embodiments, wherein a cured adhesive composition obtained by mixing components A and B has, when measured according to the method shown in the Examples, a lap shear strength of 8 MPa or more, more preferably 9 MPa or more, particularly preferably 10 MPa or more on an aluminum substrate after curing for 7 days at 23°C and 50% relative humidity, followed by standing at 85°C and 85% relative humidity for 1,000 hours, and a thermal conductivity of 0.75 W / mK or more, more preferably 0.8 W / mK or more, when measured according to ASTM D5470. [Examples]

[0088] [Table 1]

[0089] Manufacturing of Solution A (Isocyanate component) The amounts of MDI, polyether polyol, and aminosilane (Dynasilan 1124) listed in Table 2 were first placed in a planetary mixer and mixed at room temperature for 2 hours at a mixing speed of 300–1,000 rpm. Then, the fillers ATH, MPP, talc, carbon black, and amorphous silica were added to the mixture. The fillers were pre-dried in an oven at a temperature of 100–200°C until the moisture level was less than 1,000 ppm. The fillers were then mixed into the mixture at a mixing speed of 1,000–2,000 rpm for 30–60 minutes. The mixture was then filled into cartridges and stored.

[0090] Manufacturing of Solution B (Polyol component) The amounts of polyol, silane (Dynasilan), and catalyst shown in Table 2 were mixed at 500–1,000 rpm for 5–15 minutes, and then fillers, ATH, MPP, talc, amorphous silica, and molecular sieves, were added to the mixture. The fillers were pre-dried in an oven at a temperature of 100–200°C until the moisture level was less than 1,000 ppm. The fillers were then mixed into the mixture at a mixing speed of 1,000–2,000 rpm for 30–60 minutes. The mixture was then filled into cartridges and stored.

[0091] Use of adhesive Solution A and Solution B were mixed in a 1:1 volume ratio using a static mixer. This can then be applied to the substrate manually or by robot.

[0092] method flammable Adhesive samples were prepared by mixing liquids A and B in a 1:1 volume ratio and curing the mixture at 23°C and 50% relative humidity for 7 days. The flammability of the samples was measured according to the UL94 combustion test. Samples were graded V0 if combustion ceased within 10 seconds on a vertical test specimen. Particle sagging was acceptable as long as it did not ignite. The results are reported in Table 2.

[0093] Thermal conductivity Thermal conductivity was measured according to ASTM D5470. Three cured adhesive samples of three different thicknesses (1, 1.5, and 2.5 mm) were prepared by mixing liquids A and B in a static mixer, cured at 23°C and 50% relative humidity for 7 days, and then cut to the target shape and size using a cutter. Thermal conductivity tests were performed according to ASTM D5470, and a thermal gel was applied between the test rod and the surface of the cured adhesive sample to minimize the thermal impedance at the interface due to trapped air. The sample setting temperature was preferably 20-50°C, and the pressure applied to the sample was greater than 0.5 MPa.

[0094] Lapp shear test The lap shear strength was measured on aluminum alloy 3003 according to DIN EN1465. An aluminum substrate (from Novelis, AA6061 T6 1.92mm MF noPT no lub, 140×25mm, thickness 1.9mm) was used. The substrate was cleaned with isopropanol before use. The adhesive was prepared by mixing liquid A and liquid B in a 1:1 volume ratio, and after applying it to one substrate, the second substrate was joined within 5 minutes. The thickness was adjusted to 1.0mm, and the overlap area was 25mm×25mm. After curing the material and leaving it at 23°C and 50% relative humidity for 7 days, a lap shear test was performed. Subsequently, the lap shear specimen was mounted on a tensile strength meter and a lap shear test was performed using a tensile speed of 10mm / min. The deflection curve under force was observed. The strength at fracture was reported as the lap shear strength.

[0095] Lapping shear tests were performed immediately after curing, after 7 days of cataplasmic exposure (cataplasmic conditions: 70°C, 100% relative humidity for 7 days, followed by 24 hours of thermal shock at -30°C), after 168 hours at 85°C, 85% relative humidity, and after 1,000 hours at 85°C, 85% relative humidity. The results are reported in Table 2.

[0096] [Table 2]

[0097] [Table 3]

[0098] All examples and comparative examples of the present invention not only possessed the desired UL94 flame retardancy grade V0, but also had an acceptable thermal conductivity of over 0.75 W / mK. However, in Comparative Examples 4 and 5, the lap shear strength immediately after curing for 7 days at 23°C and 50% relative humidity was significantly lower than that of the examples of the present invention. Similarly, Comparative Examples 4 and 5 showed a significant decrease in lap shear strength under all accelerated aging conditions, while Examples 1 and 2 of the present invention showed no decrease in lap shear strength, and even a slight increase.

Claims

1. (A) (a1) A polyurethane prepolymer produced from at least one polyol, at least one polyisocyanate, and an aminosilane, wherein the polyurethane prepolymer is partially terminated at a silane moiety and has a reactive NCO moiety; A first liquid containing, (B) (b1) One or more polyether polyols; (b2) One or more catalysts capable of promoting the reaction between the NCO moiety of (a1) and (b1); The second liquid contains A two-component flame-retardant polyurethane adhesive compound containing, Liquid A and / or Liquid B contain aluminum hydroxide such that, when Liquid A and Liquid B are mixed together to form an adhesive compound, the aluminum hydroxide concentration is at least 50% by weight based on the total weight of the adhesive compound. A two-component flame-retardant polyurethane adhesive compound.

2. The adhesive formulation according to claim 1, wherein the polyisocyanate used in the production of the prepolymer is selected from aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof.

3. The adhesive compound according to claim 1 or 2, wherein the polyisocyanate used in the production of the prepolymer is selected from methylenediphenyl diisocyanate (MDI), polycarbodiimide-modified MDI, toluene diisocyanate (TDI), p-phenylenediisocyanate (PPDI), and naphthalene diisocyanate (NDI).

4. The adhesive compound according to any one of claims 1 to 3, wherein the polyol used in the production of the prepolymer is a polyether polyol.

5. The polyol used in the production of the prepolymer is a poly(alkylene oxide) diol (where the alkylene group is C 2 ~C 6 And, more preferably, the alkylene group is C 2 ~C 4 An adhesive formulation according to any one of claims 1 to 4, comprising a polyol selected from ( ) and mixtures thereof.

6. The aminosilane in component A is preferably of general formula I or general formula II: 【Chemistry 1】 (wherein, R 1 is independently selected from C 1 to C 6 alkyl, and R 2 is independently selected from C 2 to C 6 alkylene) An adhesive compound according to any one of claims 1 to 5, having the following characteristics.

7. The prepolymer in component A is - A mixture of MDI and polycarbodiimide-modified MDI in an amount of 20 to 32% by weight, based on the total weight of component A; - A polyether polyol based on propylene glycol having an OH value (mgKOH / g) of 109 to 115, in an amount of 9 to 12% by weight based on the total weight of component A; and - 0.5 to 4% by weight, more preferably 1 to 3% by weight, and especially preferably 1.5 to 2.5% by weight of bis-(trimethoxysilylpropyl)amine based on the total weight of component A. An adhesive compound according to any one of claims 1 to 6, manufactured using

8. The adhesive compound according to any one of claims 1 to 7, wherein the polyol used in component B is a polyether polyol.

9. The polyol used in component B is selected from poly(alkylene oxide)diols, and the alkylene group is C 2 ~C 6 The alkylene group is particularly preferably C 2 ~C 4 The adhesive compound according to any one of claims 1 to 8.

10. The adhesive compound according to claim 9, wherein the polyol used in component B is selected from poly(ethylene oxide) polyol, poly(propylene oxide) polyol, and poly(tetramethylene oxide) polyol.

11. Component B comprises a mixture of polyether polyols in an amount of 15 to 50% by weight, more preferably 16 to 45% by weight, and particularly preferably 18 to 42% by weight, based on the total weight of component B, wherein the mixture of polyether polyols is: (1) Based on the total weight of polyether polyols in component B, 30 to 45% by weight of polyether triols, 19 to 30% by weight of polyether polyols having a functional value greater than 3, and 27 to 40% by weight of polyether diols An adhesive compound according to any one of claims 1 to 10, comprising (1) or a mixture of (1).

12. The adhesive formulation according to any one of claims 1 to 11, wherein component B comprises butanediol (for example, 1,4-butanediol).

13. The adhesive formulation according to any one of claims 1 to 12, wherein component B contains glycerin.

14. The adhesive formulation according to any one of claims 1 to 13, wherein the catalyst is selected from a Lewis base and a Lewis acid.

15. The catalyst is used in an amount of 0.005 to 0.02% by weight, more preferably 0.0075 to 0.015% by weight, and especially preferably 0.01% by weight, based on the total weight of component B, or Both component A and component B are approximately 20 microns in size. 50 The adhesive compound according to any one of claims 1 to 14, comprising aluminum hydroxide having the above in an amount of 50 to 70% by weight, more preferably 55 to 68% by weight, based on the total weight of each component.

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