Curable adhesive composition for multipurpose bonding applications

Abstract

The present invention relates to curable adhesive compositions based on acetoacetate compounds and their use in multipurpose adhesive applications. In particular, the present invention relates to curable adhesive compositions based on multifunctional acetoacetate compounds and polyoxyalkylene polyamines.

Description

[Technical Field]

[0001] The present invention relates to curable adhesive compositions based on acetoacetate compounds and their use in multipurpose adhesive applications. In particular, the present invention relates to curable adhesive compositions based on multifunctional epoxy acetate compounds and polyoxyalkylene polyamines. [Background technology]

[0002] Multipurpose adhesives, also known as universal adhesives, are used to bond numerous substrates used in industrial and domestic applications, including paper, cardboard, photographs, fabrics, leather, felt, bast, cork, films, metals such as aluminum and steel, porcelain, ceramics, glass, wood, and various plastics such as PVC. These adhesives are expected to provide satisfactory adhesion to a variety of substrates with different chemical and physical surface structures, which typically require special surface treatments for bonding.

[0003] Compared to the wide variety of adhesive classes and types used in industry and workshops, only a few substances are able to meet the stringent requirements for universality in multi-purpose adhesives. Among them, polyvinyl acetate and its copolymers are widely used.

[0004] Demand or universality is a particularly difficult selection criterion for adhesive compositions. Ultimately, adhesive compositions must exhibit equally high affinity for polar and non-polar surfaces. Therefore, a statement that a particular substance is suitable for use in an adhesive does not indicate to the expert whether it can also be used in a universal adhesive composition. Therefore, efforts have been made to address this requirement.

[0005] For example, US 6602958 B2 discloses a two-component, room-temperature curing, methacrylate-based adhesive used to bond a variety of materials, including thermosetting plastics, thermoplastics, metals, wood, ceramics, other materials, and material combinations. It is reported that minimal surface preparation is required, significantly improving the adhesive's ability to bond certain difficult-to-bond composite materials.

[0006] DE 102009045197 A1 discloses an aqueous adhesive comprising a component (a) containing poly(meth)acrylic acid and / or at least one (meth)acrylic acid copolymer and a component (b) containing at least one polyurethane having at least one component capable of forming a salt by releasing a proton in water, which is suitable for use as a multipurpose adhesive.

[0007] US 5270433 A discloses a universal household adhesive composition comprising a substantially transparent, solvent-free, aqueous one-component polyurethane dispersion containing the reaction product of (a) a polyol mixture including polypropylene glycol, (b) a mixture of polyfunctional isocyanates including α,α,α',α'-tetramethylxylene diisocyanate, (c) a functional component capable of forming a salt in aqueous solution, and (d) optionally a chain extender. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 6,602,958 [Patent Document 2] DE 102009045197 [Patent Document 2] US Patent Application Publication No. 5,270,433 Summary of the Invention [Problem to be solved by the invention]

[0009] It is therefore an object of the present invention to provide alternative adhesive compositions with safer toxicological profiles for multipurpose adhesive applications.

[0010] This object is achieved by a curable adhesive composition comprising a polyfunctional heteroacetate compound and at least two polyoxyalkylene polyamines, which has a curing time of less than 5 minutes and excellent adhesive performance for bonding substrates made of various materials, such as metal, wood, and plastic. [Means for solving the problem]

[0011] In one aspect, the present invention relates to a curable adhesive composition comprising: polyfunctional acetoacetate compounds, polyoxypropylene polyamines, and O Polyoxyalkylene having at least two oxyalkylene units selected from oxypropylene units, oxyethylene units, and oxytetramethylene units. Polyamines .

[0012] In another aspect, the present invention provides a coating composition comprising a first part including a polyfunctional acetoacetate compound and a polyoxypropylene polyamine. , O Polyoxyalkylene having at least two oxyalkylene units selected from oxypropylene units, oxyethylene units, and oxytetramethylene units. Polyamines and a second part comprising the curable adhesive composition.

[0013] In yet another aspect, the present invention relates to the use of the curable adhesive composition or the two-part curable adhesive composition in bonding substrates made of or having a surface of paper, fabric, leather, metal, ceramic, porcelain, glass, wood, or plastic.

[0014] Further preferred embodiments of the invention are set forth in the claims. DETAILED DESCRIPTION OF THE INVENTION

[0015] As used herein, the terms "a," "an," and "at least one" are equivalent to the term "one or more" and can be used interchangeably.

[0016] As used herein, "one or more" refers to at least one of the referenced species, including 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. Similarly, "at least one" means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. "At least one," as used herein with respect to any moiety, refers to the number of chemically distinct molecules, i.e., the number of different types of the referenced species, but does not refer to the total number of molecules.

[0017] When referring to the molecular weight of a polymer or its components herein, this refers to the number average molecular weight Mn unless otherwise specified. The number average molecular weight Mn can be determined by gel permeation chromatography using THF as the eluent. Unless otherwise specified, all molecular weights given are determined by end group analysis. The weight average molecular weight Mw can be determined by GPC as described for Mn.

[0018] All percentages given herein with respect to compositions or preparations relate to weight % based on the total weight of the respective composition or formulation, unless expressly stated otherwise.

[0019] In accordance with the present invention, the curable adhesive composition comprises a polyfunctional acetoacetate compound, a polyoxypropylene polyamine, and Nio a polyoxyalkylene having at least two oxyalkylene units selected from an oxypropylene unit, an oxyethylene unit, and an oxytetramethylene unit; Polyamines The inventors have surprisingly found that the curable adhesive composition is suitable for bonding various types of substrates, such as paper, fabric, leather, metal, pottery, ceramic, glass, wood, or plastic.

[0020] The developed curable adhesive composition has excellent adhesive properties for multipurpose bonding and a mild toxicity profile compared to standard epoxy- or (meth)acrylate-based formulations. Based on an acetylacetonate resin cured with a polyetheramine curing agent, the formulation can be applied from a two-component cartridge and hardens into a tough polymer with a cure time of less than 5 minutes. Strong adhesive and cohesive strength was observed when bonding metals, various plastics, and wood. The rheological behavior and mixing ratio can be adjusted by fillers, and the introduction of filler particles into the formulation has been shown to improve mechanical resistance.

[0021] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of 10 MPa or greater in bonding steel substrates.

[0022] The curable adhesive composition is formulated to provide a cured product with a lap shear strength of at least 10 MPa when bonding aluminum substrates.

[0023] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of 7 MPa or greater in bonding wood substrates.

[0024] The curable adhesive composition is formulated to provide a cured product with a lap shear strength of 5 MPa or greater for bonding polycarbonate (PC) substrates.

[0025] The curable adhesive composition is formulated to provide a cured product with a lap shear strength of 3 MPa or greater for bonding polyvinyl chloride (PVC) substrates.

[0026] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of 4 MPa or greater in bonding poly(methyl methacrylate) (PMMA) substrates.

[0027] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of 3 MPa or greater in bonding acrylonitrile-butadiene-styrene (ABS) substrates.

[0028] Additionally, curable adhesive compositions offer other advantages. For example, they are solvent-free, catalyst-free, have usable viscosities and pot lives, and cure quickly at room temperature. Finally, they provide strong adhesive bonds that are resistant to moisture and chemicals such as acetone, ethyl acetate, 2-propanol, methyl ethyl ketone, ethanol, and toluene.

[0029] According to the present invention, the polyfunctional acetoacetate compound may have at least two acetoacetoxy groups, preferably 2 to 10 acetoacetoxy groups, and more preferably 2 to 4 acetoacetate groups. Thus, this component may comprise a single compound having at least two acetoacetoxy groups, or a mixture of two or more compounds, each having at least two acetoacetoxy groups. Each such compound should desirably be characterized by a number average molecular weight (Mn) of less than 12,000 g / mol, e.g., less than 10,000 g / mol, or less than 6,000 g / mol.

[0030] In a preferred embodiment, the curable adhesive composition comprises at least one acetoacetylated polyol, said acetoacetylated polyol being obtainable according to the following formula (Reaction 1): TIFF0007824888000001.tif13132(1) During the ceremony: R is C1-C 12 is an alkyl group; L represents the main chain structure of the polyol; and q≧2.

[0031] The above reaction 1 is represented by the following formula (I): This can be described as a transesterification reaction, or more specifically, a transacetyl reaction, of a polyol with an acetoacetate compound defined as TIFF0007824888000002.tif2245 formula (I) In the formula, R is the C1-C 12 The alkyl group R is preferably an alkyl group. More typically, the constituent alkyl group R has 1 to 8, preferably 1 to 6, carbon atoms. Exemplary alkyl acetoacetates include t-butyl acetoacetate; isobutyl acetoacetate; n-butyl acetoacetate; isopropyl acetoacetate; n-propyl acetoacetate; ethyl acetoacetate; and methyl acetoacetate. t-Butyl acetoacetate is preferred herein.

[0032] The polyol of Reaction 1 above is represented by the following formula (II): L-(OH) q Formula (II) where q≧2 and L represents the backbone structure. Such polyols (II) may optionally contain heteroatoms in their main chain or pendant side chains. Furthermore, polyols (II) may be monomeric polyhydric alcohols or may have an oligomeric or polymeric main chain. Regardless of this, polyols (II) preferably have a number average molecular weight (Mn) of less than 12,000 g / mol; and a hydroxyl functionality q of 2 to 10, preferably 2 to 4.

[0033] In one embodiment, the curable adhesive composition includes an acetoacetylated polyol derived from a monomeric polyhydric alcohol. Examples of suitable monomeric polyhydric alcohols include, but are not limited to, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,4-pentanediol, butylethylpropanediol, 1,4-hexanediol, 1,4-cyclohexanedimethanol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tricyclodecane dimethanol, hydroquinone bis(2-hydroxyethyl)ether, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, alkylene glycols such as pentamethylene glycol, hexamethylene glycol, hexylene glycol, and neopentyl glycol; glycerol; castor wax; sugars such as glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose, and erythrose; sugar alcohols such as erythritol, xylitol, malitol, mannitol, and sorbitol; hydroxyalkylated aliphatic diamines such as o,o'-bis(diethanolaminomethyl)-p-nonylphenol, N,N,N,N'-tetra(2-hydroxypropyl)ethylenediamine (Quadrol L, available from BASF), and N,N,N,N-tetra(2-hydroxyethyl)ethylenediamine. In a preferred embodiment, the polyfunctional acetate compound is an acetoacetylated polyol derived from glycerol, trimethylolpropane, ethanol isosorbide, neopentyl glycol, pentaerythritol, dimethylolpropane, dipentaerythritol, propoxylated monosaccharides, trimethylolethane, and combinations thereof.

[0034] The present invention does not exclude such polyfunctional acetoacetate compounds from acetoacetylated polyols obtained from oligomeric or polymeric polyhydric alcohols. In particular, polyol (II) can be selected from the group consisting of polyoxyalkylene polyols, also known as polyether polyols; polyester polyols, including polycaprolactone polyols, polyesteramide polyols; polycarbonate polyols; polybutadiene polyols; polyurethane polyols; polyacrylate polyols; and combinations thereof. Desirably, such oligomeric or polymeric polyols should be characterized by a number-average molecular weight (Mn) of up to 10,000 g / mol, preferably 250 to 6,000 g / mol. Furthermore, it is particularly important to use one or more polyether polyols or polyester polyols as starting materials. A commercially available example of a polyether polyol is Voranol CP260 (available from DowDuPont).

[0035] As is known in the art, polyester polyols can be prepared from the condensation reaction of a polybasic carboxylic acid or anhydride with a stoichiometric excess of a polyhydric alcohol, or from a mixture of polybasic carboxylic acids, monobasic carboxylic acids, and polyhydric alcohols. Suitable polybasic carboxylic acids and anhydrides for use in producing polyester polyols include those containing 2 to 18 carbon atoms, particularly those containing 2 to 10 carbon atoms. Non-limiting examples of such polybasic carboxylic acids and anhydrides include adipic acid, glutaric acid, succinic acid, malonic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and combinations thereof. Monobasic carboxylic acids that can be used include those having 1 to 18, or preferably 1 to 10, carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and combinations thereof. Suitable polyhydric alcohols have 2 to 18, preferably 2 to 10, carbon atoms. Exemplary polyhydric alcohols include, but are not limited to, ethylene glycol, propylene glycol, hexane-1,6-diol, trimethylolpropane, glycerol, neopentyl glycol, pentaerythritol, butylene glycol, 2-methyl-1,3-propanediol, hexylene glycol, and combinations thereof.

[0036] Polyether polyols may be produced by processes known in the art, such as by reacting an alkene oxide with a polyhydric starter molecule in the presence of a suitable catalyst, such as an alkali metal hydroxide, an alkali metal alkoxide, or antimony pentachloride. Alkene oxides include tetrahydrofuran, ethylene oxide, 1,2-propylene oxide, 1,2- and 2,3-butylene oxide, and styrene oxide. Suitable starter molecules include, but are not limited to, water, ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, diethylene glycol, and trimethylolpropane. Preferred polyether polyols for use herein are poly(propylene oxide) polyols, poly(ethylene oxide) polyols, PTMEG, and mixtures thereof.

[0037] The polycarbonate polyol for use herein can be selected from, but is not limited to, polycarbonate diols. Such polycarbonate diols can be prepared by reacting a diol with a dialkyl or diaryl carbonate or phosgene. The reactant diol can be selected from, but is not limited to, 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; diethylene glycol; trioxyethylene glycol; and mixtures thereof. An exemplary diaryl carbonate is diphenyl carbonate.

[0038] The transesterification (transacetylation) reaction 1 can be carried out by conventional methods known in the field of polymer chemistry. In this regard, reference can be made, inter alia, to Witzman et al., "Comparison of Methods for the Preparation of Acetoacetylated Coating Resins," Journal of Coatings Technology, Vol. 62, No. 789, October 1990; and Witzeman et al., "Transacetoacetylation with tert-Butyl Acetoacetate: Synthetic Applications," J. Org. Chemistry 1991, 56, 1713-1718. Typically, the reaction between an oligomeric or polymeric polyol and an acetoacetate involves mixing the polyol with the acetoacetate in a suitable vessel, with or without a solvent, at elevated temperatures, for example, between 50°C and 200°C or between 80°C and 150°C; preferably, the reaction is carried out without a solvent. The formed alcohol (R—OH) is distilled off under reduced pressure, driving the reaction to completion. Additionally, the reaction can be carried out in the presence of a catalytic amount of a transesterification catalyst, suitable examples of which include, but are not limited to, calcium acetate, zinc acetate, bismuth acetate, lead oxide, and trichloroacetic acid.

[0039] While the product of the transacetylation reaction can be used directly in the multipurpose adhesive composition, the reaction product can first be isolated and purified using methods known in the art, in which suitable techniques include extraction, evaporation, distillation, and chromatography.

[0040] According to the present invention, the adhesive composition also contains a polyoxypropylene polyamine, which refers to a polyamine having only oxypropylene units in its main chain structure.

[0041] In one preferred embodiment, the polyoxypropylene polyamine is selected from polyoxypropylene diamines, polyoxypropylene triamines, and combinations thereof.

[0042] An example of a polyoxypropylene diamine is represented by formula (1): TIFF0007824888000003.tif2463(1) In the formula, x is 2 to 100, preferably 2 to 80.

[0043] The polyoxypropylenediamine preferably has a number average molecular weight of 100 to 5,000, more preferably 200 to 4,000.

[0044] Such polyoxypropylene diamines are commercially available from Huntsmann as Jeffamine D series polyether polyamines, such as D-230, D-400, D-2000 and D-4000.

[0045] An example of a polyoxypropylene triamine is represented by formula (2): TIFF0007824888000004.tif41103(2) In the formula, n is 0 to 6, w, y, and z are each independently 1 to 100, more preferably 1 to 80, the sum of w, y, and z is 3 to 100, preferably 5 to 85, and R1 is hydrogen or a linear or branched C1 to C 16 It is an alkyl group, preferably hydrogen or a linear or branched C1 to C8 alkyl group.

[0046] The polyoxypropylene triamine preferably has a number average molecular weight of 100 to 8,000, more preferably 200 to 6,000.

[0047] Such polyoxypropylene triamines are commercially available from Huntsmann as Jeffamine T-series polyether polyamines, such as T-403, T-3000 and T-5000.

[0048] In accordance with the present invention, the curable adhesive composition also comprises , OPolyoxyalkylene having at least two oxyalkylene units selected from oxypropylene units, oxyethylene units, and oxytetramethylene units. Polyamines Includes:

[0049] In one embodiment, the polyoxyalkylene polyamine has oxydimethyl and oxyethylene units in the backbone structure. Such polyoxyalkylene polyamines can be represented by formula (3): TIFF0007824888000005.tif2496In the formula, a is 0 to 10, b is 2 to 60, c is 0 to 10, and the sum of a and c is 2 to 20.

[0050] The number average molecular weight of the polyoxyalkylene polyamine having an oxypropylene unit and an oxyethylene unit is preferably 100 to 5,000, more preferably 200 to 3,000.

[0051] Such polyether polyamines are commercially available from Huntsmann as the Jeffamine ED series polyether polyamines, such as ED-600, ED-900 and ED-2003.

[0052] In another embodiment, the polyoxyalkylene polyamine has oxypropylene and oxytetramethylene units in the backbone structure.

[0053] Preferably, such polyoxyalkylene polyamines having oxypropylene units and oxytetramethylene units have a number average molecular weight of 100 to 3,000, more preferably 200 to 2,000.

[0054] Such polyether polyamines are commercially available from Huntsmann as the Jeffamine THF series polyether polyamines, such as THF-100, THF-140 and THF-170.

[0055] Optionally, the curable adhesive composition includes at least one amine cure accelerator having 1 to 10, e.g., 2 to 6, or 2 to 4 primary and / or secondary amino groups according to formula (III): R 2 R 3 NH formula (III) During the ceremony, R 2 is hydrogen or a C1-C6 alkyl group; and R 3 is a hydrocarbyl group having up to 36 carbon atoms, including aromatic groups, which hydrocarbyl group may be one or more -NHR 2 groups, and may further comprise one or more O atoms and / or one or more —N(R 4 )-group(R 4 is a hydrogen atom); R 3 is C1-C 36 an aliphatic group and one or more NHR 2 groups, and optionally further substituted with one or more O atoms and / or one or more N(R 4 )-group(R 4 is a hydrogen atom); and R 2 and R 3 may form a ring together with the N atom to which they are attached.

[0056] For completeness, R 2 and R 3 It will be appreciated that when forms a ring, such ring may be heterocyclic and may contain one or more nitrogen atoms.

[0057] Good results have also been obtained when the reactant amine according to formula (III) is characterized in that: 2 is hydrogen, and R 3 is C1~C 36 Alkyl groups, preferably C1-C 12 and at least one -NHR 2and optionally substituted with one or more —N(R 4 )-group(R 4 are hydrogen atoms). Exemplary diprimary amines of this embodiment include: tetramethylenediamine; pentamethylenediamine; hexamethylenediamine; octamethylenediamine; and dodecamethylenediamine. Exemplary primary-secondary diamines of this embodiment include: N-methylethylenediamine; N-ethylethylenediamine; N-methyl-1,3-diaminopropane; 2-(isopropylamino)ethylamine; N-propylethylenediamine; N-propyl-1,3-propanediamine; N-cyclohexyl-1,3-propanediamine; 4-(aminomethyl)piperidine; 3-(aminomethyl)piperidine; 2-(aminomethyl)piperidine; and 4-aminopiperidine.

[0058] Further exemplary commercially available amines for use in the present invention include, but are not limited to, 2-methyl-1,5-diaminopentane, available from Invista Arpadis as Dytek A; 1,2-diaminocyclohexane, available from Invista Arpadis as Dytek DCH-99 as a mixture of isomers; N,N'-dimethylhexanediamine (MAHMA), available from Sigma-Aldrich; fatty acid dimer-based diamines, available from Croda as Priamine 1071, 1073, 1074, and 1075; phenalkamines, available from Cardolite Corporation as Cardolite NX-5608, NX-5607, and LITE 3060; polyethyleneimine (PEI), available from BASF under the tradenames Lupasol G20 (anhydrous) and Lupasol FG, and isophoronediamine from Sigma-Aldrich.

[0059] Further exemplary amines suitable for use in the compositions of the present invention include piperidine and pyrrolidine.

[0060] In certain circumstances, it may be advantageous for the amine cure accelerator to comprise a primary amine according to formula (III), characterized in that R2 is hydrogen and R3 is a C1-C12 alkyl group, preferably a C1-C6 alkyl group. Exemplary amines of this type include: n-butylamine; n-hexylamine; n-octylamine; n-decylamine; and n-dodecylamine.

[0061] In one preferred embodiment, the amine cure accelerator is a cycloaliphatic amine preferably selected from isophoronediamine, menthanediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-di(aminomethyl)cyclohexane, 4,4′-methylenedicyclohexylamine, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexyl-methane, and combinations thereof.

[0062] When present, the molar equivalent ratio of amine groups in the amine cure accelerator to amine groups in the polyether polyamine ranges from 1:10 to 10:1, preferably from 1:5 to 5:1, more preferably from 1:3 to 3:1.

[0063] It should be noted that the compositions of the present invention can contain a large excess of either the amine from the polyether polyol and amine cure accelerator (if present) or the acetoacetate. For example, the compositions can be broadly characterized as having a molar equivalent ratio of acetoacetate to amine of 1:10 to 10:1. However, the total amount of amine in the compositions of the present invention can generally be selected so that the molar equivalent ratio of acetoacetate to amine is in the range of 2:1 to 1:2, e.g., 1.2:1 to 0.8:1. Thus, it is preferred that one mole of amine is available for every equivalent of acetoacetate in the composition, although variations on this preferred 1:1 equivalent ratio are permissible.

[0064] An advantage of the chemistry of the present curable compositions is that their cure rate can be tuned or moderated to control the rate at which the cured material develops its mechanical properties on various types of substrates. For example, a fast cure reaction and the associated rapid development of these mechanical properties can be advantageous in multipurpose adhesive applications.

[0065] To form a multipurpose curable adhesive composition, the reactive components are assembled and mixed in a manner that induces their curing. More specifically, the components can be mixed in predetermined amounts by hand, machine, (co)extrusion, or any other means that can ensure their fine and highly uniform mixing. At initial mixing (herein "initial" means up to one minute after the components are combined), the curable adhesive composition is a liquid or paste at room temperature. However, this fact does not exclude the mixing temperature from being higher than room temperature, for example, up to 15°C above room temperature.

[0066] Of course, curable adhesive compositions may contain auxiliary ingredients and additives. However, adhesive compositions should generally be formulated to exhibit an initial viscosity suitable for paste or liquid materials. For unfilled adhesive compositions, this is less than 30,000 mPa·s at 25°C, preferably less than 15,000 mPa·s, and more preferably less than 7,500 mPa·s. For filled adhesive compositions, this is less than 2,000 Pa·s, preferably less than 1,000 Pa·s, and more preferably less than 500 Pa·s.

[0067] Independently of, or in addition to, the viscosity characteristics, the curable adhesive composition should be formulated to be free of bubbles (foam) upon mixing and subsequent curing. Furthermore, the curable adhesive composition should also be formulated to exhibit at least one, preferably at least two, and most preferably all of the following properties: i) bond strength after the composition has been cured for 5 minutes; ii) a peak exotherm temperature of 120°C or less, preferably 100°C or less, and more preferably 80°C or less; and iii) a Shore A hardness of at least 50, preferably 60, and more preferably at least 70, after curing and storage at room temperature and 50% relative humidity for 7 days.

[0068] The composition of the present invention may be solvent-free. Alternatively, the composition may contain one or more solvents, and at least one of the solvents is preferably miscible with water. Therefore, it is envisioned that the composition may be characterized by a solvent system consisting of two or more solvents that are miscible with water. Similarly, the composition may be characterized by a solvent system consisting of at least one solvent that is not miscible with water and at least one solvent that is miscible with water. For completeness, the term "immiscible" as used herein means that two phases exist in some proportion.

[0069] Non-limiting examples of water-miscible solvents include, but are not limited to, acetic acid, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane, ethanol, methanol, n-propanol, isopropanol, and tetrahydrofuran. Non-limiting examples of water-immiscible solvents include benzene, n-butanol, butyl acetate, carbon tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, dichloromethane, ethyl acetate, diethyl ether, heptane, hexane, methyl-1-butyl ether, methyl ethyl ketone, pentane, diisopropyl ether, toluene, trichloromethane, xylene, and combinations thereof.

[0070] When used, the amount of solvent present in the composition can be determined based on typical practical considerations. However, generally, the volume to weight ratio of the solvent to the acetoacetate-functionalized compound ranges from 1:1 to 100:1. In some embodiments, the volume to weight ratio of the solvent to the acetoacetate-functionalized compound may range from 1:1 to 50:1.

[0071] Of course, the compositions of the present invention can also include standard additives such as pigments, fillers, plasticizers, leveling agents, foam inhibitors, rheology control agents, catalysts, antioxidants, tackifiers, adhesion promoters, flame retardants, and UV stabilizers. The selection of suitable additives is limited only in that they must be compatible with the other components of the composition and not detrimental to the use of the composition in multipurpose adhesive applications.

[0072] When fillers are used, they should typically be present in amounts up to 75% by weight, e.g., up to 50% by weight, or up to 30% by weight, based on the weight of the composition. Suitable fillers for use herein include, for example, chalk, lime powder, precipitated and / or pyrogenic silicic acid, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, aluminum trihydroxide, magnesium hydroxide, and other ground mineral substances. Organic fillers, particularly carbon black, graphite, rubber particles, wood fiber, wood flour, sawdust, cellulose, melamine, cotton, pulp, wood chips, shredded straw, rice husks, ground walnut shells, and other shredded fibers, can also be used. Short fibers, such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, and polyethylene fiber, can also be added. Aluminum powder is also suitable as a filler.

[0073] In certain embodiments, a plasticizer may be included to improve the softness and flexibility of the cured curable adhesive composition. In this case, one or more plasticizers can be selected from the group consisting of vegetable oils, mineral oils, soybean oils, terpene resins, aromatic esters such as dioctyl phthalate, diundecyl phthalate, tricresyl phosphate, and triisononyl mellitate, linear esters such as ditridecyl adipate, chlorinated paraffins, aromatic and naphthenic processing oils, alkylnaphthalenes, and low molecular weight polyisoprene, polybutadiene, monofunctional and long-chain amine-containing, or polybutylene resins. Traditionally, the amount of plasticizer should be 0 to 20% by weight, preferably 0 to 10% by weight, or 0 to 5% by weight, based on the total weight of the multipurpose adhesive composition.

[0074] The curing reaction of the composition can be catalyzed. Known catalysts include, for example, stannous octoate, stannous dioleate, stannous palmitate, stannous oxalate, boron trifluoride etherate, and Bronsted acid. If used, the amount of catalyst should be determined in the absence of an applicable support and should be 0.001 to 5 wt. %, preferably 0.01 to 2 wt. %, based on the total weight of the reactant amines used. However, it is highly preferred that the composition be free of catalysts.

[0075] Preferably, organofunctional silanes, such as mercapto-functional silanes, epoxy-functional silanes, and especially amino-functional silanes, can be used as adhesion promoters to improve adhesion to metals. Examples of mercapto-functional silanes are 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, or their alkyldimethoxy or alkyldiethoxy analogs. Examples of amino-functional silanes include 3-aminopropylalkoxysilane and 2'-aminoethyl-3-aminopropylalkoxysilane. Epoxy-functional silanes can be selected from a wide range of compounds. Examples include: 3-glycidyloxymethyltrimethoxysilane, 3-glycidyloxymethyltriethoxysilane, 3-glycidoxymethyltripropoxysilane, 3-glycidoxymethyltributoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltrippropoxysilane, 2-glycidoxyethyltributoxysilane, 2-glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 1-glycidoxyethyltrippropoxysilane, 1-glycidoxyethyltributoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrippropoxysilane, 3-glycidoxypropyltri Butoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltripropoxysilane, 2-glycidoxypropyltributoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltriethoxysilane, 1-glycidoxypropyltrippropoxysilane, 1-glycidoxypropyltributoxysilane, 3-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 4-glycidoxybutyltrippropoxysilane, 4-glycidoxybutyltributoxysilane, 4-glycidoxybutyltrimethoxysilane, 3-glycidoxybutyltriethoxysilane, 3-glycidoxybutyltrippropoxysilane, 3-glycidoxybutyltributoxysilane,4-Glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 4-glycidoxybutyltrippropoxysilane, 1-glycidoxybutyltrimethoxysilane, 1-glycidoxybutyltriethoxysilane, 1-glycidoxybutyltrippropoxysilane, 1-glycidoxybutyltributoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltrippropoxysilane, (3,4-epoxycyclohexyl)methyltributoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane Examples of the adhesion promoter include methyltriethoxysilane, (3,4-epoxycyclohexyl)ethyltripropoxysilane, (3,4-epoxycyclohexyl)ethyltributoxysilane, (3,4-epoxycyclohexyl)propyltrimethoxysilane, (3,4-epoxycyclohexyl)propyltriethoxysilane, (3,4-epoxycyclohexyl)propyltripropoxysilane, (3,4-epoxycyclohexyl)propyltributoxysilane, (3,4-epoxycyclohexyl)butyltrimethoxysilane, (3,4-epoxycyclohexyl)butyltriethoxysilane, (3,4-epoxycyclohexyl)butyltripropoxysilane, and (3,4-epoxycyclohexyl)butyltributoxysilane. The adhesion promoter is preferably used in the composition in an amount of 0.1 to 10% by weight, preferably 0.5 to 4% by weight, and particularly preferably 0.5 to 2% by weight.

[0076] Flame retardants may be added to the adhesive compositions of the present invention to improve the performance of the cured product, particularly when used to bond wood. Examples of flame retardants include ammonium polyphosphate, triphenylphosphine oxide, aluminum triethylphosphinate, zinc diethyldiethylphosphinate, melamine cyanurate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, melamine borate, triphenyl phosphate, resorcinol bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), resorcinal bis-(2,6-dixylilenyl phosphate), aluminum hydroxide, aluminum hydroxide, magnesium dihydroxide, zinc oxide, molybdenum trioxide, antimony oxide, aluminum trihydroxide, zinc borate, calcium silicate, magnesium silicate, calcium sulfate, magnesium carbonate, dihydroxaphosphaphenanthrene, dihydroxaphosphaphenanthrene-hydroquinone, potassium diphenylsulfonesulfonate, polymethylphenylsiloxane, potassium butylperfluorosulfonate, and mixtures thereof. The flame retardant is preferably used in the composition in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 0.5 to 10% by weight.

[0077] In another aspect, the present invention provides a composition comprising a first component comprising a multifunctional epoxy acetate compound and a polyoxydimethylpolyamine and Bio Polyoxyalkylene having at least two oxyalkylene units selected from oxypropylene units, oxyethylene units, and oxytetramethylene units. Polyamines and a second part comprising:

[0078] The components of each part are stored in separate containers (parts) until the contents of all containers are mixed together to form the adhesive composition mixture prior to application. Once applied and cured, a solid material forms in the bond area.

[0079] Another aspect of the present invention is a method of bonding substrates together using the curable adhesive composition of the present invention. In this embodiment, the curable composition is applied to a first substrate. Application can be by any number of methods known to those skilled in the art (e.g., brushing, spraying, roller coating, gravure coating, flexo coating, flow coating, dipping, and combinations thereof) to form a continuous or discontinuous film of the composition as desired. In some embodiments, the curable composition is applied at ambient temperature (about 25°C); alternatively, the curable composition may be applied at an elevated temperature.

[0080] After the composition is applied to a first substrate, it can be contacted with another substrate to form a composite. The composite thus formed can optionally be subjected to pressure, such as by passing it through rollers, to increase contact between the substrate and the composition. In another embodiment of the present invention, the composition can be applied simultaneously or sequentially to both sides of a first substrate, and then this composition can be bonded simultaneously or sequentially to two additional substrates, which can be the same or different. It is further contemplated that the composite structure can be sequentially bonded to other substrates using the composition of the present invention or a different composition, either before or after the process described herein. The first and second substrates bonded in the methods of the present invention can be the same or different and can include, for example, paper, fabric, leather, metal (such as aluminum and steel), porcelain, ceramic, glass, wood, or plastic (such as PP, PC, PVC), and can have smooth or structured surfaces. They can be provided in the form of a roll, sheet, film, foil, or the like.

[0081] In some embodiments of the present invention, the substrate is relatively thin and flat, and the resulting composite is called a laminate. The substrate may be constructed of a multi-layer laminate structure based on polyalkylenes such as polyethylene and polypropylene, polyester, and polyamide (nylon), metallized polypropylene, aluminum foil, etc. Two-layer laminate structures include polypropylene / polypropylene, polyester / nylon, polyester / polyethylene, polypropylene / metallized polypropylene, polypropylene / aluminum foil, polyester / aluminum foil, polyamide / aluminum foil, etc.

[0082] The curable adhesive composition of the present invention is intended to undergo a chemical reaction referred to herein as "curing." While the present invention is not limited to a particular theory, it is believed that curing begins when the curable composition is formed and continues at least until the end of its pot life, and beyond. In some embodiments, a layer of the curable adhesive composition is applied to a substrate before the end of its pot life. In some of these embodiments, at least one additional substrate is contacted with the layer of curable mixture; often, this additional substrate is contacted with the layer of curable adhesive composition within the pot life. Thus, in some embodiments, curing is not complete until the curable adhesive composition and the substrate come into contact. It is believed that the cured product forms a useful adhesive bond between the substrates.

[0083] While the present invention is particularly useful as an adhesive, it is believed that it may also be applicable to coatings, polymer foams, sealants, and elastomers. When used as a coating, the curable adhesive composition is applied to a substrate and allowed to cure, with no further substrate coming into contact with the curable mixture. When used as a sealant, foam, or elastomer, the curable adhesive composition is placed, for example, in a mold or on a release surface and allowed to cure; the cured mixture can then be removed from the mold or release surface and used as intended.

[0084] Various features and embodiments of the present disclosure are described in the following examples, which are intended to be representative and not limiting. [Example]

[0085] Example material Jeffamine D-230 is a polyoxypropylene diamine having a number average molecular weight of about 230 from Huntsmann.

[0086] Jeffamine T-403 is a polyoxypropylene triamine having a number average molecular weight of about 440 from Huntsmann.

[0087] Jeffamine ED-600 is a polyoxypropylene polyoxyethylene diamine having a number average molecular weight of about 600 from Huntsmann.

[0088] Jeffamine ED-900 is a polyoxypropylene polyoxyethylene diamine having a number average molecular weight of about 900 from Huntsmann.

[0089] Jeffamine THF100 is a polyoxypropylene polyoxytetramethylene diamine having a number average molecular weight of about 1000 from Huntsmann.

[0090] Priamine 1071 is a dimer fatty acid diamine from Croda.

[0091] Jeffamine EDR148 is a diamine from Huntsmann with the following structure: TIFF0007824888000006.tif1492

[0092] Dytek DCH-99 is a 1,2-diaminocyclohexane from Invista Arpadis.

[0093] (3-aminopropyl)trimethoxysilane is an adhesion promoter from Alfa Aesar.

[0094] Omya BLH is a ground calcium carbonate from Omya.

[0095] Aerosil R202 is a hydrophobic fumed silica from Evonik.

[0096] Test Method Lap shear strength Samples were made from two 25mm wide substrates with a 10mm overlap. Samples were clamped in place and allowed to cure at room temperature for two days before testing. Tests were performed using a Zwick / Roell Z050, pulling at a rate of 10mm / min.

[0097] Fixed strength Fixture strength was rated "pass" if, when the clamps on the lap shear sample were removed after 5 minutes of curing, the sample did not separate under its own weight.

[0098] Solvent resistance Bulk polymers for the two-component formulations were prepared by mixing all components and curing at room temperature for 7 days. Solvent resistance was tested by repeatedly rubbing paper tissues soaked in various solvents back and forth on the surface of the cured bulk polymer. If no changes were observed on the polymer surface, the solvent resistance was rated "pass."

[0099] Synthesis of trimethylolpropane triacetoacetate The synthesis of trimethylolpropane triacetoacetate (AATMP) was carried out according to literature procedure WO2019 / 120923A1 with minor modifications. A 500 mL three-neck round-bottom flask was charged with trimethylolpropane or pentaerythritol (1 equivalent) and TBAA (1.1 equivalents). A Y-adapter, a mechanical stirrer, and a reflux condenser were then attached to each neck of the flask. The Y-adapter was fitted with a thermocouple and nitrogen connector. The temperature was set to 140 °C under a nitrogen atmosphere (reflux reached 92 °C in approximately 4 hours). Distillation was then carried out at atmospheric pressure for 8 hours, slowly increasing the temperature to 140 °C. Finally, after distillation stopped, vacuum distillation was carried out at 140 °C from 900 mbar to 400 mbar for 2 hours. The reaction scheme is shown below. TIFF0007824888000007.tif32153

[0100] Example 1 0.175 equivalents (20.83 g) of Jeffamine D230, 0.65 equivalents (37.11 g) of 1,2-diaminocyclohexane, 0.15 equivalents (46.65 g) of Jeffamine ED600, and 0.025 equivalents (4.48 g) of (3-aminopropyl)trimethoxysilane were mixed in a PP speed mixer cup. Next, 148.09 g of Omya BLH and 16.45 g of Aerosil R202 were added and mixed in the mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in the mixer cup. The mixture was then mixed in the speed mixer at 3500 rpm for 30 seconds to obtain the adhesive composition.

[0101] Example 2 0.175 equivalents (27.65 g) of Jeffamine T403, 0.65 equivalents (37.11 g) of 1,2-diaminocyclohexane, 0.15 equivalents (46.65 g) of Jeffamine ED600, and 0.025 equivalents (4.48 g) of (3-aminopropyl)trimethoxysilane were mixed in a PP speed mixer cup. Next, 152.37 g of Omya BLH and 16.93 g of Aerosil R202 were added and mixed in the mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in the mixer cup. The mixture was then mixed in the speed mixer at 3500 rpm for 30 seconds to obtain the adhesive composition.

[0102] Example 3 0.175 equivalents (20.83 g) of Jeffamine D230, 0.65 equivalents (37.11 g) of 1,2-diaminocyclohexane, 0.15 equivalents (74.03 g) of Jeffamine ED900, and 0.025 equivalents (4.48 g) of (3-aminopropyl)trisilane were mixed in a PP speed mixer cup. Next, 165.13 g of Omya BLH and 18.34 g of Aerosil R202 were added and mixed in the mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in the mixer cup. The mixture was then mixed in the speed mixer at 3500 rpm for 30 seconds to obtain the adhesive composition.

[0103] Example 4 0.175 equivalents (20.83 g) of Jeffamine D230, 0.65 equivalents (37.11 g) of 1,2-diaminocyclohexane, 0.15 equivalents (76.43 g) of Jeffamine THF100, and 0.025 equivalents (4.48 g) of (3-aminopropyl)trimethoxysilane were mixed in a PP speed mixer cup. Next, 166.63 g of Omya BLH and 18.51 g of Aerosil R202 were added and mixed in the mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in the mixer cup. The mixture was then mixed in the speed mixer at 3500 rpm for 30 seconds to obtain the adhesive composition.

[0104] Example 5 0.15 equivalents (18.30 g) of Jeffamine D230, 0.57 equivalents (32.61 g) of 1,2-diaminocyclohexane, 0.25 equivalents (77.75 g) of Jeffamine ED600, and 0.025 equivalents (4.48 g) of (3-aminopropyl)trimethoxysilane were mixed in a PP speed mixer cup. Next, 94.87 g of Omya BLH and 8.50 g of Aerosil R202 were added and mixed in the mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in the mixer cup. The mixture was then mixed in the speed mixer at 3500 rpm for 30 seconds to obtain the adhesive composition.

[0105] Comparative Example 1 0.2 equivalents (23.80 g) of Jeffamine D230, 0.65 equivalents (37.11 g) of 1,2-diaminocyclohexane, and 0.15 equivalents (44.06 g) of Priamine 1071 were mixed in a PP speed mixer cup. Next, 210.39 g of Omya BLH and 23.38 g of Aerosil R202 were added and mixed in the mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in the mixer cup. The mixture was then mixed in the speed mixer at 3500 rpm for 30 seconds to obtain the adhesive composition.

[0106] Comparative Example 2 0.25 equivalents (29.75 g) of Jeffamine D230, 0.65 equivalents (37.11 g) of 1,2-diaminocyclohexane, and 0.10 equivalents (7.85 g) of Jeffamine EDR148 were mixed in a PP speed mixer cup. Next, 183.16 g of Omya BLH and 20.35 g of Aerosil R202 were added and mixed in the mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in the mixer cup. The mixture was then mixed in the speed mixer at 3500 rpm for 30 seconds to obtain the adhesive composition.

[0107] The adhesive composition thus obtained was tested for its bond strength to various substrates and lap shear strength. The results are shown in Table 1.

[0108] Table 1 Test results TIFF0007824888000008.tif82150

[0109] Additionally, the resistance of the examples to solvents was also tested, and all examples according to the invention passed the test without showing any noticeable change after rubbing with a tissue soaked in the solvent.

[0110] As is clear from Table 1, the examples of the present invention exhibited excellent bond strength and lap shear strength to various types of substrates, while the comparative examples failed to achieve good adhesive performance in bonding plastics. Preferred aspects of the present invention include the following. [1] A polyfunctional acetoacetate compound, polyoxypropylene polyamines, and Polyoxyalkylene having at least two oxyalkylene units selected from polyamineoxypropylene units, oxyethylene units, and oxytetramethylene units. 1. A curable adhesive composition comprising: [2] The curable adhesive composition according to [1], wherein the polyfunctional acetoacetate compound has at least two acetoacetoxy groups, preferably 2 to 10 acetoacetoxy groups, and more preferably 3 to 4 acetoacetoxy groups. [3] The curable adhesive composition according to [1] or [2], wherein the polyfunctional acetoacetate compound is an acetoacetylated polyol obtained from glycerol, trimethylolpropane, ethanol isosorbide, neopentyl glycol, pentaerythritol, dimethylolpropane, dipentaerythritol, a propoxylated monosaccharide, trimethylolethane, or a combination thereof. [4] The curable adhesive composition according to any one of [1] to [3], wherein the polyoxypropylene polyamine is selected from polyoxypropylene diamine, polyoxypropylene triamine, and a combination thereof. [5] Polyoxypropylenediamine is represented by the formula (1) TIFF0007824888000009.tif2463 (1) [wherein x is 2 to 100, preferably 2 to 80] The curable adhesive composition according to [4], [6] Polyoxypropylene triamine is represented by the formula (2) TIFF0007824888000010.tif41103 (2) [In the formula, n is 0 to 6; w, y, and z each independently represent 1 to 100, more preferably 1 to 80; the sum of w, y, and z is 3 to 100, more preferably 5 to 85; and R 1 is hydrogen or straight or branched C 1 ~C 16 is an alkyl group, preferably hydrogen or a straight or branched C 1 ~C 8 alkyl group] The curable adhesive composition according to [4], [7] The curable adhesive composition according to any one of [1] to [6], wherein the polyoxyalkylene polyamine has an oxypropylene unit and an oxyethylene unit and preferably has a weight average molecular weight of 100 to 5,000, particularly 200 to 3,000. [8] The curable adhesive composition according to any one of [1] to [7], wherein the polyoxyalkylene polyamine has an oxypropylene unit and an oxytetramethylene unit and preferably has a weight average molecular weight of 100 to 5,000, particularly 200 to 3,000. [9] Formula (3): R 2 R 3 NH (3) [In the formula, R 2 is hydrogen or C 1 -C 6 is an alkyl group; and R 3 is a hydrocarbyl group having up to 36 carbon atoms, including aromatic groups, which hydrocarbyl group may be one or more -NHR 2 and optionally substituted by one or more O atoms and / or one or more —N(R 4 )-group(R 4 is a hydrogen atom); or R 3 is C 1 -C 36 an aliphatic group and one or more NHR 2 groups, and optionally further substituted with one or more O atoms and / or one or more N(R 4 )-group(R 4 is a hydrogen atom); and R 2 and R 3 may form a ring together with the N atom to which they are attached. The curable adhesive composition according to any one of [1] to [8], further comprising at least one amine curing accelerator according to the formula:

[10] The curable adhesive composition according to any one of [1] to [9], wherein the molar equivalent ratio of acetoacetate to amine in the curable adhesive composition is in the range of 2:1 to 1:2, preferably in the range of 1.2:1 to 0.8:1, and more preferably 1:1.

[11] The curable adhesive composition according to any one of [1] to

[10] , optionally containing one or more additives selected from pigments, fillers, plasticizers, leveling agents, foam inhibitors, rheology control agents, catalysts, antioxidants, tackifiers, adhesion promoters, flame retardants, UV stabilizers, and combinations thereof.

[12] The curable adhesive composition according to any one of [1] to

[11] , wherein the curable adhesive composition does not contain a catalyst.

[13] A first liquid containing a polyfunctional acetoacetate compound, and A second liquid containing polyoxypropylene polyamine and polyoxyalkylene having oxyalkylene units selected from at least two of polyamine oxypropylene units, oxyethylene units, and oxytetramethylene units. A two-part curable adhesive composition comprising:

[14] A cured product of the curable adhesive composition according to any one of [1] to

[12] or the two-component curable adhesive composition according to

[13] .

[15] Use of the curable adhesive composition according to any one of [1] to

[12] or the two-component curable adhesive composition according to

[13] in bonding substrates made of paper, fabric, leather, metal, ceramics, porcelain, glass, wood, or plastic, or having a surface thereof.

Claims

1. polyfunctional acetoacetate compounds, polyoxypropylene polyamines, and Polyoxyalkylene polyamine having oxyalkylene units selected from at least two of oxypropylene units, oxyethylene units, and oxytetramethylene units. wherein the multifunctional acetoacetate compound is an acetoacetylated polyol derived from glycerol, trimethylolpropane, ethanol isosorbide, neopentyl glycol, pentaerythritol, dimethylolpropane, dipentaerythritol, a propoxylated monosaccharide, trimethylolethane, or a combination thereof.

2. The curable adhesive composition of claim 1 , wherein the multifunctional acetoacetate compound has at least two acetoacetoxy groups.

3. The curable adhesive composition of claim 1, wherein the polyfunctional acetoacetate compound has 2 to 10 acetoacetoxy groups.

4. The curable adhesive composition according to any one of claims 1 to 3, wherein the polyoxypropylene polyamine is selected from polyoxypropylene diamine, polyoxypropylene triamine, and combinations thereof.

5. Polyoxypropylenediamine is represented by the formula (1) （１） wherein x is 2 to 100. The curable adhesive composition according to claim 4, wherein

6. Polyoxypropylene triamine is represented by the formula (2): （２） wherein n is 0 to 6, w, y, and z are each independently 1 to 100, the sum of w, y, and z is 3 to 100, and R 1 is hydrogen or a straight-chain or branched C １ ~C １６ alkyl group] The curable adhesive composition according to claim 4, wherein

7. 7. The curable adhesive composition according to claim 1, wherein the polyoxyalkylene polyamine has an oxypropylene unit and an oxyethylene unit and has a weight average molecular weight of 100 to 5,000.

8. 8. The curable adhesive composition according to claim 1, wherein the polyoxyalkylene polyamine has an oxypropylene unit and an oxytetramethylene unit and has a weight average molecular weight of 100 to 5,000.

9. Formula (3): R ２ R ３ NH (3) [In the formula, R ２ is hydrogen or C １ -C ６ is an alkyl group; and R ３ is a hydrocarbyl group having up to 36 carbon atoms, including aromatic groups, which hydrocarbyl group is ２ groups, and may further comprise one or more O atoms and / or one or more —N(R ４ )-group (R ４ is a hydrogen atom); or R ３ is C １ -C ３６ an aliphatic group, and one or more NHR ２ groups, and optionally further substituted with one or more O atoms and / or one or more N(R ４ )-group (R ４ is a hydrogen atom); and R ２ and R ３ may form a ring together with the N atom to which they are attached.

9. The curable adhesive composition of claim 1, further comprising at least one amine cure accelerator according to

10. 10. The curable adhesive composition of claim 1, wherein the molar equivalent ratio of acetoacetate to amine in the curable adhesive composition ranges from 2:1 to 1:

2.

11. 11. The curable adhesive composition of any of claims 1 to 10, optionally comprising one or more additives selected from pigments, fillers, plasticizers, leveling agents, foam inhibitors, rheology control agents, catalysts, antioxidants, tackifiers, adhesion promoters, flame retardants, UV stabilizers, and combinations thereof.

12. The curable adhesive composition of any one of claims 1 to 11, wherein the curable adhesive composition does not contain a catalyst.

13. a first part comprising a polyfunctional acetoacetate compound; and A second liquid containing a polyoxypropylene polyamine and a polyoxyalkylene polyamine having oxyalkylene units selected from at least two of an oxypropylene unit, an oxyethylene unit, and an oxytetramethylene unit. wherein the multifunctional acetoacetate compound is an acetoacetylated polyol derived from glycerol, trimethylolpropane, ethanol isosorbide, neopentyl glycol, pentaerythritol, dimethylolpropane, dipentaerythritol, a propoxylated monosaccharide, trimethylolethane, or a combination thereof.

14. A cured product of the curable adhesive composition according to any one of claims 1 to 12 or the two-component curable adhesive composition according to claim 13.

15. Use of the curable adhesive composition according to any one of claims 1 to 12 or the two-component curable adhesive composition according to claim 13 in bonding substrates made of paper, fabric, leather, metal, ceramic, porcelain, glass, wood, or plastic, or having a surface thereof.

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