Reactive hot melt adhesive composition and its use

Abstract

The present invention relates to a reactive hot melt adhesive composition and its use. In particular, the present invention provides an adhesive composition comprising at least one reactive polyurethane prepolymer obtained by reacting a reactant mixture comprising (A), (a) at least one polyol, and (b) at least one polyisocyanate having at least two isocyanate groups per molecule; (B) at least one vinyl acetate homopolymer having a weight average molecular weight (Mw) of 15,000 to less than 100,000 g / mol and present in an amount of less than 70 wt. % based on the total weight of the adhesive composition.

Description

Technical Field

[0001] Technical Field The present invention relates to a reactive hot melt adhesive composition and its use. In particular, the present invention relates to a reactive hot melt adhesive composition containing a vinyl acetate homopolymer, whereby it can meet the needs of various applications.

Background Art

[0002] Background Moisture-curable polyurethane hot melt adhesives have been used for many years and are widely popular. For example, they are described in H.F. Hueber and H. Mueller “Shaping Reactive Hotmelts Using LMW Copolyesters”, (Adhesives Age, November 1987, pages 32-35). In industrial applications, moisture-curable polyurethane hot melt adhesives are solid at room temperature, but when heated to a suitable temperature, they melt into a viscous liquid, are applied to a substrate, and adhered. The molten adhesive composition is then cooled and solidified to form an initial bond with the substrate. Further, it reacts with moisture to form a crosslinked structure, achieving high final strength. Such adhesives can be composed of a polyol component and an isocyanate component having two or more functional groups. These adhesives are preferred over other adhesives in various applications because they have excellent adhesive strength, flexibility, and resistance to impact and fatigue.

[0003] Currently, moisture-curing polyurethane hot-melt adhesives are commonly used in the industry to improve the inherent cohesiveness and initial adhesive strength of adhesives to various materials by mixing them with resins such as acrylic, ethylene vinyl acetate (EVA), and thermoplastic polyurethane (TPU) resins. Polyvinyl acetate (PVAc) has long been used in various applications across various technical fields due to its excellent adhesive strength to various substrates and low odor. For example, polyvinyl acetate is a film-forming component in many water-based (latex) adhesives and paints. However, due to compatibility issues, polyvinyl acetate is rarely mixed with polyurethane hot-melt adhesives. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] HF Hueber and H. Mueller “Shaping Reactive Hotmelts Using LMW Copolyesters”, (Adhesives Age, November 1987, pp. 32-35) [Overview of the project] [Problems that the invention aims to solve]

[0005] Therefore, in this technical field, there is a need for a moisture-curing polyurethane hot-melt adhesive that can incorporate polyvinyl acetate as a component in order to realize an adhesive composition that has a wide range of open times and good initial adhesive strength to different substrates during curing. [Means for solving the problem]

[0006] Summary of the Invention Disclosed herein are: (A) A reaction mixture containing at least one reactive polyurethane prepolymer obtained by reacting the reaction mixture, (a) at least one polyol, and (b) at least one polyisocyanate having at least two isocyanate groups in one molecule; and (B) At least one vinyl acetate homopolymer having a weight-average molecular weight (Mw) of 15,000 to less than 100,000 g / mol and present in an amount of less than 70% by weight based on the total weight of the adhesive composition. This is a hot-melt adhesive composition of moisture-curing polyurethane containing [a specific ingredient].

[0007] Furthermore, curing products of moisture-curing hot-melt adhesive compositions according to the present invention are also disclosed herein.

[0008] Furthermore, this specification also discloses 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, textile, wood, and metal, and the adhesive layer is formed by curing an adhesive composition according to the present invention.

[0009] Furthermore, this specification also discloses the use of the moisture-curing hot-melt adhesive composition according to the present invention in the manufacture of consumer goods, automotive parts, electronic devices, and home appliances.

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

[0011] Detailed explanation Those skilled in the art will understand that this description is merely an illustrative description of exemplary embodiments and is not intended to limit broader aspects of the present invention.

[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" used in this book include both singular and plural forms.

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

[0015] As used herein, the terms "at least one" or "one or more" used to define a component refer to the type of component and not to an absolute numerical value of the molecule. For example, "one or more polyols" means one type of polyol or a mixture of multiple 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 about 20 °C to about 25 °C, preferably about 25 °C.

[0019] Unless otherwise specified, the recitation of numerical endpoints includes not only the recited endpoints but also all numbers and fractions subsumed within each range.

[0020] Unless otherwise specified, the molecular weight refers to the weight average molecular weight (Mw). All molecular weight data refers to values obtained by gel permeation chromatography (GPC) unless otherwise specified, such as DIN 55672.

[0021] 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.

[0022] Unless otherwise defined, all terms used in this invention, including technical and scientific terms, have the meanings generally understood by an ordinary person skilled in the art to which this invention pertains.

[0023] According to the first aspect, the present invention generally relates to, (A) A reaction mixture containing at least one reactive polyurethane prepolymer obtained by reacting the reaction mixture, (a) at least one polyol, and (b) at least one polyisocyanate having at least two isocyanate groups in one molecule; and (B) At least one vinyl acetate homopolymer having a weight-average molecular weight (Mw) of 15,000 to less than 100,000 g / mol and present in an amount of less than 70% by weight based on the total weight of the adhesive composition. This invention relates to a moisture-curing polyurethane hot-melt adhesive composition containing [a specific compound / ing].

[0024] (A) Reactive polyurethane prepolymer According to the present invention, a moisture-curing polyurethane hot-melt adhesive composition comprises at least one reactive polyurethane prepolymer obtained by reacting a reagent mixture containing (a) at least one polyol and (b) at least one polyisocyanate having at least two isocyanate groups in one molecule.

[0025] In some embodiments, the reactive 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.

[0026] In some embodiments, component (A) is present in an amount of more than 30% by weight and less than 100% by weight, preferably 40% to 99% by weight, more preferably 45% to 90% by weight, and even more preferably 50% to 65% by weight, based on the total weight of the adhesive composition.

[0027] (a) Polyol In some embodiments, the reactant (a) can be selected from polyester polyols, polyether polyols, and combinations thereof.

[0028] In a preferred embodiment, a polyester polyol can be used as the reactant (a), which can be 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.

[0029] If present, crystalline polyester polyols can be used in the present invention, which can provide good adhesive strength to the adhesive composition.

[0030] Examples of such crystalline polyester polyols can be obtained by ring-opening polymerization of lactones such as ε-caprolactone and / or derived from diols and diacids. Examples of diols useful for producing 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 producing preferred polyester polyols include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and 1,12-dodecanediol, dimer acids, and combinations thereof. The range of useful diacids includes various diacid derivatives such as carboxylate esters (especially methyl and ethyl esters), acid halides (such as acid chlorides), acid anhydrides, and combinations thereof.

[0031] Specific examples of suitable crystalline polyester polyols include poly(hexanediol adipate) polyol, poly(butanediol adipate) polyol, polyepsilon-caprolactone polyol, poly(hexanediol-decanediic acid) polyol, poly(hexanediol-adipate terephthalate) polyol, and combinations thereof.

[0032] Suitable commercially available crystalline polyester polyols are sold under the trademark name DYNACOLL 7300 series by Evonik Industries AG, which includes DYNACOLL 7360, 7361, 7362, 7363, 7380, 7381, 7390, etc. Also sold under the trademark name CAPA series by Perstorp Polyols Inc., which includes CAPA 2201, 2205, 2209, 2302, 2304, 2402, etc. Caprolactone polyols and AR U 2720, available from Yong Shun Chemicals Co., Ltd. are also included.

[0033] If present, amorphous polyester polyols can also be used in the production of the reactive polyurethane prepolymer of the present invention.

[0034] Amorphous polyester polyols include reaction products of polyacid components (e.g., polyacids, polyacid anhydrides, polyacid esters, polyacid halides) with stoichiometrically excess polyols. 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, dimethylterephthalic acid, diethylterephthalic acid, phthalic acid, phthalic anhydride, methylhexahydrophthalic acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, tetrahydrophthalic acid Examples 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, dimerizable acids, dimerized fatty acids, trimerized fatty acids, fumaric acid), and alicyclic dicarboxylic acids (e.g., 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), and mixtures thereof.Suitable examples of polyols include aliphatic polyols, e.g., ethylene glycol, propanediols (e.g., 1,2-propanediol and 1,3-propanediol), butanediols (e.g., 1,3-butanediol, 1,4-butanediol, 1,2-butanediol), 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 glycol. Examples include polyethylene glycol, propylene glycol, polypropylene glycol (e.g., dipropylene glycol, 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.

[0035] Specific examples of useful amorphous polyester polyols, if present, include 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.

[0036] Useful amorphous polyester polyols are commercially available under various brand names, such as DYNACOLL 7110, 7130, 7140, and 7150 from Evonik Industries AG, and FLP PA-1000N from Xuchuan Chemical (Suzhow) Co., Ltd.

[0037] 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, it is preferable that the liquid polyester polyol 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 a liquid state.

[0038] Suitable liquid polyester polyols include those obtained by ring-opening polymerization of lactones such as ε-caprolactone, and / or those derived from diols and diacids. Examples of diols useful for producing 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 producing preferred polyester polyols include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and 1,12-dodecanediol, dimer acids, and combinations thereof. The range of useful diacids includes various diacid derivatives such as carboxylate esters (especially methyl and ethyl esters), acid halides (such as acid chlorides), acid anhydrides, and combinations thereof.

[0039] Specific examples of suitable liquid polyester polyols include poly(hexanediol adipate) polyol, poly(butanediol adipate) polyol, polyepsilon caprolactone polyol, poly(hexanediol decanedioic acid) polyol, poly(hexanediol adipate terephthalate) polyol, and mixtures thereof.

[0040] Suitable commercially available liquid polyester polyols are sold under the trademark names of Evonik Industries AG's DYNACOLL 7200 series (DYNACOLL 7210, 7230, 7231, 7250, etc.) and Stepan Corporation's Stepan PDP 70.

[0041] In some embodiments, the reactant (a) may be a polyether polyol.

[0042] 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.

[0043] Preferred polyether polyols can be selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, polyethylene oxide, polybutylene oxide, and any of the aforementioned ethylene oxide-terminated versions, as well as combinations thereof. The most preferred polyether polyols are polytetramethylene ether glycol, poly(oxypropylene) glycol, ethylene oxide-terminated poly(oxypropylene) glycol, and combinations thereof.

[0044] In preferred embodiments, 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.

[0045] In this invention, commercially available products can also be used. Examples include Voranol 2104, 2110, 2120, and 2140 from Dow Chemical.

[0046] In some embodiments, the reactant (a) is a combination of a polyester polyol and a polyether polyol. Preferably, the reactant (a) does not contain a polyether polyol in order to form the reactive polyurethane prepolymer of the present invention.

[0047] Particularly preferably, the reactant (a) may be present in an amount of 20% to 85% by weight, more preferably 40% to 80% by weight, based on the total weight of the adhesive composition.

[0048] (b) Polyisocyanates According to the present invention, a moisture-curing polyurethane hot-melt adhesive composition comprises at least one reactive polyurethane prepolymer obtained by reacting a reagent mixture containing (a) at least one polyol and (b) at least one polyisocyanate having at least two isocyanate groups in one molecule.

[0049] Polyisocyanates useful as reagent (b) include, for example, any suitable isocyanates having at least two isocyanate groups in a single molecule, including aliphatic, alicyclic, aromatic aliphatic, arylalkyl, aromatic isocyanates, and combinations thereof.

[0050] Preferred reagents (b) include 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), partially hydrogenated MDI (H6MDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, diarylylenediphenylmethane diisocyanate, tetraalkylenephenylmethane diisocyanate, and 4,4'-diphenyl 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, and 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 Polyisocyanates can be selected from diisocyanates (MIT), bisisocyanatoethyl phthalate, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, dimer fatty acid diisocyanates, lysine ester diisocyanates, 4,4'-dicyclohexylmethane diisocyanate, 1,3-cyclohexane or 1,4-cyclohexane diisocyanate, and combinations thereof. The most preferred polyisocyanates are 4,4'-diphenylmethane diisocyanate (MDI) and its isomers, chain-extended MDI, and combinations thereof.

[0051] Useful commercially available polyisocyanates for use as reagent (b) include Covestro's DESMODUR 44C FUSED, Desmodur 0118 I, Desmodur 44M, Wanhua Chemicals' Vannate MDI 100F, and HUNTSMAN's Supresec 1809.

[0052] Particularly preferably, the reactant (b) may be present in an amount of 5% to 25% by weight, preferably 10% to 20% by weight, based on the total weight of the adhesive composition.

[0053] (B) Vinyl acetate homopolymer According to the present invention, the moisture-curing polyurethane hot melt adhesive composition contains (B) at least one vinyl acetate homopolymer having a weight-average molecular weight (Mw) of 15,000 to less than 100,000 g / mol and present in an amount of less than 70% by weight based on the total weight of the adhesive composition.

[0054] In preferred embodiments, component (B) used in the present invention may be a vinyl acetate homopolymer in the range of 30,000 to 60,000 g / mol, more preferably in the range of 45,000 to 55,000 g / mol.

[0055] A suitable vinyl acetate homopolymer used as component (B) of the present invention can typically be produced by emulsion polymerization techniques, which may include, in addition to vinyl acetate monomer and water, small amounts of wetting agents, protective colloids, polymerization initiators, and molecular weight modifiers.

[0056] Useful commercially available vinyl acetate homopolymers that can be used as component (B) include Vinnapas™ N 1.5 SP, Vinnapas™ N 17 SP, and Vinnapas™ N 30 SP, manufactured by Wacker Chemicals (China) Co., Ltd.

[0057] Particularly preferably, component (B) may be present in an amount greater than 0% by weight and less than 70% by weight, preferably 1% to 60% by weight, and more preferably 5% to 45% by weight, based on the total weight of the adhesive composition.

[0058] (C)Catalyst If necessary, the moisture-curing polyurethane hot-melt adhesive composition may also include (C) a catalyst to facilitate the reaction between (a) a polyol and (b) a polyisocyanate having at least two isocyanate groups in one molecule.

[0059] Suitable components (C) include, for example, strongly basic amides such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tris-(dialkylaminoalkyl)-s-hexahydrotriazine, such as tris-(N,N-dimethylaminopropyl)-s-hexahydrotriazine, or common tertiary amines, such as 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',N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, tetramethyl Examples include organometallic compounds such as diaminoethyl ether, bis-(dimethylaminopropyl)-urea, N,N'-dimethylpiperazine, 1,2-dimethylimidazole, di-(4-N,N-dimethylaminocyclohexyl)-methane, and titanate esters, 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 above catalysts, and synergistic combinations of strongly basic amines and organometallic compounds.

[0060] Particularly preferably, the catalyst may be present in the adhesive composition in an amount of 0 to 1% by weight, preferably 0.01% to 0.5% by weight, based on the total weight of the adhesive composition.

[0061] (D) Additives In some cases, the 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, antioxidants, leveling agents, and anti-yellowing agents.

[0062] Examples of colorants include metal oxide pigments, titanium dioxide (optionally surface-treated), zirconium oxide or cerium oxide, zinc oxide, iron oxide (black, yellow, or red), chromium oxide, manganese, and pigments that can be selected from combinations thereof.

[0063] Examples of antioxidants include phenols such as BHT (butylated hydroxytoluene), octadecyl-3,5-bis(1,1-dimethyl)-4-hydroxybenzenepropanoate, and pyrogallol; phosphites such as triphenyl phosphite and tris(nonylphenyl) phosphite; thioesters such as dilauryl thiodipropionate; and combinations thereof.

[0064] Particularly preferably, the additive may be present in an amount of 0 to 5% by weight, preferably 0.05% to 2% by weight, based on the total weight of the adhesive composition.

[0065] Adhesive composition In a particularly preferred embodiment, the moisture-curing polyurethane hot-melt adhesive composition is based on the total weight of the adhesive composition. More than 30% by weight and less than 100% by weight, preferably 40% to 99% by weight, more preferably 45% to 90% by weight, and even more preferably 50% to 65% by weight, (a) at least one polyol, and (b) At least one polyisocyanate having at least two isocyanate groups in one molecule (A) at least one reactive polyurethane prepolymer obtained by reacting a reactant mixture containing the following: (B) At least one vinyl acetate homopolymer having a weight-average molecular weight (Mw) of 15,000 to less than 100,000 g / mol, in an amount greater than 0% by weight and less than 70% by weight, preferably 1% to 60% by weight, and more preferably 5% to 45% by weight. 0 to 1% by weight, preferably 0.01 to 0.5% by weight of (C) catalyst, and 0-5% by weight, preferably 0.05-2% by weight of additive (D) Includes.

[0066] Preparation method The moisture-curing polyurethane hot-melt adhesive composition according to the present invention can be manufactured and obtained by the following steps: (i) Mixing the reactant (a) and component (B) at a temperature of 125°C to 150°C, followed by vacuuming; (ii) A step of lowering the temperature to 100°C to 120°C, adding reactant (b), and controlling the reaction temperature to 120°C to 130°C; and (iii) A process of mixing under vacuum for 1 to 2 hours to make it homogenized, and then discharging it.

[0067] The equipment used for mixing, stirring, and dispersion is not particularly limited. Automatic mortars equipped with stirrers and heaters, Henschel mixers, three-roll mills, ball mills, planetary mixers, bead mills, etc., can be used. These devices may also be used in appropriate combinations. The method for producing the moisture-curing polyurethane hot-melt adhesive composition is not particularly limited as long as the composition is uniformly mixed with the above components.

[0068] Hardened products and laminates The moisture-curing polyurethane hot-melt adhesive composition of the present invention can be cured in 1 to 7 days at 15°C to 35°C, preferably at room temperature, and at a relative humidity of 50%.

[0069] As is understood, each moisture-curing polyurethane hot-melt adhesive composition has a different curing time and temperature profile, and different compositions can be designed to provide a curing profile suitable for specific industrial manufacturing processes.

[0070] According to a second aspect of the present invention, a cured product of the moisture-curing polyurethane hot-melt adhesive of the present invention is provided.

[0071] According to a third aspect of the present invention, a laminate is provided comprising a first substrate, a second substrate, and an adhesive layer provided between them, wherein the first and second substrates are independently selected from glass, resin, textile, wood, and metal, and the adhesive layer is formed by curing the adhesive composition of the present invention.

[0072] Specifically, the moisture-curing polyurethane reactive hot-melt adhesive composition according to the present invention has component (B) present in an amount of less than 30% by weight, preferably less than 20% by weight, of the total weight of the adhesive composition, and can be used for bonding textiles together in clothing, or for bonding textiles to foam. On the other hand, the moisture-curing polyurethane reactive hot-melt adhesive composition according to the present invention has component (B) present in an amount of 30% by weight or more and less than 70% by weight, preferably 45% by weight or more and less than 70% by weight, of the total weight of the adhesive composition, and can be used for bonding wood substrates.

[0073] The first substrate and / or the second substrate may consist of 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.

[0074] The substrates of the articles described herein may have a variety of properties, including rigidity (for example, in the case of a hard substrate, i.e., the substrate cannot be bent with both hands, or breaks when bent with both hands), flexibility (for example, in the case of a flexible substrate, i.e., the substrate can be bent with less force than that of both hands), porosity, conductivity, lack of conductivity, and combinations thereof.

[0075] The base material of an article can take various forms, such as fibers, threads, yarns, textiles, nonwovens, films (e.g., polymer films, metallized polymer films, continuous films, discontinuous films, and combinations thereof), foils (e.g., metallic foils), sheets (e.g., metallic sheets, polymer sheets, continuous sheets, discontinuous sheets, and combinations thereof), and combinations thereof.

[0076] 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 glass and bare glass, and resins such as polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyamide, and polyvinyl chloride. More suitable metals include copper, gold, palladium, platinum, aluminum, indium, silver-plated copper, silver-plated aluminum, tin, and tin-plated copper. Preferably, both substrates are selected from any of the aforementioned materials.

[0077] 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 coating, jet coating, slot die coating, roll coating, gravure coating, transfer coating, pattern coating, screen printing, spray coating, filament coating, extrusion, air knife, trailing blade, brushing, dipping, doctor blade, offset gravure coating, funnel gravure coating, and combinations thereof. The moisture-curing polyurethane hot melt adhesive composition can be applied as a continuous or discontinuous coating, in single layers or multilayers, or in combinations thereof.

[0078] use According to the present invention, moisture-curing polyurethane reactive hot-melt adhesive compositions are useful in the manufacture of consumer goods, automotive parts, electronic devices, and household appliances.

[0079] Appropriate consumer goods include, but are not limited to, textiles and clothing, wood products and furniture, paper and plastic packaging, and other components.

[0080] Examples of suitable electronic devices include, but are not limited to, wearable electronic devices (e.g., watches and glasses), handheld electronic devices (e.g., telephones (e.g., mobile phones and smartphones), cameras, tablets, e-readers, monitors (e.g., monitors used by hospitals and medical professionals, athletes, and individuals), clocks, calculators, mice, touchpads, and joysticks), computers (e.g., desktop and laptop computers), computer monitors, televisions, media players, and other electronic components.

[0081] Examples of suitable household appliances include, but are not limited to, refrigerators, washing machines, dryers, ovens, microwave ovens, etc., light bulbs (e.g., incandescent bulbs, light-emitting diodes, fluorescent lamps, etc.), and other items. [Examples]

[0082] Examples The following examples are intended to help those skilled in the art to understand and implement the invention. The scope of the invention is not limited by the examples but is defined by the appended claims. Unless otherwise specified, all quantities and percentages are based on weight.

[0083] raw materials AR U 2720 is a polyester polyol available from Yong Shun Chemicals Co., Ltd.

[0084] Desmodur TM The 44M is a 4,4'-MDI available from Covestro.

[0085] Vinnapas TM N 17 SP is a vinyl acetate homopolymer with a weight-average molecular weight (Mw) of 45,000 g / mol, available from Wacker Chemicals (China) Co. Ltd.

[0086] Vinnapas TM N 1.5 SP is a vinyl acetate homopolymer with a weight-average molecular weight (Mw) of 15,000 g / mol, available from Wacker Chemicals (China) Co. Ltd.

[0087] Vinnapas TM N 30 SP is a vinyl acetate homopolymer with a weight-average molecular weight (Mw) of 55,000 g / mol, available from Wacker Chemicals (China) Co. Ltd.

[0088] Vinnapas TM N 100 SP is a vinyl acetate homopolymer with a weight-average molecular weight (Mw) of 100,000 g / mol, available from Wacker Chemicals (China) Co. Ltd.

[0089] Hanwha 1540 is an ethylene-vinyl acetate copolymer available from Hanwha Chemicals.

[0090] Elvacite TM 2013 is an acrylic resin available from Mitsubishi Chemical Corporation.

[0091] Pearlbond TM 521 is a polycaprolactone copolyester polyurethane available from Lubrizol.

[0092] Sample preparation The samples were prepared according to the formulations listed in Tables 1, 2, and 3. The total weight of all components was 100 parts by weight. In the following table, the compositions were prepared by the following procedure: (i) Mix the reagent (a) with component (B) or another resin substitute for component (B) at a temperature of 125°C to 150°C, and then evacuate; (ii) A step of lowering the temperature to 100°C to 120°C, adding reactant (b), and controlling the reaction temperature to 120°C to 130°C; and (iii) Mix under vacuum for 1-2 hours, then discharge.

[0093] The state of the resulting compositions was recorded as "homogeneous" or "phase separated" based on visual observation. Compositions exhibiting "phase separation" are unacceptable because they have compatibility issues between the components, resulting in reduced workability.

[0094] Test method: Viscosity of hot melt adhesive compositions The viscosity in this invention was measured using a Brookfield viscometer with a 27# spindle over a temperature range of 130°C. A viscosity of less than 10,000 cps is acceptable.

[0095] Initial bond strength after 2 minutes and 10 minutes Each sample prepared as described above was coated to a thickness of 50 μm between two layers of 1 m x 0.18 m PET film (available from Lianrui Corporation in Dongguan) using a roller heater (available from Weite Corporation in Taiwan) at 105°C to create a laminated sample.

[0096] The laminated samples were cured at 23°C and 50% relative humidity for 2 minutes. The 180° peel strength was recorded as the initial adhesive strength of the cured laminated samples. The laminated samples were placed on a tensile testing machine (Shenzhen SANS Testing Machine Co., Ltd.) and the initial adhesive strength was measured at a peeling speed of 300 mm / min. The initial adhesive strength after 2 minutes was measured three times for each sample, and the average value was recorded. An initial adhesive strength of 0.2 N / inch or higher at 10 minutes in 100% cohesive failure mode is considered acceptable. The "cohesive failure mode" referred to here is a state in which the adhesive splits, and some of the adhesive remains attached to each bonded surface. A failure mode in which the adhesive is cleanly removed from the substrate is called "adhesive failure mode". Adhesives with cohesive failure mode are considered to be more robust than adhesives with adhesive failure mode.

[0097] The laminated samples were cured at 23°C and 50% relative humidity for 10 minutes. The initial adhesive strength of the cured laminated samples was measured according to JIS L1093 Method A-1. The initial adhesive strength after 10 minutes was measured three times for each sample, and the average value was recorded. An initial adhesive strength of 0.2 N / inch or higher at 10 minutes in 100% cohesive failure mode is considered acceptable.

[0098] Opening hours 10 g of the adhesive composition prepared as described above was coated onto paper to a thickness of 100 μm at 130°C using an automatic film applicator (Elecometer 4340). A 2.5 cm x 10 cm strip of paper was pressed onto the coated paper with a finger every 10 to 30 seconds. The open time was defined as the time until tearing of the paper stripe fibers was observed. Adhesive compositions with open times ranging from 1 minute to over 20 minutes were acceptable.

[0099] Invention Example 1 and Comparative Examples 1-3 In this series of examples, one moisture-curing polyurethane reactive hot-melt adhesive composition of the present invention (Example 1) and three compositions (Comparative Examples 1 to 3) in which component (B) of the present invention was replaced with another resin were prepared based on the weight percentages specified in Table 1.

[0100] [Table 1]

[0101] As can be seen from Table 1, the compositions of Comparative Examples 1 to 3, which included resins other than component (B), had compatibility issues, but the composition of the present invention (Example 1) showed excellent performance.

[0102] Invention Examples 2-4 (Example 2 is a reference example) and Comparative Examples 4-5 In this series of examples, the moisture-curing polyurethane reactive hot-melt adhesive compositions of the present invention (Examples 2-4) and two compositions having component (B) outside the claimed weight percentage of the present invention (Comparative Examples 4-5) were prepared based on the weight percentages specified in Table 2.

[0103] [Table 2]

[0104] As can be seen from Table 2, compositions having component (B) outside the claimed weight percentage of the present invention (Comparative Examples 4-5) showed almost zero open time or unacceptable initial adhesive strength at 2 minutes and 10 minutes, while compositions of the present invention (Examples 2-4) showed superior performance.

[0105] Invention Examples 5-7 and Comparative Example 6 In this series of examples, moisture-curable polyurethane reactive hot-melt adhesive compositions having components (B) with different weight-average molecular weights (Mw) were prepared based on the weight percentages specified in Table 3.

[0106] [Table 3]

[0107] As shown in the test results in Table 3, the adhesive composition containing component (B) with a weight-average molecular weight (Mw) of 100,000 g / mol (Comparative Example 6) underwent phase separation.

[0108] These modifications and changes to the present invention, as well as other modifications and changes, can be carried out by those skilled in the art without departing from the spirit and scope of the invention. Furthermore, it should be understood that aspects of the various embodiments are interchangeable, either whole or within the reagent. Moreover, those skilled in the art will understand that the foregoing description is for illustrative purposes only and is not intended to limit the invention as further described in the appended claims. The description in the initial application, such as the specification, includes at least the following aspects: [1] At least one reactive polyurethane prepolymer obtained by reacting a reagent mixture containing (A), (a) at least one polyol, and (b) at least one polyisocyanate having at least two isocyanate groups in one molecule; (B) At least one vinyl acetate homopolymer having a weight-average molecular weight (Mw) of less than 15,000 to 100,000 g / mol and present in an amount of less than 70% by weight based on the total weight of the adhesive composition. A moisture-curing polyurethane hot-melt adhesive composition containing [the specified ingredient]. [2] The moisture-curing polyurethane hot-melt adhesive composition according to [1], wherein reactant (a) is selected from polyester polyols, polyether polyols, and combinations thereof. [3] The moisture-curing polyurethane hot-melt adhesive composition according to [2], wherein the polyester polyol used as the reactant (a) is selected from solid polyester polyols, liquid polyester polyols, and combinations thereof, preferably selected from crystalline polyester polyols, amorphous polyester polyols, liquid polyester polyols, and combinations thereof. [4] The moisture-curing polyurethane hot melt adhesive composition described in [3], wherein the polyester polyol used as the reactant (a) has a number 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. [5] The polyether polyol used as the reactant (a) is selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, polyethylene oxide, polybutylene oxide and any of the ethylene oxide end cap versions thereof, and combinations thereof, preferably selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, ethylene oxide end cap poly(oxypropylene) glycol, and combinations thereof, as described in [2], for the moisture-curing polyurethane hot melt adhesive composition. [6] Reactant (b) is 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H12MDI), partially hydrogenated MDI (H6MDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), 4,4-diphenyldimethylmethane diisocyanate, diaryl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1 ,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, isomers of 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), tetramethoxybutane-1,4-diiso Cyanates, 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), bisisocyanate phthalate A moisture-curing polyurethane hot-melt adhesive composition according to [1], selected from toethyl esters, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, dimer fatty acid diisocyanate, lysine ester diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,3-cyclohexane or 1,4-cyclohexane diisocyanate, and combinations thereof. [7] A moisture-curing polyurethane hot-melt adhesive composition according to any one of [1] to [6], wherein component (B) has a weight-average molecular weight (Mw) in the range of 30,000 to 60,000 g / mol, more preferably 45,000 to 55,000 g / mol. [8] 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 [6], further comprising at least one catalyst (C) selected from ',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 combinations thereof. [9] The adhesive composition hot melt is a moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to [6], further comprising (D) at least one additive.

[10] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to [6], wherein the reactant (a) is present in an amount of 20% to 85% by weight, more preferably 40% to 80% by weight, based on the total weight of the adhesive composition.

[11] The moisture-curing polyurethane hot melt adhesive composition according to any one of [1] to [6], wherein the reactant (b) is present in an amount of 5% to 25% by weight, preferably 10% to 20% 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 [6], wherein component (B) is present in an amount preferably 1% to 60% by weight, and preferably 5% to 45% by weight, based on the total weight of the adhesive composition.

[13] A cured product of a reactive hot melt adhesive composition as described in any of [1] to

[12] .

[14] 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, textile, wood, and metal, and the adhesive layer is formed by curing an adhesive composition described in any of [1] to

[12] .

[15] Use of the reactive hot melt adhesive composition described in any of [1] to

[12] in the manufacture of consumer goods, automotive parts, electronic devices, and home appliances.

Claims

1. (A) (a) at least one polyol, and (b) At least one polyisocyanate having at least two isocyanate groups in one molecule At least one reactive polyurethane prepolymer obtained by reacting a mixture of reagents containing the following: (B) At least one vinyl acetate homopolymer having a weight-average molecular weight (Mw) of 30,000 to 60,000 g / mol and present in an amount of 20% to less than 70% by weight based on the total weight of the adhesive composition. A moisture-curing polyurethane hot-melt adhesive composition containing [the specified ingredient].

2. The moisture-curing polyurethane hot-melt adhesive composition according to claim 1, wherein reactant (a) is selected from polyester polyols, polyether polyols, and combinations thereof.

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

4. The moisture-curing polyurethane hot-melt adhesive composition according to claim 3, wherein the polyester polyol used as the reactant (a) has a number-average molecular weight (Mn) of 800 to 20,000 g / mol.

5. The moisture-curing polyurethane hot-melt adhesive composition according to claim 2, wherein the polyether polyol used as the reactant (a) is selected from polytetramethylene ether glycol, poly(oxypropylene) glycol, polyethylene oxide, polybutylene oxide and any of the ethylene oxide end-cap versions thereof, and combinations thereof.

6. Reactant (b) 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-phenylenediisocyanate, 1,4-phenylenediisocyanate, isomers of 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), tetramethoxybutane-1,4-diiso Cyanates, 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), bisisocyanate phthalate A moisture-curing polyurethane hot-melt adhesive composition according to claim 1, selected from toethyl ester, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, dimer fatty acid diisocyanate, lysine ester diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,3-cyclohexane or 1,4-cyclohexane diisocyanate, and combinations thereof.

7. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 6, wherein component (B) has a weight-average molecular weight (Mw) in the range of 45,000 to 55,000 g / mol.

8. A moisture-curing polyurethane hot adhesive composition according to any one of claims 1 to 6, wherein the adhesive composition comprises 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 A moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 6, further comprising at least one catalyst (C) selected from '-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 combinations thereof.

9. The adhesive composition hot melt further comprises (D) at least one additive, the moisture-curing polyurethane hot melt adhesive composition according to any one of claims 1 to 6.

10. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 6, wherein the reactant (a) is present in an amount of 20% to 85% by weight relative to the total weight of the adhesive composition.

11. The moisture-curing polyurethane hot-melt adhesive composition according to any one of claims 1 to 6, wherein the reactant (b) is present in an amount of 5% to 25% 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 6, wherein component (B) is present in an amount of 20% to 60% by weight based on the total weight of the adhesive composition.

13. A cured product of a reactive hot melt adhesive composition according to any one of claims 1 to 12.

14. 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, textile, wood, and metal, and the adhesive layer is formed by curing an adhesive composition according to any one of claims 1 to 12.

15. Use of the reactive hot melt adhesive composition according to any one of claims 1 to 12 in the manufacture of consumer goods, automotive parts, electronic devices, and home appliances.

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