Moisture-curing polyurethane hot melt adhesive composition

Abstract

The present invention provides at least one polyurethane prepolymer obtained by reacting a reactant mixture comprising: (A) (A1) a polyol mixture comprising: (a) at least one polyester polyol; and (b) at least one polyether polyol; and (A2) at least one polyisocyanate having at least two isocyanate groups in one molecule; (B) at least one (meth)acrylic polymer present in an amount of 14% by weight or less, based on the total weight of the adhesive composition; and (C) at least one amorphous polyalphaolefin having a softening point less than 100° C., present in an amount of 20% by weight or less, based on the total weight of the adhesive composition; The present invention provides a moisture-curable polyurethane hot melt adhesive composition comprising:

Description

Technical Field

[0001] Technical Field The present invention relates to a moisture-curable polyurethane hot melt adhesive composition, a cured product thereof, and its use.

Background Art

[0002] Background of the Invention Polyurethane hot melt adhesives have a long history and are widely spread. In the context of industrial applications, polyurethane hot melt adhesives are solids at room temperature, melt into viscous liquids when heated to a suitable temperature, and are applied to the substrates to be adhered. Thereafter, the molten adhesive composition cools and solidifies to form an initial adhesion to the substrate. Further, it reacts with moisture to form a crosslinked structure, and high final strength can be achieved. Such adhesives are composed of a polyol component and a polyisocyanate component having two or more functional groups. These adhesives are preferred over other adhesives in many applications because of their excellent adhesive strength, flexibility, impact resistance, and fatigue resistance.

[0003] Polyurethane hot melt adhesives exhibit excellent adhesive strength in applications in many fields. However, the adhesives of this type known so far are not suitable for structural adhesion of plastic or metal workpieces because they do not have sufficient impact toughness. In particular, for the manufacture of electronic applications that require rapid curing, it is difficult to simultaneously achieve a high initial tensile cross strength and excellent impact resistance of the cured adhesive. This is probably because a large amount of crystalline polyester polyol is required to create a high initial cross-tensile strength, but it reduces the impact resistance of the adhesive when cured.

Summary of the Invention

Problems to be Solved by the Invention

[0004] From the above, there is still a need for a moisture-curable polyurethane hot melt adhesive that exhibits high initial cross-tensile strength and excellent impact resistance upon curing.

Means for Solving the Problems

[0005] Summary of the Invention According to a first aspect of the present invention, disclosed herein is a moisture-curing polyurethane hot-melt adhesive composition comprising: (A) At least one polyurethane prepolymer obtained by reacting a reagent mixture containing the following (A1) Polyol mixture containing the following (a) at least one polyester polyol, and (b) at least one polyether polyol, and (A2) At least one polyisocyanate having at least two isocyanate groups in one molecule, (B) At least one (meth)acrylic polymer present in an amount of 14% by weight or less based on the total weight of the adhesive composition, (C) At least one amorphous polyalphaolefin having a softening point of less than 100°C, present in an amount of 20% by weight or less based on the total weight of the adhesive composition.

[0006] A second aspect of the present invention provides a method for preparing a moisture-curing polyurethane hot-melt adhesive composition.

[0007] According to a third aspect of the present invention, provided herein is a laminate comprising a first substrate, a second substrate, and an adhesive layer sandwiched between them, wherein the first substrate and the second substrate are independently selected from glass, resin, and metal, and the adhesive layer is formed by curing the adhesive composition of the present invention.

[0008] According to a fourth aspect of the present invention, provided herein are electronic devices comprising a laminate of the present invention or manufactured using an adhesive composition according to the present invention.

[0009] According to a fifth aspect of the present invention, what is provided herein is the use of an adhesive composition or a laminate according to the present invention in the manufacture of an electronic device.

[0010] Other features and aspects of the subject will be discussed in more detail below. [Modes for carrying out the invention]

[0011] Detailed description of the invention Those skilled in the art should understand that the present invention describes only exemplary embodiments and is not intended to limit the broader aspects of the invention. Each aspect described herein can be combined with other aspects unless explicitly indicated otherwise. In particular, features indicated as preferred or advantageous can be combined with other features or characteristics indicated as preferred or advantageous.

[0012] Unless otherwise specified, terms used in the context of this invention shall be interpreted according to the following definitions.

[0013] Unless otherwise specified, the terms "a," "an," and "the" in this specification include singular and plural references.

[0014] As used herein, the terms “comprising” and “comprises” are synonymous with “including,” “includes,” or “containing,” and “contains,” and are inclusive or open-ended, and do not exclude any additional unlisted members, elements, or process steps.

[0015] The terms “at least one” or “one or more” used herein to define components refer to the types of components, not the absolute number of molecules. For example, “one or more polyols” means one type of polyol or a mixture of several different polyols.

[0016] As used herein, the term "amorphous" means that there is no melting transition when measured using differential scanning calorimetry (DSC).

[0017] As used herein, the term "crystalline" means that there is a melting transition when measured using differential scanning calorimetry (DSC).

[0018] As used herein, the term "room temperature" refers to a temperature of from about 20 °C to about 25 °C, preferably about 25 °C.

[0019] Unless otherwise specified, the recitation of numerical endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints themselves.

[0020] All documents cited herein are hereby incorporated by reference in their entirety.

[0021] Unless otherwise indicated, molecular weights refer to number-average molecular weight (Mn). All molecular weight data refer to values obtained by gel permeation chromatography (GPC), unless otherwise specified, for example by regulations such as DIN 55672.

[0022] In this context, the glass transition temperature (Tg) or melting point of a particular polymer is determined using DSC in accordance with DIN 53 765.

[0023] The softening point referred to herein is determined using the ring-and-ball method in accordance with DIN ISO 4625.

[0024] Unless otherwise defined, all terms used in the present invention, including technical and scientific terms, have the meaning commonly understood by a person of ordinary skill in the art to which this invention pertains.

[0025] In one aspect, the present disclosure generally relates to a moisture-curable polyurethane hot melt adhesive composition comprising the following: (A) At least one polyurethane prepolymer obtained by reacting a reagent mixture containing the following (A1) Polyol mixtures containing the following: (a) at least one polyester polyol, and (b) at least one polyether polyol, and (A2) At least one polyisocyanate having at least two isocyanate groups in one molecule; (B) At least one (meth)acrylic polymer present in an amount of 14% by weight or less based on the total weight of the adhesive composition, (C) At least one amorphous polyalphaolefin having a softening point of less than 100°C, present in an amount of 20% by weight or less based on the total weight of the adhesive composition.

[0026] (A) Polyurethane prepolymer According to the present invention, a moisture-curing polyurethane hot-melt adhesive composition is (A1) A polyol mixture comprising: (a) at least one polyester polyol, and (b) at least one polyether polyol, and (A2) at least one polyisocyanate having at least two isocyanate groups in one molecule. It comprises at least one polyurethane prepolymer obtained by reacting a reactant mixture containing the above.

[0027] In some embodiments, the polyurethane prepolymer has a number-average molecular weight (Mn) of 5,000 to 30,000 g / mol, preferably 8,000 to 20,000 g / mol.

[0028] In some embodiments, component (A) is present in an amount of preferably 66% to 99% by weight, more preferably 70% to 90% by weight, based on the total weight of the adhesive composition.

[0029] (A1) Polyol mixture In some embodiments, the polyol mixture (A1) used in the present invention comprises (a) at least one polyester polyol (a).

[0030] (a) Polyester polyol The polyester polyol used in this invention can be selected from solid polyester polyols, liquid polyester polyols, and combinations thereof. The solid polyester polyol can be a crystalline polyester polyol, an amorphous polyester polyol, or a combination thereof.

[0031] In some embodiments, crystalline polyester polyols can be used in the present invention to provide good adhesive strength to the adhesive composition.

[0032] Examples of such crystalline polyester polyols include those obtained by ring-opening polymerization of lactones such as ε-caprolactone, and / or those obtained from diols or diacids. Examples of diols useful for the preparation of preferred polyester polyols include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and combinations thereof. Examples of diacids useful for the preparation of preferred polyester polyols include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanediol, dimer acid, and combinations thereof. The range of useful diacids includes various diacid derivatives such as carboxylic acid esters (especially methyl and ethyl esters), acid halides (such as acid chlorides), and acid anhydrides, and combinations thereof.

[0033] Specific examples of suitable crystalline polyester polyols include poly(hexanediol adipate) polyol, poly(butanediol adipate) polyol, poly-epsilon-caprolactone polyol, poly(dodecanediol hexanediol) polyol, poly(hexanediol adipate terephthalate) polyol, and combinations thereof.

[0034] Suitable commercially available crystalline polyester polyols are sold under the DYNACOLL 7300 series from Evonik Industries AG, including DYNACOLL 7360, 7361, 7362, 7363, 7380, and 7390, and the CAPA series from Perstorp Polyols Inc., which includes caprolactone polyols such as CAPA 2201, 2205, 2209, 2302, 2304, and 2402.

[0035] In some embodiments, amorphous polyester polyols can also be used when preparing the polyurethane prepolymers of the present invention.

[0036] Amorphous polyester polyols contain reaction products of a polyacid component (e.g., polyacid, polyacid anhydride, polyacid ester, polyacid halide) and a stoichiometric excess amount of polyol. At least one of the polyacid component and the polyol contains an aromatic group. Suitable polyacids include, for example, diacids (e.g., dicarboxylic acids), triacids (e.g., tricarboxylic acids), and higher-order acids, such as aromatic dicarboxylic acids, their anhydrides and esters (e.g., terephthalic acid, isophthalic acid, dimethyl terephthalate, diethyl terephthalate, phthalic acid, phthalic anhydride, methyl-hexahydrophthalic acid, methyl-hexahydrophthalic anhydride, methyl-tetrahydrophthalic acid, methyl-tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, tetrahydrophthalic acid, etc.). These include aliphatic dicarboxylic acids and their anhydrides (e.g., maleic acid, maleic anhydride, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, chlorendic acid, 1,2,4-butanetricarboxylic acid, decanedicarboxylic acid, octadecanedicarboxylic acid, dimer acid, dimerized fatty acid, trimer fatty acid, fumaric acid), and alicyclic dicarboxylic acids (e.g., 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.), as well as mixtures thereof.Suitable examples of polyols include aliphatic polyols, such as ethylene glycol, propanediols (e.g., 1,2-propanediol, 1,3-propanediol, etc.), butanediols (e.g., 1,3-butanediol, 1,4-butanediol, 1,2-butanediol, etc.), 1,3-butenediol, 1,4-butenediol, 1,4-butynediol, pentanediol (e.g., 1,5-pentanediol), pentenediol, pentynediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and tetraethylene Examples include glycols, polyethylene glycol, propylene glycol, polypropylene glycol (e.g., dipropylene glycol and tripropylene glycol), 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, dimergol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, glycerol, tetramethylene glycol, polytetramethylene glycol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, trimethylolpropane, pentaerythritol, sorbitol, glucose, and combinations thereof.

[0037] If present, useful amorphous polyester polyols include specific examples such as poly(hexanediol phthalate) polyol, poly(neopentyl glycol adipate) polyol, poly(neopentyl glycol phthalate) polyol, poly(neopentyl glycol hexanediol phthalate) polyol, poly(diethylene glycol phthalate) polyol, poly(ethylene glycol adipate terephthalate) polyol, polyethylene terephthalate polyol, random copolymer diols of ethylene glycol, hexanediol, neopentyl glycol, adipic acid, and terephthalic acid, and combinations thereof.

[0038] Useful amorphous polyester polyols are commercially available under various trade names, including, for example, DYNACOLL 7110, 7130, 7140, and 7150 from Evonik Industries AG, and FLP PA-1000N from Xu Chuan Chemical (Suzhou) Co., Ltd.

[0039] In some embodiments, the polyester polyol used in the present invention can be liquid at room temperature, thereby imparting wettability to the adhesive composition and impact resistance to the cured product. Therefore, the liquid polyester polyol preferably has a glass transition temperature (Tg) of 0°C or lower. If the Tg of the liquid polyester polyol is too high, it becomes difficult to maintain its liquid state.

[0040] Suitable liquid polyester polyols include those obtained by ring-opening polymerization of lactones such as ε-caprolactone, and / or those obtained from diols and diacids. Examples of diols useful for the preparation of preferred polyester polyols include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and combinations thereof. Examples of diacids useful for the preparation of preferred polyester polyols include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanediol, dimer acids, and combinations thereof. The range of useful diacids includes various diacid derivatives such as carboxylic acid esters (especially methyl and ethyl esters), acid halides (such as acid chlorides), and acid anhydrides, and combinations thereof.

[0041] Specific examples of suitable liquid polyester polyols include poly(hexanediol adipate) polyol, poly(butanediol adipate) polyol, poly-epsilon-caprolactone polyol, poly(dodecanediol hexanediol) polyol, poly(hexanediol adipate terephthalate) polyol, and mixtures thereof.

[0042] Suitable commercially available liquid polyester polyols are sold under product names such as the DYNACOLL 7200 series (DYNACOLL 7210, 7230, 7231, 7250, etc.) from Evonik Industries AG, and Stepan PDP 70 from Stepan Corporation.

[0043] Preferably, a combination of at least one crystalline polyester polyol, at least one amorphous polyester polyol, and at least one liquid polyester polyol can be used as the reactant (a) in the present invention.

[0044] In a preferred embodiment, the reactant (a) has a number-average molecular weight (Mn) of 800 to 20,000 g / mol, preferably 1,000 to 10,000 g / mol, and more preferably 1,000 to 5,000 g / mol.

[0045] Particularly preferably, the reactant (a) may be present in an amount of 30% to 70% by weight, more preferably 35% to 65% by weight, based on the total weight of the adhesive composition.

[0046] (b) Polyether polyol In some embodiments, the polyol mixture (A1) used in the present invention comprises (b) at least one polyether polyol.

[0047] The polyether polyols used in the present invention are well known to those skilled in the art. These polyether polyols are obtained by copolymerizing at least one compound, such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran, with at least one compound having an average of at least two active hydrogen atoms per molecule, such as the polyhydric alcohols mentioned above, including ethylene glycol, propylene glycol, dipropylene glycol, glycerol, and combinations thereof. Other suitable polyhydric compounds include sucrose, ethylenediamine, propylenediamine, triethanolamine, 1,2-propanedithiol, and combinations thereof.

[0048] Preferred polyether polyols can be selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, polyethylene oxide, polybutylene oxide, and any of the aforementioned ethylene oxide end-cap versions, as well as combinations thereof. The most preferred polyether polyols are polytetramethylene ether glycol, poly(oxypropylene) glycol, ethylene oxide end-cap poly(oxypropylene) glycol, and combinations thereof.

[0049] In a preferred embodiment, the polyether polyol has a number-average molecular weight (Mn) of 200 to 8,000 g / mol, preferably 400 to 4,000 g / mol, and more preferably 400 to 2,000 g / mol.

[0050] In this invention, commercially available products can also be used. Examples include Dow Chemical's Voranol 2104, 2110, 2120, and 2140.

[0051] Particularly preferably, the reactant (b) may be present in an amount of 10% to 40% by weight, more preferably 15% to 36% by weight, based on the total weight of the adhesive composition.

[0052] (A2) Polyisocyanate The moisture-curing polyurethane hot melt adhesive composition is a polyol mixture comprising (A1) the following: (a) at least one polyester polyol, and (b) at least one polyether polyol, and (A2) at least one polyisocyanate having at least two isocyanate groups in one molecule. It comprises at least one polyurethane prepolymer obtained by reacting a mixture of reagents containing the above.

[0053] Polyisocyanates useful as reagents (A2) include any suitable isocyanates having at least two isocyanate groups in one molecule, such as aliphatic, cyclopaliphatic, aralliphatic, arylalkyl, aromatic isocyanates, and combinations thereof.

[0054] Preferred reagents (A2) include 4,4-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), partially hydrogenated MDI (H6MDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), 4,4-diphenyldimethylmethane diisocyanate, dialkylenediphenylmethane diisocyanate, tetraalkylenediphenylmethane diisocyanate, and 4,4-dibenzyl Isomers of diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, toluenediisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (IPDI), tetra Lamethoxybutane-1,4-diisocyanate, naphthalene-1,5-diisocyanate (NDI), butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexane-2,3,3-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, methylenetriphenyltriiso Polyisocyanates (MIT), bisisocyanatoethyl phthalate, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, and dimer fatty acid diisocyanates, lysine ester diisocyanates, 4,4-dicyclohexylmethane diisocyanate, 1,3-cyclohexane or 1,4-cyclohexane diisocyanate, and combinations thereof can be selected. The most preferred polyisocyanates are 4,4-diphenylmethane diisocyanate (MDI) and its isomers, chain-extended MDI, and combinations thereof.

[0055] Useful commercially available polyisocyanates that can be used as reagents (A2) include Bayer's DESMODUR 44C FUSED, Covestro's Desmodur 0118 I and Desmodur 44M, Wanhua Chemicals' Vannate MDI 100F, and HUNTSMAN's Supresec 1809.

[0056] Particularly preferably, the reactant (A2) may be present in an amount of 10% to 25% by weight, preferably 10% to 20% by weight, based on the total weight of the adhesive composition.

[0057] (B)(meth)acrylic polymer According to the present invention, the moisture-curing polyurethane hot-melt adhesive composition contains (B) at least one (meth)acrylic polymer in an amount of 14% by weight or less based on the total weight of the adhesive composition, and provides the adhesive composition with excellent initial cross-tensile strength when cured. The (meth)acrylic polymer used as component (B) in the present invention may be linear or branched, and may consist of copolymerized alkyl-functional (meth)acrylic monomers, acid-functional (meth)acrylic monomers, or tertiary amine-functional (meth)acrylic monomers, and may contain other functional groups that do not react rapidly with isocyanate functional groups. Branching of the (meth)acrylic polymer can be induced by copolymerizing a polyfunctional comonomer and / or by using a polyfunctional chain transfer agent and / or a polyfunctional initiator.

[0058] Suitable comonomers used to form the (meth)acrylic polymer of the present invention include, but are not limited to, C1-C12 esters of methacrylic acid and acrylic acid, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl (lauryl) methacrylate, or the corresponding acrylate. Mixtures of compatible (meth)acrylate monomers can also be used. Methacrylic acid and acrylic acid comonomers based on esters of methacrylic acid and acrylic acid with poly(ethylene glycol) and / or poly(propylene glycol) and / or glycol ethers can also be used. Other vinyl comonomers that can be used include vinyl esters (such as vinyl acetate and vinyl propionate); vinyl ethers; esters of crotonic acid, maleic acid, fumaric acid, and itaconic acid; styrene; alkylstyrene; acrylonitrile; butadiene, and their comonomers. The specific monomer selected largely depends on the intended end use of the adhesive.

[0059] Suitable acid-functional comonomers used to form the (meth)acrylic polymer of the present invention include, but are not limited to, methacrylic acid and acrylic acid.

[0060] Suitable hydroxyl-functionalized comonomers used to form the (meth)acrylic polymer of the present invention that can be incorporated include, but are not limited to, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxybutyl methacrylate or their corresponding acrylates.

[0061] Suitable amine-functionalized comonomers used to form the (meth)acrylic polymer of the present invention include, but are not limited to, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or the corresponding acrylate.

[0062] Component (B) can be prepared by free radical polymerization, and the molecular weight (Mn) is controlled by using a chain transfer agent, such as a catalytic chain transfer agent based on a thiol or transition metal complex, like dodecyl mercaptan. Branched (meth)acrylic polymers are produced by copolymerizing polyfunctional monomers and / or using a polyfunctional chain transfer agent and / or a polyfunctional initiator.

[0063] In a preferred embodiment, component (B) has a number-average molecular weight (Mn) of 5,000 to 100,000 g / mol, preferably 5,000 to 80,000 g / mol, and more preferably 8,000 to 50,000 g / mol.

[0064] Useful ingredients (B) are commercially available, such as Elvacite 2013 from Lucite International.

[0065] According to the present invention, the (meth)acrylic polymer must be present in an amount of 14% by weight or less based on the total weight of the adhesive composition; otherwise, as the content of the (meth)acrylic polymer increases, it becomes insoluble in the adhesive composition. Particularly preferably, component (B) can be present in an amount of 0.1% to 12% by weight, preferably 1% to 10% by weight, based on the total weight of the adhesive composition.

[0066] (C) Amorphous polyalphaolefin According to the present invention, the moisture-curing polyurethane hot-melt adhesive composition contains (C) at least one amorphous polyalphaolefin having a softening point of less than 100°C in an amount of 20% by weight or less based on the total weight of the adhesive composition, and provides the adhesive composition of the present invention with excellent initial cross-tensile strength when cured.

[0067] According to the present invention, component (C) has a softening point of less than 100°C, which is below the reaction temperature when preparing the adhesive composition of the present invention. If the softening point of amorphous polyalphaolefin is 100°C or higher, amorphous polyalphaolefin precipitates during the reaction and forms granules in the adhesive composition. In a preferred embodiment, component (C) used in the present invention has a softening point of 70°C to 95°C.

[0068] In some embodiments, component (C) has a molecular weight (Mn) of less than 200,000 g / mol, preferably less than 100,000 g / mol.

[0069] In some embodiments, component (C) has a Brookfield viscosity of 50,000 mPa·s or less, preferably less than 30,000 mPa·s, at 190°C.

[0070] Useful amorphous polyalphaolefins used as component (C) in the present invention include homopolymers, copolymers, terpolymers, and combinations thereof of polyalphaolefins. The amorphous polyalphaolefin used as component (C) may be a random copolymer or a block copolymer. The amorphous polyalphaolefin can be derived from a variety of monomers, including, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene, 1-undecene, and combinations thereof.

[0071] The useful component (C) is commercially available from Evonik Industrials as Vestoplast 508 and Vestoplast 520.

[0072] According to the present invention, component (C) is present in an amount of 20% by weight or less based on the total weight of the adhesive composition. In a preferred embodiment, component (C) used in the present invention is present in an amount of 1% to 15% by weight, preferably 1% to 8% by weight, based on the total weight of the adhesive composition. Using component (C) in the above range is advantageous because such an amount of component (C) can impart excellent impact resistance to the adhesive composition without reducing the initial cross-tensile strength of the adhesive composition when cured.

[0073] (D)Catalyst Optionally, the moisture-curing polyurethane hot-melt adhesive composition may also contain a catalyst (D) to facilitate the reaction between (A1) a polyol and (A2) a polyisocyanate having at least two isocyanate groups in one molecule.

[0074] Suitable components (D) include, for example, strongly basic amides such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tris-(dialkylaminoalkyl)-s-hexahydrotriazine, such as tris-(NN-dimethylaminopropyl)-s-hexahydrotriazine, or common tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-ethyl-, N-methyl-, N-cyclohexylmoles. Foline, dimethylcyclohexylamine, dimorpholinodiethyl ether, 2-(dimethylaminoethoxy)-ethanol, 1,4-diazabicyclo[2,2,2]octane, 1-azabicyclo[3,3,0]octane, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, tetramethyl Examples include didiaminoethyl ether, bis-(dimethylaminopropyl)-urea, N,N'-dimethylpiperazine, 1,2-dimethylimidazole, di-(4-N,N-dimethylaminocyclohexyl)-methane, and organometallic compounds, such as titanates, iron compounds, such as iron(III) acetylacetonate, tin compounds, such as tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) salt of 2-ethylhexanoic acid (tin(II) octoate), tin(II) dilaurate, or dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin(IV) diacetate, dibutyltin(IV) dilaurate, dibutyltin(IV) maleate, or dioctyltin(IV) diacetate, and dibutyltin(IV) dimercaptide, or mixtures of two or more of the catalysts listed above, and synergistic combinations of strongly basic amines and organometallic compounds.

[0075] If present, the catalyst is present in the adhesive composition in an amount of 0.05% to 1% by weight, preferably 0.05% to 0.5% by weight, based on the total weight of the adhesive composition.

[0076] (E) Additives Optionally, a moisture-curing polyurethane hot-melt adhesive composition may contain at least one additive. Such additives may include those commonly used in the art, such as colorants and antioxidants.

[0077] Examples of colorants include pigments that can be selected from metal oxide pigments, titanium dioxide, optionally surface-treated zirconium oxide or cerium oxide, zinc oxide, iron oxides (black, yellow, red), chromium oxide, manganese, and combinations thereof.

[0078] Examples of antioxidants include phenols such as BHT (butylated hydroxytoluene), octadecyl-3,5-bis(1,1-dimethyl)-4-hydroxybenzenepropanoate, and pyrogallol; phosphite esters such as triphenyl phosphite and tris(nonylphenyl) phosphite; or thioesters such as dilauryl thiodipropionate, and combinations thereof.

[0079] If present, the additive may be present in an amount of 0.01% to 1% by weight, preferably 0.05% to 0.5% by weight, based on the total weight of the adhesive composition.

[0080] Adhesive composition In a particularly preferred embodiment, the moisture-curing polyurethane hot-melt adhesive composition comprises, based on the total weight of the adhesive composition, the following: A reaction mixture containing the following is obtained by reacting it to obtain at least one polyurethane prepolymer in a weight of 66% to 99% of the wt, preferably 70% to 90% of the wt, (A1) Polyol mixtures containing the following: (a) at least one polyester polyol, and (b) at least one polyether polyol, and (A2) At least one polyisocyanate having at least two isocyanate groups in one molecule; At least one (meth)acrylic polymer in an amount of 14% by weight or less, preferably 0.1% to 12% by weight, more preferably 1% to 10% by weight, At least 20% by weight or less, preferably 1% to 15% by weight, more preferably 1% to 8% by weight, of at least one amorphous polyalphaolefin having a softening point of less than 100°C. At least one catalyst in an amount of 0.05% to 1% by weight, preferably 0.05% to 0.5% by weight, and At least one additive in an amount of 0.01% to 1% by weight, preferably 0.05% to 0.5% by weight.

[0081] Preparation method The moisture-curing polyurethane hot-melt adhesive composition according to the present invention can be prepared by the following procedure: (i) Mix the reactant (A1), components (B) and (C), and optional component (E) at a temperature of 120°C to 140°C, then evacuate the mixture; (ii) A step of lowering the temperature from 80°C to 100°C, adding the reactant (A2), and controlling the reaction temperature to 100°C to 110°C; and (iii) Optionally, adding component (D) to the mixture and mixing it uniformly.

[0082] The apparatus for mixing, stirring, and dispersing is not particularly limited. Automatic mortars, Henschel mixers, three-roll mills, ball mills, planetary mixers, bead mills, and other devices equipped with a stirrer and heater can be used. These devices can also be used in appropriate combinations. The method for preparing the moisture-curing polyurethane hot-melt adhesive composition is not particularly limited, as long as the composition is one in which the above components are uniformly mixed.

[0083] Lamination and electronics According to a third aspect of the present invention, provided herein is a laminate comprising a first substrate, a second substrate, and an adhesive layer sandwiched between them, wherein the first substrate and the second substrate are independently selected from glass, resin, and metal, and the adhesive layer is formed by curing the adhesive composition of the present invention.

[0084] The first substrate and / or the second substrate may be a single material and a single layer, or it may consist of multiple layers of the same or different materials. The layers may be continuous or discontinuous.

[0085] The substrates of the articles described herein may have a variety of properties, including rigidity (i.e., they cannot be bent with both hands, or they break when bent with both hands), flexibility (e.g., flexible substrates, i.e., substrates that can be bent with less force than that of both hands), porosity, conductivity, lack of conductivity, and combinations thereof.

[0086] The base material of the article may take various forms, including, for example, fibers, threads, yarns, woven fabrics, nonwoven fabrics, films (e.g., polymer films, metallized polymer films, continuous films, discontinuous films, and combinations thereof), foils (e.g., metal foils), sheets (e.g., metal sheets, polymer sheets, continuous sheets, discontinuous sheets, and combinations thereof), and combinations thereof.

[0087] In preferred embodiments, at least one of the substrates can be selected from metal-fired paste, metals such as aluminum, tin, molybdenum, and silver, conductive metal oxides such as indium tin oxide (ITO), fluorine-doped tin oxide, and aluminum-doped zinc oxide, glass such as ink-filled glass and bare glass, and resins such as polycarbonate, polybutylene terephthalate, and polyamide. More suitable metals include copper, gold, palladium, platinum, aluminum, indium, silver-coated copper, silver-coated aluminum, tin, and tin-coated copper. Preferably, both substrates are selected from any of the aforementioned materials.

[0088] The moisture-curing polyurethane hot-melt adhesive composition of the present invention can be cured in 1 to 7 days at room temperature in the range of 15°C to 35°C and relative humidity of 50%.

[0089] As can be understood, the curing profiles of each moisture-curing polyurethane hot-melt adhesive composition vary in terms of time and temperature, and different compositions can be designed to provide curing profiles particularly suitable for industrial manufacturing processes.

[0090] According to a fourth aspect of the present invention, provided herein are electronic devices comprising a laminate of the present invention or manufactured using an adhesive composition according to the present invention.

[0091] The moisture-curing polyurethane hot-melt adhesive composition of the present invention can be applied to a substrate using any suitable application method, including, for example, automatic fine-line application, jet application, slot die application, roll application, gravure application, transfer application, pattern application, screen printing, spray application, filament application, extrusion application, air knife application, trailing blade application, brush application, dipping application, doctor blade application, offset gravure application, gravure rotary application, and combinations thereof. The moisture-curing polyurethane hot-melt adhesive composition can be applied as a continuous or discontinuous coating, in single layers, multi-layers, or combinations thereof.

[0092] use According to a fifth aspect of the present invention, what is provided herein is the use of an adhesive composition or a laminate according to the present invention in the manufacture of an electronic device.

[0093] Examples of suitable electronic devices include, but are not limited to, wearable electronic devices (e.g., watches, glasses), portable electronic devices (e.g., telephones (e.g., mobile phones, smartphones), cameras, tablets, e-readers, monitors (e.g., monitors used in hospitals, by medical professionals, athletes, and by individuals), clocks, calculators, mice, touchpads, joysticks), computers (e.g., desktop computers and laptop computers), computer monitors, televisions, media players, or other electronic components. [Examples]

[0094] Examples The following examples are intended to help those skilled in the art to better understand and implement the present invention. The scope of the present invention is not limited by the examples but is defined by the appended claims. Unless otherwise specified, all parts and percentages are by weight.

[0095] raw materials: VORANOL2110 is a polyether polyol with a number-average molecular weight (Mn) of 1,000 g / mol and is available from DOW.

[0096] Dynacoll 7360 is a crystalline polyester polyol with a number-average molecular weight (Mn) of 3,500 g / mol and is available from Evonik Industries AG.

[0097] Dynacoll 7250 is a liquid polyester polyol with a number-average molecular weight (Mn) of 5,500 g / mol and a glass transition temperature of -50°C, and is available from Evonik Industries AG.

[0098] Stepan PDP 70 is a liquid diethylene glycol-phthalic anhydride-based modified polyester polyol with a number-average molecular weight (Mn) of 1,600 g / mol and is available from Stepan Corporation.

[0099] FLP PA-1000N is an amorphous polyester polyol with a number-average molecular weight (Mn) of 1,000 g / mol, and is available from Xu Chuan Chemical (Suzhou) Co., Ltd.

[0100] Vestoplast 708 is an amorphous polyalphaolefin with a softening point of 106±4℃ and is available from Evonik.

[0101] Vestoplast 408 is an amorphous polyalphaolefin with a softening point of 118±4℃ and is available from Evonik.

[0102] Vestoplast 520 is an amorphous polyalphaolefin with a softening point of 87±4℃ and is available from Evonik.

[0103] Vestoplast 508 is an amorphous polyalphaolefin with a softening point of 84±4℃ and is available from Evonik.

[0104] Elvacite 2013 is a (meth)acrylic polymer with a number-average molecular weight (Mn) of 34,000 g / mol and is available from Lucite International.

[0105] GRK 830 is a carbon black paste available from Spectrum Dispersions.

[0106] The DESMODUR 44C FUSED is an MDI (Multi-Diode Injector) and is available from Bayer.

[0107] JEFFCAT DMDEE is a 2,2'-dimorpholinyl diethyl ether catalyst and is available from HUNTSMAN.

[0108] Preparation method: Example 1 (Ex.1) 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 10 g of Elvacite 2013, 1 g of Vestoplast 508, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was further mixed at a temperature of 105 to 115°C for 80 minutes. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition was obtained.

[0109] Example 2 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 10 g of Elvacite 2013, 5 g of Vestoplast 508, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was mixed for a further 80 minutes at a temperature of 105 to 115°C. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition was obtained.

[0110] Example 3 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 10 g of Elvacite 2013, 3 g of Vestoplast 508, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was further mixed at a temperature of 105 to 115°C for 80 minutes. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition was obtained.

[0111] Example 4 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 10 g of Elvacite 2013, 3 g of Vestoplast 520, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was mixed for a further 80 minutes at a temperature of 105 to 115°C. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition was obtained.

[0112] Example 5 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 8 g of Elvacite 2013, 5 g of Vestoplast 508, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was further mixed at a temperature of 105 to 115°C for 80 minutes. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition was obtained.

[0113] Comparative example 1 (CE.1) 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 11 g of Elvacite 2013, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was further mixed at a temperature of 105 to 115°C for 80 minutes. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition was obtained.

[0114] Comparative example 2 (CE.2) 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 10 g of Elvacite 2013, 25 g of Vestoplast 508, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was mixed for a further 80 minutes at a temperature of 105 to 115°C. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition could not be obtained because amorphous polyalphaolefins having a weight % outside the scope of the present invention were insoluble in the adhesive composition.

[0115] Comparative example 3 (CE.3) 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 10 g of Elvacite 2013, 3 g of Vestoplast 408, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was mixed for a further 80 minutes at a temperature of 105 to 115°C. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. Amorphous polyalphaolefins with softening points outside the scope of the present invention precipitated during the reaction and formed granules in the adhesive composition, making it impossible to obtain a homogeneous adhesive composition.

[0116] Comparative example 4 (CE.4) 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 10 g of Elvacite 2013, 3 g of Vestoplast 708, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was mixed for a further 80 minutes at a temperature of 105 to 115°C. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. Amorphous polyalphaolefins with softening points outside the scope of the present invention precipitated during the reaction and formed granules in the adhesive composition, making it impossible to obtain a homogeneous adhesive composition.

[0117] Comparative example 5 (CE.5) 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 3 g of Vestoplast 508, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was further mixed at a temperature of 105 to 115°C for 80 minutes. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition was obtained.

[0118] Comparative example 6 (CE.6) 19 g of VORANOL 2110, 18.6 g of Dynacoll 7250, 19.4 g of Dynacoll 7360, 6 g of Stepan PDP 70, 8 g of FLP PA-1000N, 15 g of Elvacite 2013, 3 g of Vestoplast 508, and 1 g of GRK 830 were added to the reactor and mixed at 130 to 140°C for 30 minutes, after which the vacuum was reduced to less than 30 mBar and the mixture was incubated for 2.5 hours. The temperature of the mixture was then reduced to 95°C, 16.6 g of MDI was added, and the mixture was further mixed at a temperature of 105 to 115°C for 80 minutes. Finally, 0.4 g of JEFFCAT DMDEE was added to the reactor and stirred for a further 10 minutes. A homogeneous adhesive composition could not be obtained because (meth)acrylic polymers having a weight % outside the scope of the present invention were insoluble in the adhesive composition.

[0119] Test method: Initial cross-tensile strength: Sample preparation: I. First, a polycarbonate substrate containing 20% ​​by weight of 101.6 x 25.4 x 1 mm glass fibers and an ink glass sheet measuring 101.6 x 25.4 x 3 mm were prepared. The substrates were cleaned with isopropanol and allowed to idle for several minutes under ambient conditions to ensure the surface was completely dry. The polycarbonate substrate and the ink glass substrate were arranged in a cross shape, and an adhesive layer was sandwiched between the overlapping portions to form the substrate.

[0120] II. Next, two spacers with a diameter of 0.127 mm were placed to control the thickness of the adhesive layer. Before dispersing the adhesive composition, the spacers were placed at the edge of the ink glass, at a distance of 3 mm from the edge of the overlapping portion.

[0121] III. The adhesive composition was then heated to 110°C for 30 minutes in a Loctite 400D dispenser. A #21 needle was used to apply the adhesive composition to the surface of the ink glass. During the dispensing process, two bond lines were formed by the adhesive beads dispensed from the needle. The two bond lines were applied in parallel, and the distance between each bond line and the edge of the overlapping portion of the two substrates was 1 to 1.5 mm. Furthermore, the distance between each adhesive bead was controlled to 8 mm, and the distance from the adhesive bead to the edge of the overlapping portion of the two substrates was also 8 mm.

[0122] IV. After dispensing, polycarbonate substrates containing 20% ​​by weight of glass fibers were pressed onto the substrates, leaving two free ends on each substrate, to form a sandwich structure in the overlapping areas. The laminates were then prepared.

[0123] V. A 2-kilogram weight was applied to the overlapping sandwich structure for 15 seconds. The weight was then removed, and the resulting sample was left at 23°C and 50% relative humidity for 1 hour to cure the adhesive composition.

[0124] Sample Testing: To measure the initial cross-tensile strength at the time of rupture of the adhesive layer, the cross-tensile strength of the sample was measured using an INSTRON tensile testing machine at a test speed of 10 mm / min. If the initial cross-tensile strength is greater than 2.5 MPa, the adhesive composition is suitable for use in electronic devices.

[0125] DuPont impact energy test: The impact resistance of the cured adhesive composition was evaluated by DuPont impact energy using a lap shear assembly.

[0126] Sample preparation: I. First, we prepared a polycarbonate substrate with 20% fiberglass and dimensions of 101.6 × 25.4 × 1 mm, a magnesium-aluminum alloy substrate with dimensions of 1 inch wide × 4 inches long and a 10 mm diameter hole in the center, and a 0.12 mm thick polyethylene terephthalate (PET) film with a 12 mm diameter hole in the center. The PET film had tape on one side for adhesion to the magnesium-aluminum alloy substrate to control the width and thickness of the adhesive layer. The substrates were cleaned with isopropanol and allowed to idle for several minutes under ambient conditions to ensure the surface was completely dry.

[0127] II. A PET film was bonded to a magnesium-aluminum alloy substrate, and the position of the central hole in the PET film was aligned with the position of the central hole in the magnesium-aluminum alloy substrate. The diameter of the magnesium-aluminum alloy substrate was 2 mm larger than that of the PET film, forming a circular ring region with a width of 1 mm.

[0128] III. The adhesive composition was extruded into the circular ring region of the magnesium-aluminum alloy substrate, and a polycarbonate substrate was placed horizontally so as to cover the central hole of the magnesium-aluminum alloy substrate. An adhesive layer with a width of 1 mm and a thickness of 0.12 mm was then formed in the overlapping portion, i.e., the circular ring region.

[0129] IV. The test specimens were cured for 72 hours under conditions of 23°C and 60% humidity.

[0130] V. The test specimens were secured to a holder at the bottom of the DuPont testing machine (BGD301) and subjected to testing.

[0131] Sample test: As a starting point, a 50g weight was dropped onto the test specimen from a height of 2cm. If the magnesium-aluminum alloy substrate did not detach from the polycarbonate substrate three times, the weight was raised to a height 2cm higher than the previous drop and dropped again. If the magnesium-aluminum alloy substrate did not detach from the polycarbonate substrate using a 50g weight at a height of 50cm, the test was repeated using a 60g weight. The DuPont impact energy was calculated using the following formula.

[0132] E=m*g*h*0.01,

[0133] Here, E is the impact energy (mJ), m is the weight required to separate the substrates (g), h is the height of the loosened weight when separating the substrates (cm), and g is 9.8 m / s². 2 A DuPont impact energy value of less than 350 mJ is considered unacceptable impact resistance.

[0134] The test results are shown in Table 1.

[0135] TIFF0007837403000001.tif44160

[0136] As can be seen from Table 1, the moisture-curing polyurethane hot-melt adhesive composition of the present invention showed excellent impact resistance and initial cross-tensile strength during curing, while the comparative composition showed unsatisfactory performance.

[0137] While several preferred embodiments have been described, many modifications and variations can be made to them in light of the above teachings. Therefore, it should be understood that the present invention can be carried out in ways other than those specifically described without departing from the scope of the appended claims. Preferred embodiments of the present invention include the following: [1] At least one polyurethane prepolymer obtained by reacting a reagent mixture containing (A) or the following (A1) Polyol mixture containing the following (a) at least one polyester polyol, and (b) at least one polyether polyol, and (A2) At least one polyisocyanate having at least two isocyanate groups in one molecule, (B) At least one (meth)acrylic polymer present in an amount of 14% by weight or less based on the total weight of the adhesive composition, (C) At least one amorphous polyalphaolefin having a softening point of less than 100°C, present in an amount of 20% by weight or less based on the total weight of the adhesive composition. A moisture-curing polyurethane hot-melt adhesive composition containing [a specific compound / substance]. [2] The moisture-curing polyurethane hot-melt adhesive composition according to [1], wherein the reactant (a) is selected from solid polyester polyols, liquid polyester polyols, and combinations thereof, preferably from crystalline polyester polyols, amorphous polyester polyols, liquid polyester polyols, and combinations thereof. [3] The reactant (a) is a moisture-curing polyurethane hot-melt adhesive composition according to [1] or [2], having a number-average molecular weight (Mn) of 800 to 20,000 g / mol, preferably 1,000 to 10,000 g / mol, and more preferably 1,000 to 5,000 g / mol. [4] The reactant (b) is selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, polyethylene oxide, polybutylene oxide, and any of the aforementioned ethylene oxide end-cap type, as well as combinations thereof, preferably selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, ethylene oxide end-cap type poly(oxypropylene) glycol, and combinations thereof, as described in any of [1] to [3]. [5] Reactants (A2) include 4,4-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), partially hydrogenated MDI (H6MDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), 4,4-diphenyldimethylmethane diisocyanate, dialkylenediphenylmethane diisocyanate, tetraalkylenediphenylmethane diisocyanate, 4,4-dibenzyl diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylenediisocyanate, isomers of toluene diisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (IPDI), tetramethoxybutane-1,4-diisocyanate, Naphthalene-1,5-diisocyanate (NDI), butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexane-2,3,3-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, methylenetriphenyl triisocyanate (MIT), bisisocyanatoethyl phthalate, A moisture-curing polyurethane hot-melt adhesive composition according to any one of [1] to [4], selected from trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, and dimer fatty acid diisocyanate, lysine ester diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,3-cyclohexane or 1,4-cyclohexane diisocyanate, and combinations thereof. [6] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to [5], wherein component (B) has a number average molecular weight (Mn) of 5,000 to 100,000 g / mol, preferably 5,000 to 80,000 g / mol, and more preferably 8,000 to 50,000 g / mol. [7] A moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to [6], wherein component (C) has a softening point of 70°C to 95°C. [8] The moisture-curing polyurethane hot-melt adhesive composition according to any one of [1] to [7], wherein component (C) has a molecular weight (Mn) of less than 200,000 g / mol, preferably less than 100,000 g / mol. [9] The adhesive composition is a strong basic amide, triethylamine, tributylamine, dimethylbenzylamine, N-ethyl-, N-methyl-, N-cyclohexylmorpholine, dimethylcyclohexylamine, dimorpholinodiethyl ether, 2-(dimethylaminoethoxy)-ethanol, 1,4-diazabicyclo[2,2,2]octane, 1-azabicyclo[3,3,0]octane, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N' A moisture-curing polyurethane hot-melt adhesive composition according to any one of [1] to [8], further comprising N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis-(dimethylaminopropyl)-urea, N,N'-dimethylpiperazine, 1,2-dimethylimidazole, di-(4-N,N-dimethylaminocyclohexyl)-methane, organometallic compounds, and at least one catalyst (D) selected from combinations thereof.

[10] The adhesive composition is a moisture-curing polyurethane hot-melt adhesive composition according to any one of [1] to [9], further comprising (E) at least one additive.

[11] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to

[10] , wherein component (A) is present in an amount preferably 66% to 99% by weight, more preferably 70% to 90% by weight, based on the total weight of the adhesive composition.

[12] The moisture-curing polyurethane hot-melt adhesive composition according to any one of [1] to

[11] , wherein the reactant (a) is present in an amount of 30% to 70% by weight, more preferably 35% to 65% by weight, based on the total weight of the adhesive composition.

[13] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to

[12] , wherein the reactant (b) is present in an amount of 10% to 40% by weight, more preferably 15% to 36% by weight, based on the total weight of the adhesive composition.

[14] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to

[13] , wherein the reactant (A2) is present in an amount of 10% to 25% by weight, preferably 10% to 20% by weight, based on the total weight of the adhesive composition.

[15] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to

[14] , wherein component (B) is present in an amount preferably 0.1% to 12% by weight, more preferably 1% to 10% by weight, based on the total weight of the adhesive composition.

[16] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to

[15] , wherein component (C) is present in an amount of 1% to 15% by weight, preferably 1% to 8% by weight, based on the total weight of the adhesive composition.

[17] A moisture-curing polyurethane hot-melt adhesive composition according to any one of [9] to

[16] , wherein component (D) is present in an amount of 0.05% to 1% by weight, preferably 0.05% to 0.5% by weight, based on the total weight of the composition.

[18] (i) Mixing the reactant (A1), components (B) and (C), and optional component (E) at a temperature of 120°C to 140°C, followed by vacuuming; (ii) A step of lowering the temperature from 80°C to 100°C, adding the reactant (A2), and controlling the reaction temperature to 100°C to 110°C; and (iii) Optionally, add component (D) to the mixture and mix it uniformly. A method for preparing a hot melt adhesive composition according to any one of [1] to

[17] , comprising the above.

[19] A laminate comprising a first substrate, a second substrate, and an adhesive layer sandwiched between them, wherein the first substrate and the second substrate are independently selected from glass, resin, and metal, and the adhesive layer is formed by curing an adhesive composition described in any of [1] to

[17] .

[20] An electronic device comprising the laminate described in

[19] or manufactured using an adhesive composition described in any of [1] to

[17] .

[21] Use of an adhesive composition according to any of [1] to

[17] or a laminate according to

[19] in the manufacture of an electronic device.

Claims

1. (A) At least one polyurethane prepolymer obtained by reacting a reagent mixture containing the following (A1) Polyol mixture containing the following (a) at least one polyester polyol, and (b) at least one polyether polyol, and (A2) At least one polyisocyanate having at least two isocyanate groups in one molecule, (B) At least one (meth)acrylic polymer present in an amount of 10% by weight or less based on the total weight of the adhesive composition, (C) At least one amorphous polyalphaolefin having a softening point of less than 100°C, present in an amount of 20% by weight or less based on the total weight of the adhesive composition. A moisture-curing polyurethane hot-melt adhesive composition containing [a specific compound / substance].

2. The moisture-curing polyurethane hot-melt adhesive composition according to claim 1, wherein the reactant (a) is selected from a solid polyester polyol, a liquid polyester polyol, and a combination thereof.

3. The reactant (a) has a number-average molecular weight (Mn) of 800 to 20,000 g / mol, as described in claim 1 or 2 of the moisture-curing polyurethane hot-melt adhesive composition.

4. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 3, wherein the reactant (b) is selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, polyethylene oxide, polybutylene oxide, and any of the aforementioned ethylene oxide end-cap types, and combinations thereof.

5. The reagent (A2) is 4,4-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), partially hydrogenated MDI (H6MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4-diphenyldimethylmethane diisocyanate, dialkylenediphenylmethane diisocyanate, tetraalkylenediphenylmethane diisocyanate, 4,4-dibenzyl diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylenediisocyanate, isomers of toluene diisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (IPDI), tetramethoxybutane-1,4-diisocyanate, Naphthalene-1,5-diisocyanate (NDI), butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexane-2,3,3-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, methylenetriphenyl triisocyanate (MIT), bisisocyanatoethyl phthalate A moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 4, selected from trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, and dimer fatty acid diisocyanate, lysine ester diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,3-cyclohexane or 1,4-cyclohexane diisocyanate, and combinations thereof.

6. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 5, wherein component (B) has a number-average molecular weight (Mn) of 5,000 to 100,000 g / mol.

7. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 6, wherein component (C) has a softening point of 70°C to 95°C.

8. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 7, wherein component (C) has a molecular weight (Mn) of less than 200,000 g / mol.

9. The adhesive composition includes a strong basic amide, triethylamine, tributylamine, dimethylbenzylamine, N-ethyl-, N-methyl-, N-cyclohexylmorpholine, dimethylcyclohexylamine, dimorpholinodiethyl ether, 2-(dimethylaminoethoxy)-ethanol, 1,4-diazabicyclo[2,2,2]octane, 1-azabicyclo[3,3,0]octane, and N,N,N'. A moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 8, further comprising N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis-(dimethylaminopropyl)-urea, N,N'-dimethylpiperazine, 1,2-dimethylimidazole, di-(4-N,N-dimethylaminocyclohexyl)-methane, organometallic compounds, and at least one catalyst (D) selected from combinations thereof.

10. The adhesive composition is a moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 9, further comprising (E) at least one additive.

11. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 10, wherein component (A) is present in an amount of 66% to 99% by weight based on the total weight of the adhesive composition.

12. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 11, wherein the reactant (a) is present in an amount of 30% to 70% by weight based on the total weight of the adhesive composition.

13. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 12, wherein the reactant (b) is present in an amount of 10% to 40% by weight based on the total weight of the adhesive composition.

14. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 13, wherein the reactant (A2) is present in an amount of 10% to 25% by weight based on the total weight of the adhesive composition.

15. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 14, wherein component (B) is present in an amount of 1% to 10% by weight based on the total weight of the adhesive composition.

16. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 15, wherein component (C) is present in an amount of 1% to 15% by weight based on the total weight of the adhesive composition.

17. The moisture-curing polyurethane hot-melt adhesive composition according to claim 9, wherein component (D) is present in an amount of 0.05% to 1% by weight based on the total weight of the composition.

18. (i) Mixing the reactant (A1), components (B) and (C), and optional component (E) at a temperature of 120°C to 140°C, followed by vacuuming; (ii) A step of lowering the temperature from 80°C to 100°C, adding the reactant (A2), and controlling the reaction temperature to 100°C to 110°C; and (iii) Optionally, add component (D) to the mixture and mix it uniformly. A method for preparing a hot melt adhesive composition according to any one of claims 1 to 17, comprising the above.

19. A laminate comprising a first substrate, a second substrate, and an adhesive layer sandwiched between them, wherein the first and second substrates are independently selected from glass, resin, and metal, and the adhesive layer is formed by curing an adhesive composition according to any one of claims 1 to 17.

20. An electronic device comprising the laminate described in claim 19, or manufactured using the adhesive composition described in any one of claims 1 to 17.

21. Use of the adhesive composition according to any one of claims 1 to 17 or the laminate according to claim 19 in the manufacture of an electronic device.

Images