Curable adhesive compositions for multi-purpose bonding applications

Abstract

The present invention relates to a curable adhesive composition based on an acetoacetate compound and to its use in multi-purpose adhesive applications. In particular, the present invention relates to a curable adhesive composition based on a multifunctional acetoacetate compound and a polyoxyalkylene polyamine.

Description

[0001] The present invention relates to a curable adhesive composition based on an acetoacetate compound and to its use in multi-purpose adhesive applications. In particular, the present invention relates to a curable adhesive composition based on a multifunctional acetoacetate compound and a polyoxyalkylene polyamine.

[0002] Multipurpose adhesives, also called general-purpose adhesives, are used to bond many substrates encountered in industrial manufacturing or domestic use, such as 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. Such adhesives are expected to produce adequate adhesion on these diverse substrates, which have chemically and physically different surface structures and are often subjected to special surface treatments prior to bonding.

[0003] Compared to the vast variety of adhesives used in industry and the workplace, only a few substances meet the stringent requirements for versatility as multi-purpose adhesives. Among these substances, polyvinyl acetate and its copolymers are widely used.

[0004] Demand or versatility is a very difficult selection criterion for adhesive compositions. Ultimately, adhesive compositions must exhibit equally high affinity for polar and nonpolar surfaces. Therefore, stating that a substance is suitable for use in adhesives does not indicate to the expert whether it is also suitable for use in general-purpose adhesive compositions. Consequently, numerous efforts have been made to address this need.

[0005] For example, US Pat. No. 6,602,958 B2 discloses a two-component, room-temperature curing methacrylate-based adhesive for bonding a variety of materials, including thermosets, thermoplastics, metals, wood, ceramics, and combinations thereof. This reportedly significantly improves the adhesive's ability to bond certain difficult-to-bond composite materials with minimal surface preparation.

[0006] DE 102009045197 A1 discloses an aqueous adhesive suitable for use as a multi-purpose 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, wherein at least one component is capable of forming a salt by releasing protons in water.

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

[0008] It is therefore an object of the present invention to provide an alternative adhesive composition for multi-purpose bonding applications having a safer toxicological profile.

[0009] This object is achieved by a curable adhesive composition comprising a polyfunctional acetoacetate compound and at least two polyoxyalkylene polyamines, which has a fixture time of not more than 5 minutes and has excellent adhesive properties in bonding substrates made of various materials such as metal, wood, plastic, etc.

[0010] In one aspect, the present invention relates to a curable adhesive composition comprising:

[0011] Multifunctional acetoacetate compounds,

[0012] Polyoxypropylene polyamine, and

[0013] A polyoxyalkylene polyamine having at least two oxyalkylene units selected from the group consisting of oxypropylene units, oxyethylene units, and oxytetramethylene units.

[0014] In another aspect, the present invention relates to a two-component curable adhesive composition comprising a first component and a second component, wherein the first component comprises a polyfunctional acetoacetate compound and the second component comprises a polyoxypropylene polyamine and a polyoxyalkylene polyamine having at least two oxyalkylene units selected from oxypropylene units, oxyethylene units and oxytetramethylene units.

[0015] In a further aspect, the present invention relates to the use of the curable adhesive composition or the two-component curable adhesive composition for bonding substrates made of paper, textile, leather, metal, porcelain, pottery, glass, wood or plastic or substrates having a surface of paper, textile, leather, metal, porcelain, pottery, glass, wood or plastic.

[0016] Further preferred embodiments of the invention are set forth in the claims.

[0017] In this specification, the terms "a", "an" and "at least one" are the same as the term "one or more" and can be used interchangeably.

[0018] As used herein, "one or more" refers to at least one, and includes 1, 2, 3, 4, 5, 6, 7, 8, 9 or more, of the referenced substances. Similarly, "at least one" means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. As used herein with respect to any component, "at least one" refers to the number of chemically distinct molecules, i.e., the number of different types of the referenced substances, but not the total number of molecules.

[0019] If not otherwise specified, the molecular weight of a polymer or its components herein refers to the number-average molecular weight M. n . Number average molecular weight M n The determination can be made by gel permeation chromatography using THF as the eluent. If not stated otherwise, all given molecular weights are determined by end group analysis. w It can be determined by GPC, such as n described.

[0020] If not expressly stated otherwise, all percentages given herein with respect to compositions or preparations refer to % by weight relative to the total weight of the respective composition or preparation.

[0021] According to the present invention, a curable adhesive composition comprises a multifunctional acetoacetate compound, a polyoxypropylene polyamine, and a polyoxyalkylene polyamine having at least two oxyalkylene units selected from oxypropylene units, oxyethylene units, and oxytetramethylene units. The inventors surprisingly discovered that the curable adhesive composition is suitable for bonding various types of substrates, such as paper, fabric, leather, metal, porcelain, pottery, glass, wood, or plastic.

[0022] Compared to formulations based on standard epoxy resins or (meth)acrylates, the curable adhesive compositions developed have excellent adhesive properties for multi-purpose bonding and a mild toxicological profile. Based on acetylacetonate resins cured with polyetheramine hardeners, a formulation with a settling time of no longer than 5 minutes has been developed that can be applied from, for example, a two-component cartridge and cured to a tough polymer. It has been found to have strong adhesion and cohesion for bonding metals, various plastics, and wood. The rheological behavior and mixing ratio can be adjusted by fillers, and by introducing filler particles into the formulation, an increase in mechanical resistance has been observed.

[0023] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of not less than 10 MPa when bonded to a steel substrate.

[0024] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of not less than 10 MPa when bonded to aluminum substrates.

[0025] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of not less than 7 MPa when bonded to a wood substrate.

[0026] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of not less than 5 MPa when bonding a polycarbonate (PC) substrate.

[0027] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of not less than 3 MPa when bonding a polyvinyl chloride (PVC) substrate.

[0028] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of not less than 4 MPa when bonding a poly(methyl methacrylate) (PMMA) substrate.

[0029] The curable adhesive composition is formulated to provide a cured product having a lap shear strength of not less than 3 MPa when bonded to an acrylonitrile-butadiene-styrene (ABS) substrate.

[0030] In addition, the curable adhesive composition also has other advantages. For example, the adhesive composition is solvent-free, catalyst-free, has a processable viscosity and pot life, and is also fast-curing even at room temperature. Finally, the curable adhesive composition provides a strong adhesive property that is resistant to moisture and chemicals such as acetone, ethyl acetate, 2-propyl alcohol, methyl ethyl ketone, ethanol, and toluene.

[0031] According to the present invention, the multifunctional acetoacetate compound may have at least two acetoacetoxy groups, preferably 2 to 10 acetoacetoxy groups, more preferably 2 to 4 acetoacetate groups. Thus, the 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 of the compounds should ideally have a number average molecular weight (M) of less than 12,000 g / mol, for example less than 10,000 g / mol or less than 6,000 g / mol. n ).

[0032] In a preferred embodiment, the curable adhesive composition comprises at least one acetoacetylated polyol obtainable according to the following formula (Reaction 1):

[0033]

[0034] Where: R is C1-C 12 alkyl;

[0035] L represents the main chain structure of the polyol; and

[0036] q≥2.

[0037] The above reaction 1 can be described as a transesterification reaction, or more specifically, a transacetylation reaction, of a polyol with an acetoacetate compound as defined by the following formula (I):

[0038]

[0039] Where R is the C1-C 12 Alkyl group. More typically, the alkyl group R has 1 to 8, preferably 1 to 6, carbon atoms. Exemplary alkyl acetoacetates include: tert-butyl acetoacetate, isobutyl acetoacetate, n-butyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, ethyl acetoacetate, and methyl acetoacetate. Tert-butyl acetoacetate is preferred.

[0040] The polyol of the above reaction 1 is represented by the following formula (II):

[0041] L-(OH) q Formula (II)

[0042] Wherein q≥2, and L represents the main chain structure. Such polyol (II) may optionally contain heteroatoms in its main chain or pendant side chains. In addition, polyol (II) may be a monomeric polyol, or may have an oligomeric or polymeric main chain. Regardless of this, it is preferred that the number average molecular weight (M) of polyol (II) is n ) is less than 12000 g / mol; and its hydroxyl functionality q is 2 to 10, preferably 2 to 4.

[0043] In one embodiment, the curable adhesive composition comprises an acetoacetylated polyol obtained from a monomeric polyol. Examples of suitable monomeric polyols 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; alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol , pentylene glycol, hexamethylene glycol, hexylene glycol and neopentyl glycol; glycerol; castor oil; castor wax; sugars such as glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose and erythrose; sugar alcohols such as erythritol, xylitol, maltitol, mannitol and sorbitol; and hydroxyalkylated aliphatic diamines such as o,o'-bis(diethanolaminomethyl)-p-nonylphenol, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (Quadrol L, from BASF) and N,N,N,N-tetrakis(2-hydroxyethyl)ethylenediamine. In a preferred embodiment, the multifunctional acetoacetate compound is an acetoacetylated polyol obtained from glycerol, trimethylolpropane, ethanol isosorbide, neopentyl glycol, pentaerythritol, dimethylolpropane, dipentaerythritol, propoxylated monosaccharides, trimethylolethane, and combinations thereof.

[0044] The present invention also does not exclude that such multifunctional acetoacetate compounds comprise acetoacetylated polyols obtained from oligomeric or polymeric polyols. In particular, polyol (II) may 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. Ideally, such oligomeric or polymeric polyols should be characterized by a number average molecular weight (M) of 1.5 wt %. n ) is at most 10000 g / mol, preferably 250 to 6000 g / mol. In addition, it is particularly interesting to use one or more polyether polyols or polyester polyols as starting materials. A commercial example of a polyether polyol is Voranol CP260 (available from DowDuPont).

[0045] As known in the art, polyester polyol can be prepared by polycarboxylic acid or acid anhydride and stoichiometric excess polyol generation condensation reaction, or by the mixture preparation of polycarboxylic acid, monocarboxylic acid and polyvalent alcohol.Suitable polycarboxylic acid and acid anhydride for the preparation of polyester polyol include those with 2 to 18 carbon atoms, particularly those with 2 to 10 carbon atoms.The limiting examples of this type of polycarboxylic acid and acid anhydride 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. Monocarboxylic acids that can be used include those having 1 to 18 carbon atoms, or preferably 1 to 10 carbon atoms, of which the following examples can be mentioned: 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 polyols have 2 to 18 carbon atoms, ideally 2 to 10 carbon atoms. Exemplary polyols include, but are not limited to, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, glycerol, neopentyl glycol, pentaerythritol, butanediol, 2-methyl-1,3-propanediol, hexylene glycol, and combinations thereof.

[0046] Polyether polyols can be prepared by methods known in the art, for example, by reacting olefin oxides with polybasic initiator molecules in the presence of a suitable catalyst such as an alkali metal hydroxide, an alkali metal alkoxide, or antimony pentachloride. Examples of olefin oxides include tetrahydrofuran, ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and styrene oxide. Examples of suitable initiator molecules include, but are not limited to, water, ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol, 1,4-butylene glycol, diethylene glycol, and trimethylolpropane. Preferred polyether polyols for use herein are poly(propylene oxide) polyols, poly(ethylene oxide) polyols, PTMEG, and mixtures thereof.

[0047] The polycarbonate polyols used herein may be selected from, but are not limited to, polycarbonate diols. Such polycarbonate diols may be prepared by reacting a diol with a dialkyl carbonate or a diaryl carbonate or phosgene. The reactant diol may be selected from, but is not limited to, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, trioxyethylene glycol, and mixtures thereof. An exemplary diaryl carbonate is diphenyl carbonate.

[0048] The transesterification (transacetylation) reaction 1 can be carried out by conventional methods known in the art of polymer chemistry. In this regard, particular mention may be made of: 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-butylacetoacetate: Synthetic Applications", J. Org. Chemistry 1991, 56, 1713-1718. Typically, the reaction between an oligomeric or polymeric polyol and an acetoacetate will comprise mixing the polyol and the acetoacetate in a suitable vessel with or without a solvent at an elevated temperature, for example, from 50° C. to 200° C. or from 80° C. to 150° C.; preferably, the reaction is carried out in the absence of a solvent. The reaction is driven to completion by distilling off the alcohol (R—OH) formed under reduced pressure. Furthermore, the reaction may 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.

[0049] Although the product of the above-mentioned transacetyl reaction can be directly used in the multi-purpose adhesive composition of the present invention, the reaction product can also be first isolated and purified using methods known in the art. In this regard, extraction, evaporation, distillation and chromatography can serve as suitable techniques.

[0050] According to the present invention, the curable adhesive composition further comprises polyoxypropylene polyamine. Polyoxypropylene polyamine refers to a polyamine having only oxypropylene units in the main chain structure.

[0051] In a preferred embodiment, the polyoxypropylene polyamine is selected from the group consisting of polyoxypropylene diamine, polyoxypropylene triamine, and combinations thereof.

[0052] Examples of polyoxypropylenediamines are those represented by formula (1),

[0053]

[0054] wherein x is 2 to 100, preferably 2 to 80.

[0055] Preferably, the number average molecular weight of the polyoxypropylenediamine is 100 to 5,000, more preferably 200 to 4,000.

[0056] Such polyoxypropylene diamines are commercially available from Huntsmann as the Jeffamine D series polyether polyamines, for example, D-230, D-400, D-2000, and D-4000.

[0057] Examples of polyoxypropylene triamines are those represented by formula (2),

[0058]

[0059] wherein 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, R1 is hydrogen or a linear or branched C1-C 16 An alkyl group, and preferably hydrogen or a linear or branched C1-C8 alkyl group.

[0060] Preferably, the number average molecular weight of the polyoxypropylenetriamine is 100 to 8,000, more preferably 200 to 6,000.

[0061] Such polyoxypropylene triamines are commercially available from Huntsmann as the Jeffamine T series polyether polyamines (eg, T-403, T-3000, and T-5000).

[0062] According to the present invention, the curable adhesive composition also comprises a polyoxyalkylene polyamine having at least two oxyalkylene units selected from the group consisting of oxypropylene units, oxyethylene units and oxytetramethylene units.

[0063] In one embodiment, the polyoxyalkylene polyamine has oxypropylene units and oxyethylene units in the main chain structure. Such polyoxyalkylene polyamine can be represented by formula (3)

[0064]

[0065] wherein 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.

[0066] Preferably, the number average molecular weight of such polyoxyalkylene polyamine having propylene oxide units and ethylene oxide units is from 100 to 5,000, more preferably from 200 to 3,000.

[0067] Such polyether polyamines are commercially available from Huntsmann as the Jeffamine ED series of polyether polyamines, for example, ED-600, ED-900, and ED-2003.

[0068] In another embodiment, the polyoxyalkylene polyamine has oxypropylene units and oxytetramethylene units in the backbone structure.

[0069] Preferably, the number average molecular weight of such polyoxyalkylene polyamine having oxypropylene units and oxytetramethylene units is from 100 to 3,000, more preferably from 200 to 2,000.

[0070] Such polyether polyamines are commercially available from Huntsmann as the Jeffamine THF series of polyether polyamines, for example, THF-100, THF-140, and THF-170.

[0071] Optionally, the curable adhesive composition comprises at least one amine curing accelerator having 1 to 10, for example 2 to 6 or 2 to 4, primary and / or secondary amino groups according to the following formula (III):

[0072] R 2 R 3 NH Formula (III)

[0073] Where: R 2 is hydrogen or a C1-C6 alkyl group; and

[0074] R 3 is a hydrocarbon group having up to 36 carbon atoms containing an aromatic group, the hydrocarbon group being optionally substituted by one or more -NHR 2 and optionally substituted by one or more O atoms and / or by one or more -N(R 4 )-group interruption, where R 4 is a hydrogen atom, or

[0075] R 3 C1-C 36 An aliphatic group, optionally substituted with one or more -NHR 2 and optionally substituted by one or more O atoms and / or by one or more -N(R 4 )-group interruption, where R 4 is a hydrogen atom; and

[0076] R 2 and R 3 Together with the nitrogen atom to which they are bonded, they may form a ring.

[0077] For the sake of completeness, when R 2 and R 3 Where rings are formed, it is recognized that such rings may be heterocyclic and may contain one or more nitrogen atoms.

[0078] Good results were also obtained where the reactant amine according to formula (III) is characterized by: R 2 is hydrogen; and R 3 It is C1-C 36 Alkyl groups, preferably C1-C12 Alkyl groups, which are optionally substituted with at least one -NHR 2 and optionally substituted with one or more -N(R 4 )-group interruption, where R 4 is a hydrogen atom. Exemplary primary diamines 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-propylenediamine, N-cyclohexyl-1,3-propylenediamine, 4-(aminomethyl)piperidine, 3-(aminomethyl)piperidine, 2-(aminomethyl)piperidine, and 4-aminopiperidine.

[0079] Other exemplary commercial amines for use in the present invention include, but are not limited to, 2-methyl-1,5-diaminopentane available under the trade name Dytek A from Invista Arpadis; 1,2-diaminocyclohexane as a mixture of isomers available under the trade name Dytek DCH-99 from Invista Arpadis; N,N'-dimethylhexanediamine (MAHMA) available from Sigma-Aldrich; dimerized fatty acid-based diamines available from Croda under the trade names Priamine 1071, 1073, 1074, and 1075; phenalkamines available from Cardolite Corporation under the trade names Cardolite NX-5608, NX-5607, and LITE 3060; polyethyleneimine (PEI) available from BASF under the trade names Lupasol G 20 (anhydrous) and Lupasol FG; and isophorone diamine available from Sigma-Aldrich.

[0080] Other exemplary amines suitable for use in the compositions of the present invention include piperidine and pyrollidine.

[0081] In some cases, the amine curing accelerator may advantageously comprise a primary amine according to formula (III) characterized in that R 2 is hydrogen, and R 3 C1-C 12 Alkyl groups, preferably C1-C6 alkyl groups. Exemplary amines of this type include: n-butylamine, n-hexylamine, n-octylamine, n-decylamine, and n-dodecylamine.

[0082] In a preferred embodiment, the amine curing accelerator is an alicyclic amine, preferably selected from isophorone diamine, menthane diamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-methylenedicyclohexylamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and combinations thereof.

[0083] If present, the molar equivalent ratio of amine groups in the amine curing accelerator to amine groups in the polyether polyamine is from 1:10 to 10:1, preferably from 1:5 to 5:1, and more preferably from 1:3 to 3:1.

[0084] It should be noted that the compositions of the present invention may contain a large excess of amine or the acetoacetate from the polyether polyol and amine curing accelerator (if present). Such compositions may, for example, be broadly characterized by 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 is typically selected such that the molar equivalent ratio of acetoacetate to amine may be from 2:1 to 1:2, e.g., from 1.2:1 to 0.8:1. Thus, while it is preferred that one mole of amine be available for each equivalent of acetoacetate in the composition, variations from this preferred 1:1 equivalent ratio are permissible.

[0085] An advantage of the chemistry of the curable compositions of the present invention is that the cure rate can be adjusted to control the rate of development of mechanical properties of the cured material on various types of substrates. For example, a rapid cure reaction and the accompanying rapid development of those mechanical properties can be advantageous in multi-purpose adhesive applications.

[0086] In order to form the multi-purpose curable adhesive composition, the reactive components are put together and mixed in a manner that induces their hardening. More specifically, these components can be mixed in predetermined amounts by hand, by machine, by (co)extrusion or by any other means that can ensure their fine and highly uniform mixing. During initial mixing - "initial" in this article means at most 1 minute after the components are combined - the curable adhesive composition is liquid or paste at room temperature. However, this fact does not exclude that the mixing temperature is higher than room temperature, for example, up to 15 ° C higher than room temperature.

[0087] Of course, the curable adhesive composition may contain auxiliary ingredients and additives. However, the adhesive composition should generally be formulated to exhibit an initial viscosity suitable for a paste or liquid material. In the case of an adhesive composition that does not contain fillers, it 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. In the case of an adhesive composition that contains fillers, it is less than 2,000 mPa·s, preferably less than 1,000 mPa·s, and more preferably less than 500 mPa·s.

[0088] Independent of or in addition to the viscosity characteristics, the curable adhesive composition should be formulated to be free of bubble (foam) generation upon mixing and subsequent curing. In addition, the curable adhesive composition should also be formulated to exhibit at least one of the following characteristics, ideally at least two, and more ideally all of the following characteristics: i) a fixture strength after the composition has cured for 5 minutes; ii) a maximum exotherm temperature of no more than 120°C, preferably no more than 100°C, and more preferably no more than 80°C; and iii) a Shore A hardness of at least 50, preferably at least 60, and more preferably at least 70 after curing and storage for 7 days at room temperature and 50% relative humidity.

[0089] The compositions of the present invention may be solvent-free. Alternatively, the composition may comprise one or more solvents, at least one of which is preferably miscible with water. Thus, it is contemplated that the composition may be characterized by a solvent system comprised of two or more water-miscible solvents. Similarly, the composition may be characterized by a solvent system comprised of at least one water-immiscible solvent and at least one water-miscible solvent. For completeness, the term "immiscible" as used herein refers to the presence of two phases in a certain proportion.

[0090] 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, but are not limited to, 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, chloroform, xylene, and combinations thereof.

[0091] When used, the amount of solvent present in the composition can be determined based on normal practical considerations. However, generally, the volume to mass ratio of solvent to acetoacetate functionalized compound will be in the range of 1:1 to 100:1. In some embodiments, the volume to mass ratio of solvent to acetoacetate functionalized compound can be in the range of 1:1 to 50:1.

[0092] Of course, the compositions of the present invention may also contain 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 only limitation in selecting appropriate additives is that they must be compatible with the other components of the composition and do not interfere with the use of the composition in multi-purpose adhesive applications.

[0093] When using fillers, the amount of filler should be at most 75 wt %, for example at most 50 wt %, or at most 30 wt % based on the weight of the composition. Suitable for use as fillers in this article are, for example, chalk, lime powder, precipitated and / or pyrolytic silicic acid, zeolite, bentonite, magnesium carbonate, diatomaceous earth, aluminum oxide, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, aluminum trihydrate, magnesium hydroxide and other ground minerals. Organic fillers can also be used, particularly carbon black, graphite, rubber particles, wood fiber, wood powder, sawdust, cellulose, melamine, cotton, paper pulp, wood chips, chopped straw, husks, ground walnut shells and other chopped fibers. Short fibers, for example glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber or polyethylene fiber can also be added. Aluminum powder is equally suitable for use as filler.

[0094] In certain embodiments, a plasticizer may be included to adjust the softness and elasticity of the cured adhesive composition. In this case, one or more plasticizers may be selected from the following groups: vegetable oils; mineral oils; soybean oils; terpene resins; aromatic esters such as dioctyl phthalate, diundecyl phthalate, tricresyl phosphate, and triisononyl benzene trimellitate; linear esters such as ditridecyl adipate; chlorinated paraffins; aromatic and naphthenic process oils; alkyl naphthalenes; and low molecular weight polyisoprene, polybutadiene, monofunctional and long-chain amine-containing or polybutene resins. Typically, the amount of the plasticizer should be 0 to 20% by weight, preferably 0 to 10% by weight, or 0 to 5% by weight, based on the gross weight of the multi-purpose adhesive composition.

[0095] 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. Furthermore, when used, the amount of catalyst, as measured in the absence of any suitable carrier, should be from 0.001% to 5% by weight, preferably from 0.01% to 2% by weight, based on the total weight of the reactant amine used. However, it is highly preferred that the composition of the present invention be catalyst-free.

[0096] Organofunctional silanes, such as mercaptofunctional silanes, epoxyfunctional silanes, and in particular aminofunctional silanes, can preferably be used as adhesion promoters to improve adhesion to metals. Examples of mercaptofunctional silanes are 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, or their alkyldimethoxy or alkyldiethoxy analogs. Examples of aminofunctional silanes include 3-aminopropylalkoxysilane and 2'-aminoethyl-3-aminopropylalkoxysilane. Epoxyfunctional silanes can be selected from a large number of compounds.As examples, the following may be mentioned: 3-glycidoxymethyltrimethoxysilane, 3-glycidoxymethyltriethoxysilane, 3-glycidoxymethyltripropoxysilane, 3-glycidoxymethyltributoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltripropoxysilane, 2-glycidoxyethyltributoxysilane, 2-glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 1-glycidoxyethyltripropoxysilane, 1-glycidoxyethyltributoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 ...3-glycidoxyethyltriethoxysilane, 3-glycidoxyethyltrimethoxysilane, 3-glycidoxyethyltriethoxysilane, 3-glycidoxyethyltripropoxysilane, 3-glycidoxyethyltributoxysilane, 3-glycidoxyethyltrimethoxysilane, 3-glycidoxyethyltriethoxysilane, 3-glycidoxyethyltrimethoxysilane, 3-glycidoxyethyltriethoxysilane, 3-glycidoxyethyltripropoxysilane, 3-glycidoxyethyltributoxysilane, 3- -Glycidoxypropyl tripropoxysilane, 3-glycidoxypropyltributoxysilane, 2-glycidoxypropyl trimethoxysilane, 2-glycidoxypropyl triethoxysilane, 2-glycidoxypropyl tripropoxysilane, 2-glycidoxypropyl tributoxysilane, 1-glycidoxypropyl trimethoxysilane, 1-glycidoxypropyl triethoxysilane, 1-glycidoxypropyl tripropoxysilane, 1-glycidoxypropyl tributoxysilane, 3-glycidoxybutyl trimethoxysilane, 4-glycidoxybutyl triethoxysilane, 4-glycidoxybutyl tripropoxysilane, 4-glycidoxybutyl tributoxysilane, 4-glycidoxybutyl trimethoxysilane. Methoxysilane, 3-glycidoxybutyltriethoxysilane, 3-glycidoxybutyltripropoxysilane, 3-glycidoxybutyltributoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 4-glycidoxybutyltripropoxysilane, 1-glycidoxybutyltrimethoxysilane, 1-glycidoxybutyltriethoxysilane, 1-glycidoxybutyltripropoxysilane, 1-glycidoxybutyltributoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltripropoxysilane, (3,4-epoxycyclohexyl)methyl Tributyloxysilane, (3,4-epoxycyclohexyl)propyltrimethoxysilane, (3,4-epoxycyclohexyl)ethyltriethoxysilane, (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, (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, particularly preferably 0.5% to 2% by weight.

[0097] Flame retardants may be added to the adhesive composition according to the present invention to improve the properties of the cured product, especially when used for wood bonding. Examples of flame retardants are ammonium polyphosphate, triphenylphosphine oxide, triethylaluminum hypophosphite, zinc diethylphosphinate, 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), resorcinol bis(2,6-dixylylenylphosphate), aluminum hydroxide, aluminum hydroxide, dihydroxide The flame retardant is preferably used in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and particularly preferably 0.5 to 10% by weight in the composition.

[0098] In another aspect, the present invention relates to a two-component curable adhesive composition comprising a first component and a second component, wherein the first component comprises a polyfunctional acetoacetate compound and the second component comprises a polyoxypropylene polyamine and a polyoxyalkylene polyamine having at least two oxyalkylene units selected from oxypropylene units, oxyethylene units and oxytetramethylene units.

[0099] The ingredients of each component are stored separately from one another in containers (parts) until just before application, when the contents of all containers are mixed together to form a mixture of the adhesive composition. After application and curing, a solid material is formed in the bonded area.

[0100] Another embodiment of the present invention is a method for bonding substrates to each other using a curable adhesive composition of the present invention. In this embodiment, the curable composition is applied to a first substrate. As needed, the application method can be carried out by various means known to those of ordinary skill in the art (e.g., brushing, spraying, roller coating, gravure coating, flexographic coating (flexographic coating), flow coating, dip coating and combinations thereof) to form a continuous or discontinuous film of the composition. In some embodiments, the curable composition is applied at ambient temperature (about 25 ° C); or, the curable composition is applied at an elevated temperature.

[0101] After composition is applied on the first substrate, it can be contacted with another substrate, to form composite material.The composite material so formed is optionally subjected to applied pressure, for example, passed between two rollers, to strengthen the contact of substrate and composition. In another embodiment of the present invention, composition can be applied to the two surfaces of the first substrate simultaneously or sequentially, then said composition is bonded to two other substrates that can be identical or different simultaneously or sequentially. It is also envisioned that before or after technique as herein described, composite construction can be bonded to other substrates using composition of the present invention or different compositions. In the method of the present invention, the first substrate to be bonded and the second substrate can be identical or different, and comprise for example paper, fabric, leather, metal (for example, aluminum and steel), porcelain, pottery, glass, timber or plastics (for example, PP, PC, PVC etc.), it can have smooth or structured surface, and can provide with forms such as roll, sheet, film, foil.

[0102] In some embodiments of the present invention, the substrate is relatively thin and flat, and the resulting composite material is referred to as a laminate. The substrate can be constructed as a multilayer laminate based on polyalkylenes such as polyethylene and polypropylene, polyester and polyamide (nylon), metallized polypropylene, aluminum foil, etc. Examples of double-layer laminates include polypropylene / polypropylene, polyester / nylon, polyester / polyethylene, polypropylene / metallized polypropylene, polypropylene / aluminum foil, polyester / aluminum foil, polyamide / aluminum foil, etc.

[0103] It is envisioned that the curable adhesive composition of the present invention will undergo a chemical reaction referred to herein as "curing". Although the present invention is not limited to any particular theory, it is believed that curing begins when the curable composition is formed and continues at least until the end of the pot life, and may also continue after the end of the pot life. In some embodiments, a layer of the curable adhesive composition is applied to a substrate before the end of the pot life. In some of these embodiments, at least one additional substrate will contact the layer of the curable mixture; Typically, this additional substrate will contact this layer of curable adhesive composition before the end of the pot life. Therefore, in some embodiments, curing will not end until the curable adhesive composition contacts the substrate. It is envisioned that the cured product will form an effective adhesive bond between substrates.

[0104] Although the present invention is particularly used as adhesive, it is expected that it is also applicable to coatings, polymer foams, sealants and elastomers. When used as coating, curable adhesive composition will be applied on the base material, then solidify it, and there will not be other base material to contact with this curable mixture. When used as sealant, foam or elastomer, curable adhesive composition can for example be placed in a mould or on a demoulding surface, and solidify it; Then the solidified mixture can be removed from mould or demoulding surface, and used according to expectation.

[0105] Various features and embodiments of the invention are described in the following examples, which are intended to be representative and not limiting. Example

[0106] Material

[0107] Jeffamine D-230 is a polyoxypropylene diamine from Huntsmann having a number average molecular weight of about 230.

[0108] Jeffamine T-403 is a polyoxypropylene triamine from Huntsmann having a number average molecular weight of about 440.

[0109] Jeffamine ED-600 is a polyoxypropylene polyoxyethylene diamine from Huntsmann having a number average molecular weight of approximately 600.

[0110] Jeffamine ED-900 is a polyoxypropylene polyoxyethylene diamine from Huntsmann having a number average molecular weight of about 900.

[0111] Jeffamine THF100 is a polyoxypropylene polyoxytetramethylene diamine from Huntsmann having a number average molecular weight of approximately 1000.

[0112] Priamine 1071 is a dimerized fatty acid diamine from Croda.

[0113] Jeffamine EDR148 is a diamine from Huntsmann having the following structure.

[0114]

[0115] Dytek DCH-99 is 1,2-diaminocyclohexane from Invista Arpadis.

[0116] (3-Aminopropyl)trimethoxysilane is an adhesion promoter from Alfa Aesar.

[0117] Omya BLH is heavy calcium carbonate from Omya.

[0118] Aerosil R202 is a hydrophobic fumed silica from Evonik.

[0119] Test Method

[0120] Lap shear strength

[0121] Samples were made from two 25mm wide substrates with a 10mm overlap. The samples were fixed in place with a clamp and allowed to cure at room temperature for 2 days before testing. Tensile testing was performed using a Zwick / Roell Z050 at a speed of 10mm / min.

[0122] Fixture strength

[0123] The fixing strength was rated as "pass" if the sample did not separate under its own weight when the clamps of the lap shear sample were removed after 5 minutes of curing.

[0124] Solvent resistance

[0125] The bulk polymer of the two-part formulation was prepared by mixing all components and curing at room temperature for 7 days. Solvent resistance was tested by rubbing a paper towel soaked in different solvents back and forth across the surface of the cured bulk polymer multiple times. If no visible change in the polymer surface occurred, the solvent resistance was rated "pass."

[0126] Synthesis of Trimethylolpropane Triacetoacetate

[0127] The synthesis of trimethylolpropane triacetoacetate (AATMP) was carried out according to the literature process WO2019 / 120923A1 with slight modifications. Trimethylolpropane or pentaerythritol (1 equivalent) and TBAA (1.1 equivalent) were charged into a 500mL 3-neck round-bottom flask. A Y-type adapter, a mechanical stirring rod, and a reflux condenser were then installed in each neck of the flask. In the Y-type adapter, a thermocouple and a nitrogen connector were adjusted. The temperature was set to 140°C under a nitrogen atmosphere (refluxed for about 4 hours to reach 92°C). Thereafter, distillation was performed for 8 hours at atmospheric pressure while the temperature was slowly raised to 140°C. Finally, when the distillation stopped, distillation was performed for 2 hours at 140°C under a reduced pressure of 900 mbar to 400 mbar. The reaction scheme is shown below.

[0128]

[0129] Example 1

[0130] 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 high-speed mixing cup. 148.09 g of Omya BLH and 16.45 g of Aerosil R202 were then added to the mixing cup and mixed. Finally, 1 equivalent (128.80 g) of AATMP was added to the mixing cup and mixed. The mixture was then mixed in a high-speed mixer at 3500 rpm for 30 seconds to produce an adhesive composition.

[0131] Example 2

[0132] 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 high-speed mixing cup. 152.37 g of Omya BLH and 16.93 g of Aerosil R202 were then added to the mixing cup and mixed. Finally, 1 equivalent (128.80 g) of AATMP was added to the mixing cup and mixed. The mixture was then mixed in a high-speed mixer at 3500 rpm for 30 seconds to produce an adhesive composition.

[0133] Example 3

[0134] 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)trimethoxysilane were mixed in a PP high-speed mixing cup. 165.13 g of Omya BLH and 18.34 g of Aerosil R202 were then added to the mixing cup and mixed. Finally, 1 equivalent (128.80 g) of AATMP was added to the mixing cup and mixed. The mixture was then mixed in a high-speed mixer at 3500 rpm for 30 seconds to produce an adhesive composition.

[0135] Example 4

[0136] 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 high-speed mixing cup. 166.63 g of Omya BLH and 18.51 g of Aerosil R202 were then added to the mixing cup and mixed. Finally, 1 equivalent (128.80 g) of AATMP was added to the mixing cup and mixed. The mixture was then mixed in a high-speed mixer at 3500 rpm for 30 seconds to produce an adhesive composition.

[0137] Example 5

[0138] 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 high-speed mixing cup. 94.87 g of Omya BLH and 8.50 g of Aerosil R202 were then added to the mixing cup and mixed. Finally, 1 equivalent (128.80 g) of AATMP was added to the mixing cup and mixed. The mixture was then mixed in a high-speed mixer at 3500 rpm for 30 seconds to produce an adhesive composition.

[0139] Comparative Example 1

[0140] 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 high-speed mixing cup. 210.39 g of Omya BLH and 23.38 g of Aerosil R202 were then added to the mixing cup and mixed. Finally, 1 equivalent (128.80 g) of AATMP was added to the mixing cup and mixed. The mixture was then mixed in a high-speed mixer at 3500 rpm for 30 seconds to produce an adhesive composition.

[0141] Comparative Example 2

[0142] 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 high-speed mixing cup. 183.16 g of Omya BLH and 20.35 g of Aerosil R202 were then added to the mixing cup and mixed. Finally, 1 equivalent (128.80 g) of AATMP was added to the mixing cup and mixed. The mixture was then mixed in a high-speed mixer at 3500 rpm for 30 seconds to produce an adhesive composition.

[0143] The obtained adhesive composition was tested for its fixing strength and lap shear strength (LSS) on various types of substrates. The results are shown in Table 1.

[0144] Table 1. Test results

[0145]

[0146] In addition, the examples were tested for solvent resistance, and all of the examples of the present invention passed the test without showing significant changes after being rubbed with a solvent-soaked paper towel.

[0147] As apparent from Table 1, the examples of the present invention exhibited excellent fixing strength and lap shear strength on various types of substrates, while the comparative examples failed to achieve good bonding performance when bonding plastics.

Claims

1. A curable adhesive composition comprising: a polyfunctional acetoacetate compound having 3 to 4 acetoacetoxy groups, Polyoxypropylene polyamine, and A polyoxyalkylene polyamine having at least two oxyalkylene units selected from the group consisting of oxypropylene units, oxyethylene units, and oxytetramethylene units.

2. The curable adhesive composition according to claim 1, wherein The polyfunctional acetoacetate compound having 3 to 4 acetoacetoxy groups is an acetoacetylated polyol obtained from glycerol, trimethylolpropane, pentaerythritol or trimethylolethane.

3. The curable adhesive composition according to claim 1 or 2, wherein The polyoxypropylene polyamine is selected from polyoxypropylene diamine, polyoxypropylene triamine and a combination thereof.

4. The curable adhesive composition according to claim 3, wherein The polyoxypropylene diamine is represented by formula (1), where x is from 2 to 100.

5. The curable adhesive composition according to claim 4, wherein x is 2 to 80.

6. The curable adhesive composition according to claim 3, wherein The polyoxypropylene triamine is represented by formula (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, R1 is hydrogen or a linear or branched C1-C 16 Alkyl group.

7. The curable adhesive composition according to claim 6, wherein w, y and z are each independently 1 to 80.

8. The curable adhesive composition according to claim 6, wherein The sum of w, y and z is 5 to 85.

9. The curable adhesive composition according to claim 6, wherein R1 is hydrogen or a linear or branched C1-C8 alkyl group.

10. The curable adhesive composition according to claim 1 or 2, wherein The polyoxyalkylene polyamine has propylene oxide units and ethylene oxide units.

11. The curable adhesive composition according to claim 10, wherein The polyoxyalkylene polyamine has a weight average molecular weight of 100 to 5,000.

12. The curable adhesive composition according to claim 10, wherein The polyoxyalkylene polyamine has a weight average molecular weight of 200 to 3,000.

13. The curable adhesive composition according to claim 1 or 2, wherein The polyoxyalkylene polyamine has oxypropylene units and oxytetramethylene units.

14. The curable adhesive composition according to claim 13, wherein The polyoxyalkylene polyamine has a weight average molecular weight of 100 to 5,000.

15. The curable adhesive composition according to claim 13, wherein The polyoxyalkylene polyamine has a weight average molecular weight of 200 to 3,000.

16. The curable adhesive composition according to claim 1 or 2, further comprising at least one amine curing accelerator according to formula (3): R 2 R 3 NH(3) in: R 2 is hydrogen or a C1-C6 alkyl group; and R 3 is a hydrocarbon group having up to 36 carbon atoms containing an aromatic group, the hydrocarbon group being optionally substituted with one or more -NHR 2 and optionally substituted by one or more O atoms and / or by one or more -N(R 4 )-group interruption, where R 4 is a hydrogen atom, or R 3 It is C1-C 36 An aliphatic group, optionally substituted with one or more -NHR 2 and optionally substituted by one or more O atoms and / or by one or more -N(R 4 )-group interruption, where R 4 is a hydrogen atom; and R 2 and R 3 Together with the nitrogen atom to which they are bonded, they may form a ring.

17. The curable adhesive composition according to claim 1 or 2, wherein The molar equivalent ratio of acetoacetate to amine in the curable adhesive composition is 2:1 to 1:

2.

18. The curable adhesive composition according to claim 17, wherein The molar equivalent ratio of acetoacetate to amine in the curable adhesive composition is 1.2:1 to 0.8:

1.

19. The curable adhesive composition according to claim 17, wherein The molar equivalent ratio of acetoacetate to amine in the curable adhesive composition is 1:

1.

20. The curable adhesive composition of claim 1 or 2, optionally comprising one or more additives selected from the group consisting of pigments, fillers, plasticizers, leveling agents, foam inhibitors, rheology control agents, catalysts, antioxidants, tackifiers, adhesion promoters, flame retardants, UV stabilizers, and combinations thereof.

21. The curable adhesive composition according to claim 1 or 2, wherein The curable adhesive composition is catalyst-free.

22. A two-component curable adhesive composition comprising: a first component comprising a polyfunctional acetoacetate compound having 3 to 4 acetoacetoxy groups; and The second component comprises a polyoxypropylene polyamine and a polyoxyalkylene polyamine having at least two oxyalkylene units selected from the group consisting of oxypropylene units, oxyethylene units, and oxytetramethylene units.

23. A cured product of the curable adhesive composition according to any one of claims 1 to 21 or a cured product of the two-component curable adhesive composition according to claim 22.

24. Use of the curable adhesive composition according to any one of claims 1 to 21 or the two-component curable adhesive composition according to claim 22 for bonding substrates made of paper, textile, leather, metal, porcelain, pottery, glass, wood or plastic or substrates having a surface of paper, textile, leather, metal, porcelain, pottery, glass, wood or plastic.

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