Reactive composition comprising acetoacetate and (meth) acrylate

Abstract

The present invention relates to reactive adhesive compositions based on acetoacetate compounds and to the use thereof in structural adhesive applications. In particular, the reactive composition comprises (a) a polyfunctional acetoacetate compound, (b) a polyfunctional urethane (meth) acrylate oligomer, (c) a catalyst, and (d) a filler wherein the filler is present in an amount of from 20 wt% to less than 75 wt% of the total weight of the reactive composition.

Description

Technical Field

[0001] This invention relates to reactive compositions based on acetoacetate compounds and their use in structural bonding applications, such as direct glass glazing processes. In particular, this invention relates to reactive compositions based on acetoacetate compounds and urethane (meth)acrylate oligomers, said reactive compositions exhibiting excellent mechanical strength, including tensile strength and elongation. Background Technology

[0002] In the automotive industry, particularly in automobile production, a key application of adhesives is in the direct glass assembly of vehicle windshields. Paste-like, high-viscosity adhesives are used in these applications and are typically applied to body flanges or windshields in the automotive industry. Robots can optionally slightly heat the adhesive for easier application. The technical requirements for adhesives used to bond windshields in the automotive industry are constantly increasing. In the initial conception of automotive construction, this adhesive was specifically designed to bond the windshield to the body, preventing moisture and dust from entering the interior of the vehicle. Furthermore, the windshield should be crash-resistant, meaning that in the event of an accident, it should remain firmly bonded to the body and not detach. On the one hand, pedestrians should not be at risk of windshields flying everywhere; on the other hand, conventional airbags must be able to hold the windshield in place to minimize the risk of injury to vehicle occupants.

[0003] For many years, elastomeric adhesives have played a vital role in the direct glass assembly process for vehicle windshields. Due to their high elasticity, combined with excellent tensile and tear strength, a broad adhesive spectrum with and without a primer, and their favorable price / performance ratio, they are particularly well-suited for applications in the automotive industry. For example, one-component moisture-curing polyurethane adhesives are used to address the most diverse sealing and bonding problems where high tensile and tear strength is crucial. In their one-component moisture-curing embodiments, these compositions comprise an adhesive having free reactive isocyanate groups. In the absence of moisture, these systems are stable for long-term storage in a paste-like, sometimes very viscous, form; and when moisture from the ambient air approaches them after application and bonding of the parts to be bonded, the water reacts with the isocyanate groups in a known manner, ultimately resulting in a high-strength elastomeric bond between the parts through crosslinking. In two-component embodiments, one component comprises a similar adhesive having reactive isocyanate groups, and the second component comprises an adhesive having active hydrogen, typically in the form of polyols, polyamines, or water in a paste matrix or a water-contributing substance (e.g., water-loaded molecular sieves, inorganic or organic compounds containing water of crystallization, etc.). One-component or two-component adhesive systems without isocyanate groups have also been proposed for adhesive applications, and silane-modified polymers contain reactive silyl groups (e.g., alkoxysilanes, acetoxysilanes, silazanes, or oxime silanes) instead of reactive isocyanate groups.

[0004] However, although silane-modified polymers possess favorable toxicological properties, their limited mechanical properties restrict their use to lower-performance applications. On the other hand, polyurethane-based adhesives offer sufficient bonding strength, but the formulations contain harmful isocyanate components and require careful handling.

[0005] Compared to polyurethane chemistry, Michael addition chemistry is considered to offer an alternative sustainable approach because useful polymers can be prepared in the absence of isocyanates. Michael addition chemistry (e.g., based on reaction systems containing acetoacetate and (meth)acrylate) has been investigated and applied to several adhesive applications.

[0006] EP 3889222 A discloses a curable potting composition comprising: a polyfunctional acetoacetate compound, a (meth)acrylate compound having at least three (meth)acrylate groups, a catalyst, and a filler, wherein the equivalence ratio of the (meth)acrylate compound having at least three (meth)acrylate groups to the polyfunctional acetoacetate compound is greater than 1.5.

[0007] EP 1283235 B1 discloses an adhesive composition comprising: an α,β-unsaturated polycarboxylic acid ester; and a compound (A) which is an acetoacetate-terminated polyester or an acetoacetate-terminated polyesteramide.

[0008] However, the adhesives disclosed in the prior art have limited elasticity or flexibility, so the above adhesive compositions are not suitable for structural bonding applications such as direct glass assembly processes.

[0009] Therefore, the object of the present invention is to provide a reactive composition based on Michael addition chemistry, which is suitable for structural bonding such as direct glass assembly. Summary of the Invention

[0010] This objective is achieved through a reactive composition comprising a polyfunctional acetoacetate compound, a polyfunctional urethane (meth)acrylate oligomer, a catalyst, and fillers in selectable amounts. The cured product exhibits an excellent combination of tensile strength and elongation at break, and is therefore suitable for structural bonding such as direct glass assembly.

[0011] In one aspect, the present invention relates to reactive compositions, particularly reactive compositions for adhesives or sealants, comprising: (a) Polyfunctional acetoacetate compounds, (b) Polyfunctional urethane (meth)acrylate oligomers, (c) Catalyst, and (d) Packing material, The filler is present in an amount of 20% to less than 75% by weight of the total weight of the reactive composition.

[0012] In another aspect, the present invention relates to reactive compositions, wherein, based on the total weight of the reactive composition, the composition comprises: (a) 1% to 20% by weight of polyfunctional acetoacetate compounds, (b) 15% to 65% by weight of polyfunctional urethane (meth)acrylate oligomers, (c) 0.05% to 2% by weight of catalyst, and (d) 20% to less than 75% by weight, preferably 40% to 60% by weight of filler.

[0013] In another aspect, the present invention relates to a method of bonding a windshield in a vehicle, comprising applying the reactive composition or the two- or multi-part reactive composition to bond the windshield to a vehicle frame.

[0014] Other preferred embodiments of the invention are set forth in the claims. Detailed Implementation

[0015] In this specification, the terms “a,” “an,” “one,” “at least one,” and “at least one” are the same as the terms “one or more” or “one or more types” and may be used interchangeably.

[0016] The term "one or more" as used herein refers to at least one and includes 1, 2, 3, 4, 5, 6, 7, 8, 9 or more of the mentioned substances. Similarly, "at least one" means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. When used with respect to any component herein, "at least one" refers to the number of chemically distinct molecules, i.e., the number of mentioned substances of different types, not the total number of molecules.

[0017] If the molecular weight of a polymer or its components is mentioned in this document, the reference refers to the weight-average molecular weight M. w or number-average molecular weight M n Unless otherwise explicitly stated. Weight-average molecular weight M w The number-average molecular weight M can be determined by gel permeation chromatography using tetrahydrofuran as the eluent according to DIN 55672-1:2007-08. n The molecular weights can also be determined by gel permeation chromatography using tetrahydrofuran as the eluent according to DIN 55672-1:2007-08. Unless otherwise specified, all given molecular weights are those determined by analysis of terminal groups.

[0018] All percentages given in this document for compositions or formulations refer to weight % relative to the total weight of the respective composition or formulation, unless otherwise expressly stated.

[0019] According to the present invention, a reactive composition for use as an adhesive or sealant comprises: (a) Polyfunctional acetoacetate compounds, (b) Polyfunctional urethane (meth)acrylate oligomers, (c) Catalyst, and (d) Packing material, The filler is present in an amount of 20% to less than 75% by weight of the total weight of the reactive composition.

[0020] The inventors have surprisingly discovered that the reactive composition is suitable for use as an adhesive or sealant, especially for structural bonding (e.g., direct glass assembly processes).

[0021] Compared to standard polyurethane-based formulations, the developed reactive compositions exhibit superior adhesive properties for bonding and mild toxicological characteristics. Based on the designed formulations, an excellent combination of mechanical strengths in the cured products can be achieved.

[0022] Specifically, the reactive composition, when cured, exhibits a tensile strength of not less than 2 MPa, and preferably not less than 3 MPa, according to ASTM D638.

[0023] Furthermore, the reactive composition exhibits an elongation at break of not less than 100%, and preferably not less than 300%, according to ASTM D638 when cured.

[0024] Multifunctional acetoacetate compounds 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 acetoacetoxy groups. Therefore, 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 of the compounds is preferably characterized by a number-average molecular weight (Mg) of less than 12,000 g / mol, for example less than 10,000 g / mol or less than 6,000 g / mol. n ).

[0025] In a preferred embodiment, the reactive composition for the adhesive or sealant comprises at least one acetylated polyol, which can be obtained according to the following reaction formula (reaction 1): (1) Where: R is C1-C 12 alkyl; L represents the main chain structure of the polyol; and q ≥ 2.

[0026] Reaction 1 can be described as an transesterification (or more specifically, transacetylation) of a polyol with an acetoacetate compound as defined in formula (I): Formula (I) 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 acetoacetate esters include: tert-butyl acetoacetate; isobutyl acetoacetate; n-butyl acetoacetate; isopropyl acetoacetate; n-propyl acetoacetate; ethyl acetoacetate; and methyl acetoacetate. n-Butyl acetoacetate is preferred herein.

[0027] The polyol in reaction 1 above is represented by the following formula (II) in this paper: L-(OH) q Equation (II) Where q ≥ 2 and L represents the main chain structure. Such a polyol (II) may optionally contain heteroatoms in its main chain or in its pendentive side chains. Furthermore, the polyol (II) may be a monomeric polyol or may have an oligomeric or polymeric main chain. In any case, it is preferred that the polyol (II) has: a number-average molecular weight (Mn) of less than 12000 g / mol; and a hydroxyl functionality q of 2 to 10, preferably 2 to 4.

[0028] In one embodiment, the reactive composition according to the invention comprises an acetylated 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; butyl ethyl propylene glycol; 1,4-hexanediol; 1,4-cyclohexanediol; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolpropane; bis(trimethylolpropane); tricyclodecanediol; hydroquinone bis(2-hydroxyethyl) ether; alkylene glycols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentamethylethylene glycol, hexamethylene glycol. Glycols, hexanediol and neopentyl glycol; glycerol; castor oil; castor wax; sugars, such as glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose and erythritol; 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'-tetra(2-hydroxypropyl)ethylenediamine (Quadrol L, which is available from BASF) and N,N,N,N-tetra(2-hydroxyethyl)ethylenediamine. In a preferred embodiment, the polyfunctional acetoacetate compound is an acetylated polyol obtained from the following substances: ethylene glycol, glycerol, trimethylolpropane, isosorbide diethanolate, neopentyl glycol, pentaerythritol, dimethylolpropane, dipentaerythritol, propoxylated monosaccharide, trimethylolethane, and combinations thereof.

[0029] This invention also does not exclude the inclusion of acetylated polyols obtained from oligomerized or polymerized polyols in such polyfunctional acetoacetate compounds. In particular, the polyol (II) may be selected from: 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. Desiredly, such oligomerized or polymerized polyols should be characterized by a number-average molecular weight (Mn) of at most 10,000 g / mol and preferably 250 to 6,000 g / mol. Furthermore, the use of one or more polyether polyols or polyester polyols as starting materials is of particular interest. Moreover, a commercially available example of a polyether polyol is Voranol CP260 (available from DowDuPont).

[0030] As is known in the art, polyester polyols can be prepared by the condensation reaction of polycarboxylic acids or anhydrides with a stoichiometric excess of a polyol, or by a mixture of polycarboxylic acids, monocarboxylic acids, and polyols. Suitable polycarboxylic acids and anhydrides for the preparation of polyester polyols include those having 2 to 18 carbon atoms, and particularly those having 2 to 10 carbon atoms. Non-limiting examples of such polycarboxylic acids and anhydrides include: adipic acid; glutaric acid; succinic acid; malonic acid; pimelic acid; sebacic acid; octanoic 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, among which examples may be mentioned are: formic acid; acetic acid; propionic acid; butyric acid; valeric acid; hexanoic acid; octanoic acid; decanoic acid; lauric acid; myristic acid; palmitic acid; stearic acid; and combinations thereof. Suitable polyols have 2 to 18 carbon atoms, and preferably 2 to 10 carbon atoms. Exemplary polyols include, but are not limited to: ethylene glycol; propylene glycol; hexane-1,6-diol; trimethylolpropane; glycerol; neopentyl glycol; pentaerythritol; butanediol; 2-methyl-1,3-propanediol; hexanediol; and combinations thereof.

[0031] Polyether polyols can be prepared by methods known in the art, such as reacting alkene oxides with polyhydroxyl starting molecules in the presence of a suitable catalyst (e.g., alkali metal hydroxides, alkali metal alkoxides, or antimony pentachloride). Examples of alkene oxides include tetrahydrofuran; ethylene oxide; 1,2-epoxypropane; 1,2- and 2,3-epoxybutane; and styrene oxide. Examples of suitable starting 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 used herein are poly(propylene oxide) polyols; poly(ethylene oxide) polyols; PTMEG; and mixtures thereof.

[0032] The polycarbonate polyols used herein may be selected from, but are 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 may 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; trioxanediol; and mixtures thereof. An exemplary diaryl carbonate is diphenyl carbonate.

[0033] Transesterification (transacetylation) reaction 1 can be carried out using conventional methods known in the field of polymer chemistry. In particular, it is worth mentioning 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 oligomeric or polymeric polyols and acetoacetate involves mixing the polyol and acetoacetate in a suitable vessel, with or without a solvent, at elevated temperatures (e.g., 50°C to 200°C or 80°C to 150°C); preferably, the reaction is carried out in the absence of a solvent. The reaction is brought to completion by distilling off the alcohol (R-OH) formed under reduced pressure. Furthermore, 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."

[0034] While the products of the transacetylation reactions described above can be used directly in the reactive compositions of the present invention, such reaction products can also be separated and purified first using methods known in the art. Extraction, evaporation, distillation, and chromatography are suitable techniques in this regard.

[0035] Polyfunctional acetoacetate compounds are also commercially available. Examples include acetylated ethylene glycol from Arxada under the trade name AAEG-215.

[0036] According to the present invention, the polyfunctional acetoacetate compound can be used in an amount of 1% to 20% by weight, preferably 2% to 15% by weight, of the reactive composition.

[0037] Multifunctional carbamate (meth)acrylate oligomers According to the present invention, the reactive composition further comprises a polyfunctional urethane (meth)acrylate oligomer.

[0038] Multifunctional urethane (meth)acrylate oligomers can be selected from a variety of materials, with aliphatic urethane (meth)acrylate oligomers being preferred. Available urethane (meth)acrylate oligomers include difunctional or multifunctional urethane (meth)acrylate oligomers that are capable of crosslinking with multifunctional acetoacetate compounds during curing.

[0039] Available difunctional or polyfunctional urethane (meth)acrylate oligomers include aliphatic polyester urethane diacrylates. Such oligomers can generally be described as reaction products of polyester polyols and polyisocyanates. Other difunctional or polyfunctional urethane (meth)acrylate oligomers that can be used in this invention can be described as acrylate reaction products of aliphatic alcohols (e.g., polycarbonate polyols, polyether polyols, or ethylene glycol monoacrylates) and polyisocyanates.

[0040] Representative polyether polyols that can be used to prepare urethane (meth)acrylate oligomers include linear or branched alkylene oxides having 1 to 12 carbon atoms (C1-12) prepared by methods known in the art. Desiredly, the polyether polyol has an average molecular weight, determined by vapor pressure permeation (ASTM-D 3592), sufficient to give the urethane (meth)acrylate oligomer a molecular weight of not less than 3000 g / mol. Examples include, but are not limited to, polytetramethylene polyols, polymethylene oxide polyols, polyethylene oxide polyols, polypropylene oxide polyols, polybutane oxide polyols, tetrahydrofuran (THF)-symmetric-polyether polyols, and combinations thereof.

[0041] Representative hydrocarbon polyols used to prepare urethane (meth)acrylate oligomers also include linear or branched hydrocarbon polyols having a molecular weight sufficient to give the urethane (meth)acrylate oligomers a molecular weight of not less than 3000 g / mol. Non-limiting examples include: fully or partially hydrogenated polybutadiene polyols, polybutadiene polyols hydrogenated to an iodine value of 9 to 21, and fully or partially hydrogenated polyisobutylene polyols.

[0042] Representative polycarbonate polyols used to prepare urethane (meth)acrylate oligomers include, but are not limited to, reaction products of dialkyl carbonates and alkylene glycols, optionally copolymerized with alkylene ether glycols.

[0043] Polyisocyanates used to prepare urethane (meth)acrylate oligomers include aliphatic and aromatic polyisocyanates having 4 to 20 carbon atoms. Representative aliphatic examples include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decapethylene diisocyanate, 2,2,4-trimethyl-1,5-pentamethylene diisocyanate, 2,2'-dimethyl-1,5-pentamethylene diisocyanate, 3-methoxy-1,6-hexamethylene diisocyanate, 3-butoxy-1,6-hexamethylene,ω,ω'-dipropyl ether diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, and trimethylhexylmethylene diisocyanate. diisocyanate and their combinations.

[0044] Catalysts suitable for reacting aliphatic alcohols with polyisocyanates to form the urethane moiety of urethane (meth)acrylate oligomers include materials such as: dibutyltin dilaurate, dibutyltin dioxide, dibutyltin di-2-hexanoate, stannous oleate and stannous octoate, lead octoate, ferrous acetoacetate; and amines such as triethylamine, diethylmethylamine, triethylenediamine, dimethylethylamine, morpholine, N-ethylmorpholine, piperazine, N,N-dimethylbenzylamine, N,N-dimethyllauramine, and combinations thereof.

[0045] The resulting urethane oligomer is capped with a group containing (meth)acrylate to form a urethane (meth)acrylate oligomer. Suitable hydroxyl-capping monomers include, but are not limited to, hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc. Combinations of capping monomers may be used.

[0046] In one embodiment, the weight-average molecular weight of the polyfunctional urethane (meth)acrylate oligomer is from 500 g / mol to 50,000 g / mol, preferably from 1,000 g / mol to 10,000 g / mol, and more preferably from 1,500 g / mol to 8,000 g / mol.

[0047] Commercially available urethane (meth)acrylate oligomers include, for example, SARTOMER CN996, CN9001, CN981 and CN9002 (available from Sartamomer Company, Inc.).

[0048] According to the present invention, the polyfunctional urethane (meth)acrylate oligomer can be used in an amount of 15% to 65% by weight, preferably 35% to 65% by weight, of the reactive composition.

[0049] In the reactive compositions of the present invention, the relative ratio of the polyfunctional (meth)acrylate oligomer to the polyfunctional acetoacetate compound can be characterized by the ratio of the number of acetoacetoxy groups in the polyfunctional acetoacetate compound to the number of (meth)acrylate groups in the polyfunctional (meth)acrylate compound. The polyfunctional (meth)acrylate oligomer and the polyfunctional acetoacetate compound are blended together just before application, such that the equivalent ratio is 1:0.6 to 1:2.0, preferably 1:0.75 to 1:1.25, and more preferably about 1:1.

[0050] catalyst The reactive composition includes a catalyst to allow a Michael addition reaction to occur between a polyfunctional acetoacetate compound and a polyfunctional (meth)acrylate oligomer at a temperature, for example, from room temperature to 200°C, preferably at room temperature (25°C), to form an adhesive / sealant with a high crosslinking density.

[0051] Examples of suitable catalysts in this invention are particularly 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), triazabicyclodecene (TBD), tetramethylguanidine (TMG), trioctylphosphine (TOP), triphenylphosphine (TPP), (tetrabutylammonium hydroxide) TBAOH, NaOH, KOH, NaOEt, KOEt, and phosphorazine.

[0052] The amount of catalyst in the reactive composition is from 0.05% to 2% by weight, and preferably from 0.1% to 0.5% by weight.

[0053] filler The filler is present in the reactive composition according to the invention in an amount of 20% to less than 75% by weight of the total weight of the reactive composition. Surprisingly, if the amount is below or above the above range, the tensile strength and / or elongation at break of the cured product will deteriorate, and the cured adhesive will be unsuitable for structural bonding. Preferably, the filler is present in an amount of more than 30% to 70% by weight, more preferably 35% to 65% by weight, and particularly 40% to 60% by weight of the total weight of the reactive composition.

[0054] There are no restrictions on the type of filler, as long as it can achieve the desired properties of the reactive composition and the cured product. For example, the filler can be any inorganic filler, either alone or in combination, or any organic filler.

[0055] Examples of fillers include, but are not limited to, chalk, lime powder, pyrolytic or molten silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium dioxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground minerals. Organic fillers can also be used, particularly carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, sawdust, chopped straw, rice husks, ground walnut shells, and other chopped fibers. Short fibers such as glass fiber, glass filaments, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber can also be added. Aluminum powder is also suitable as a filler.

[0056] Pyrolytic and / or molten silica can be surface-treated to impart hydrophobic properties. Advantageously, pyrolytic and / or molten silica has a surface area of ​​10 to 90 μm. 2 / g BET surface area. When used, they do not cause any additional increase in viscosity of the reactive compositions according to the invention, but help to strengthen the cured product.

[0057] Similarly, it is conceivable to use areas with a high BET surface area, advantageously 100 to 250 m². 2 / g, especially 110 to 170 m 2 / g of pyrolytic and / or molten silica is used as a filler. Due to the large surface area of ​​BET, the same effect can be achieved with a smaller weight proportion of silica, for example, to strengthen the cured product. Other substances can therefore be used to improve the cured product according to the invention in terms of different requirements.

[0058] Hollow spheres with mineral or plastic shells are also suitable as fillers. They are composed of inorganic or organic materials and each has a diameter of 1 mm or less, preferably 500 μm or less.

[0059] In one embodiment, the filler comprises calcium carbonate. In a preferred embodiment, the filler is selected from carbon black, pyrolytic silica, fused silica, calcium carbonate, and combinations thereof. In a more preferred embodiment, a combination of carbon black and calcium carbonate is used in the reactive composition. In another preferred embodiment, a combination of pyrolytic silica and calcium carbonate is included in the reactive composition. Examples of commercially available carbon black include Monarch products from Cabot, such as Monarch A 120, 430, 490, 570, 580, 460, 280, 700, and 800. Examples of commercially available pyrolytic silica include Aerosil products from Evonik Degussa, such as R 202, R 816, R 812, 200 F, 380 F, R 208, and R974. Examples of commercially available calcium carbonate include Omya BLH from Omya.

[0060] additive Reactive compositions may, of course, contain auxiliary ingredients and additives. However, reactive compositions should be broadly formulated to exhibit an initial viscosity suitable for paste or liquid materials. The viscosity range of the reactive composition is less than 2000 Pa∙s, preferably less than 1000 Pa∙s, and more preferably less than 500 Pa∙s.

[0061] The reactive compositions of the present invention may be solvent-free. Alternatively, the compositions may contain one or more solvents, wherein at least one of the solvents is preferably miscible with water. Therefore, it is envisioned that the compositions may be characterized as solvent systems consisting of two or more water-miscible solvents. Similarly, the compositions may be characterized as solvent systems consisting of at least one water-immiscible solvent and at least one water-miscible solvent. For completeness, the term "immiscible" as used herein means that two phases exist in some portions.

[0062] Non-limiting examples of water-miscible solvents include, but are not limited to, 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, chloroform, xylene, and combinations thereof.

[0063] When used, the amount of solvent present in the composition can be determined based on normal practical considerations. Preferably, the solvent is present in an amount of 0.05% to 10% by weight, more preferably 0.1% to 5% by weight, even more preferably 0.1% to 1% by weight, and particularly 0.1% to 0.5% by weight, based on the total weight of the reactive composition.

[0064] The compositions of the present invention may, of course, also contain other standard additives, such as pigments, 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 to the fact that these additives must be compatible with the other components of the composition and must not be detrimental to the use of the composition.

[0065] In some embodiments, a plasticizer may be included to adjust the softness and flexibility of the cured reactive adhesive / sealant composition. In this case, one or more plasticizers may be selected from: vegetable oils; mineral oils; soybean oils; terpene resins; aromatic esters, such as dioctyl phthalate, undecyl phthalate, tricresyl phosphate, and triisononyl mellitate; linear esters, such as bis-tridecyl adipate; chlorinated paraffins; aromatic and naphthenic process oils; alkyl naphthalenes; and low molecular weight polyisoprene, polybutadiene, monofunctional and long-chain amine or polybutene resins. Conventionally, based on the total weight of the adhesive / sealant composition, the amount of plasticizer should be 0 to 20% by weight, preferably 0 to 10% by weight or 0 to 5% by weight.

[0066] Organofunctional silanes (e.g., mercapto-functional, epoxy-functional, and especially amino-functional silanes) can be preferably used as adhesion promoters to improve adhesion on 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 large number of compounds.Examples include: 3-glycidyloxymethyltrimethoxysilane, 3-glycidyloxymethyltriethoxysilane, 3-glycidyloxymethyltripropoxysilane, 3-glycidyloxymethyltributoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 2-glycidyloxyethyltripropoxysilane, 2-glycidyloxyethyltributoxysilane, 2-glycidyloxyethyltrimethoxysilane, 1-glycidyloxyethyltriethoxysilane, 1-glycidyloxyethyltripropoxysilane, 1-glycidyloxyethyltributoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane Alkane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltributoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltripropoxysilane, 2-glycidoxypropyltributoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltriethoxysilane, 1-glycidoxypropyltripropoxysilane, 1-glycidoxypropyltributoxysilane, 3-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, 4-glycidoxybutyltripropoxysilane, 4-glycidoxybutyltributoxysilane, 4-glycidoxybutyltributoxysilane, 4-glycidoxybutyltributoxysilane 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)methyltripropoxysilane Methyltributoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, (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 5% by weight, preferably 0.5 to 4% by weight, and especially preferably 0.2 to 1% by weight.

[0067] Flame retardants can be added to the adhesive / sealant compositions according to the invention to improve the properties of the cured product, especially when used for structural bonding. Examples of flame retardants include ammonium polyphosphate, triphenylphosphine oxide, aluminum triethylphosphine, zinc diethylphosphine, melamine cyanurate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, ammonium melamine polyphosphate, ammonium melamine pyrophosphate, melamine borate, triphenyl phosphate, resorcinol bis-(diphenyl phosphate), bisphenol A-bis-(diphenyl phosphate), resorcinol-bis-(2,6-diphenyldimethyl phosphate), aluminum hydroxide, aluminum hydroxide, magnesium dihydroxyl, zinc oxide, molybdenum trioxide, antimony oxide, aluminum trihydroxyl, zinc borate, calcium silicate, magnesium silicate, calcium sulfate, magnesium carbonate, dihydroxaphosphaphenantren, dihydroxaphosphaphenantren-hydroquinone, potassium diphenyl sulfonate, polymethylphenylsiloxane, potassium perfluorosulfonate, 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, and especially preferably 0.5 to 10% by weight.

[0068] In a preferred embodiment, based on the total weight of the reactive composition, the reactive composition for the adhesive or sealant comprises or consists of the following: (a) 1% to 20% by weight, preferably 2% to 15% by weight, of a polyfunctional acetoacetate compound. (b) 15% to 65% by weight, preferably 35% to 65% by weight, of polyfunctional urethane (meth)acrylate oligomers, (c) 0.05% to 2% by weight, preferably 0.1% to 0.5% by weight, of a catalyst. (d) 20% to less than 75% by weight, preferably more than 30% to 70% by weight, and more preferably 40% to 60% by weight of filler. (e) Optional amounts of 0.05% to 10% by weight, preferably 0.1% to 5% by weight, and more preferably 0.1% to 1% by weight, particularly 0.1% to 0.5% by weight of the solvent, and (f) Optional 0.1% to 5% by weight, preferably 0.2% to 1% by weight of an adhesion promoter.

[0069] In another aspect, it relates to a bipartite or multipartite reactive composition comprising: (a) The first part comprising a polyfunctional acetoacetate compound, (b) A second portion comprising polyfunctional urethane (meth)acrylate oligomers, The catalyst is included in the first and / or second part. The first part or the second part, or preferably the first part and the second part, contains filler, and The filler is present in an amount of 20% to less than 75% by weight of the total weight of the reactive composition.

[0070] One or more components from each part are stored in separate containers (parts) until the contents of all said containers are mixed together to form a mixture of adhesive compositions prior to application. After application and curing, a solid material forms in the adhesive area.

[0071] Another embodiment of the invention is a method of using the reactive composition of the invention to bond substrates to each other. In this embodiment, the reactive composition is applied to a first substrate. The application method can be carried out by a large number of methods known to those skilled in the art (e.g., brushing, spraying, roller coating, rotary gravure coating, flexographic coating, flow coating, dipping, and combinations thereof) to form a continuous or discontinuous film of the composition as desired. In some embodiments, the reactive composition is applied at ambient temperature / room temperature (about 25°C); or, the reactive composition can be applied at an elevated temperature.

[0072] After the composition is applied to a first substrate, it can then be brought into contact with another substrate to form a composite material. Optionally, pressure is applied to the composite material thus formed, for example, by passing it between rollers to achieve increased contact between the substrate and the composition. In another embodiment of the invention, the composition can be applied simultaneously or sequentially to two surfaces of a first substrate, and then the composition can be simultaneously or sequentially bonded to two other substrates, which may be identical or different. It is also contemplated that the composite material structure can be sequentially bonded to one or more other substrates using the compositions of the present invention or different compositions before or after the methods described herein. The first and second substrates to be bonded in the methods of the present invention may be identical or different and include, for example, paper, fabric, leather, metal (e.g., aluminum and steel), ceramics, glass, wood, or plastics (e.g., PP, PC, PVC, etc.), which may have smooth or structured surfaces and may be provided in rolls, sheets, films, foils, etc.

[0073] In some embodiments of the invention, the substrate is relatively thin and flat, and the resulting composite material is referred to as a laminate. The substrate can be constructed in a multilayer laminate structure based on polyolefins (e.g., polyethylene and polypropylene), polyesters, and polyamides (nylon), metallized polypropylene, aluminum foil, etc. Examples of two-layer laminate structures include polypropylene / polypropylene, polyester / nylon, polyester / polyethylene, polypropylene / metallized polypropylene, polypropylene / aluminum foil, polyester / aluminum foil, polyamide / aluminum foil, etc.

[0074] The reactive compositions of this invention undergo a chemical reaction, referred to herein as "curing." While the invention is not limited to any particular theory, curing is considered to begin when the reactive adhesive / sealant composition is formed and to continue at least until the end of the canning period, and may continue thereafter. In some embodiments, a layer of the reactive composition is applied to a substrate before the end of the canning period. In some of these embodiments, at least one additional substrate is brought into contact with the curable mixture layer; often, said additional substrate is brought into contact with the reactive adhesive / sealant composition layer before the end of the canning period. Thus, in some embodiments, curing does not end until after the reactive composition and the substrate have come into contact. This is because the cured product forms a useful adhesive bond between the substrates.

[0075] This reactive composition is suitable for direct glass assembly in vehicle manufacturing and repair. It can be used to bond windshields in vehicles during manufacturing and repair processes, comprising the steps of applying the reactive composition to bond glass components, such as windshields, to one or more vehicle frames made of metal or alloy.

[0076] While this invention is particularly suitable for use as an adhesive, it is also applicable to sealants and elastomers. When used as an elastomer, the reactive composition can be placed 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.

[0077] The following examples illustrate various features and implementations of this disclosure, which are intended to be representative and non-limiting.

[0078] Example Material 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN) was obtained from Acros Organics.

[0079] Omya BLH is ground CaCO3 chalk obtained from Omya.

[0080] Monarch A580 is carbon black, obtained from Cabot.

[0081] Monarch A430 is carbon black, obtained from Cabot.

[0082] Aerosil R202 is pyrolytic silica, obtained from Evonik.

[0083] AAEG-215 is an acetoacetate with a functionality of 2 and an average molecular weight of 246 g / mol, which was obtained from Arxada.

[0084] CN996 is an aliphatic urethane diacrylate with a functionality of 2 and a weight-average molecular weight of 2850 g / mol, obtained from Sartamomer.

[0085] CN9002 is an aliphatic urethane diacrylate with a functionality of 2 and a weight-average molecular weight of 5450 g / mol, obtained from Sartamomer.

[0086] CN981 is an aliphatic urethane diacrylate with a functionality of 2 and a weight-average molecular weight of 1900 g / mol, obtained from Sartamomer.

[0087] The standard solvent was obtained from VWR.

[0088] Test methods Tensile strength Tensile strength testing is used to test the elasticity of a material under tensile strain according to ASTM 638. This test is performed on a Zwick universal testing machine. In this test, 3 to 5 dog-bone shaped specimens are tested for each reactive composition. The specimens are positioned such that the jaws of the universal testing machine grip each end of the dog-bone specimen. A preload of 2 N is then applied. The jaws are then disengaged at a rate of 200 mm / min until the specimen fails. The maximum tensile strength achieved is then recorded as the tensile strength.

[0089] Elongation at break Tensile strength testing was used to test the elasticity of materials under tensile strain according to ASTM 638. This test was performed on a Zwick universal testing machine. In this test, 3 to 5 dog-bone shaped specimens were tested for each reactive composition. The specimens were positioned such that the jaws of the universal testing machine gripped each end of the dog-bone specimen. A preload of 2 N was then applied. The jaws were then disengaged at a rate of 200 mm / min until the specimen failed. The elongation of the specimen at specimen failure was then recorded.

[0090] If the cured adhesive has a tensile strength of not less than 2 MPa, it is considered acceptable for structural bonding (especially direct glass assembly of vehicle windshields). If the cured adhesive has a tensile strength of not less than 3 MPa, it is considered excellent for the application. If the cured adhesive has an elongation at break of not less than 100%, it is considered acceptable for structural bonding (especially direct glass assembly of vehicle windshields). If the cured adhesive has an elongation at break of not less than 200%, it is considered excellent for the application.

[0091] Synthesis of trimethylolpropane triacetyl acetate The synthesis of trimethylolpropane triacetoacetate (AATMP) was performed according to the procedure “Transacetoacetylation with tert-Butyl Acetoacetate: Synthetic Applications”, JS Witzeman, WD Nottingham, J. Org. Chem. 1991, 56, 1713-1718. Trimethylolpropane or pentaerythritol (1 equivalent) and TBAA (1.1 equivalent) were added to a 500 mL three-necked round-bottom flask. A Y-connector, a mechanical stirring bar, and a reflux condenser were then installed in each neck of the flask. The thermocouple and nitrogen connector were adjusted in the Y-connector. The temperature was set to 140 °C under a nitrogen atmosphere (and maintained at 92 °C for approximately 4 hours under reflux). Following this, distillation was carried out at atmospheric pressure for 8 hours while the temperature was slowly increased to 140 °C. Finally, when distillation ceases, distillation is carried out under reduced pressure for 2 hours at 140°C, decreasing from 900 mbar to 400 mbar. The reaction scheme is shown below.

[0092] Example 1 Monarch A580 (11.68 g) and Omya BLH (20.98 g) were added to CN9002 (62.97 g) and homogenized in a speed mixer. AATMP (3.72 g) was added, and the mixture was homogenized in a speed mixer. DBN (0.22 g) was pre-dissolved in industrial-grade ethanol (0.43 g), and this mixture was added to the above formulation. After further homogenization, the mixture was pressed into 2 mm thick sheets and cured at 60°C for 1 day and at 23°C for 6 days. Test specimens were prepared from these sheets, and material properties were recorded according to ASTM D638. Three samples were measured, and the average results were obtained. The cured product showed a tensile strength of 6.7 MPa and an elongation at break of 380%.

[0093] Example 2 Monarch 430 (20 g) and Omya BLH (20 g) were added to CN9002 (56.83 g) and homogenized in a high-speed mixer. AAEG-215 (2.57 g) was added, and the mixture was homogenized in a high-speed mixer. DBN (0.2 g) was pre-dissolved in industrial-grade ethanol (0.4 g), and this mixture was added to the above formulation. After further homogenization, the mixture was pressed into 2 mm thick sheets and cured at 60°C for 1 day and at 23°C for 6 days. Specimens were prepared from these sheets, and material properties were recorded according to ASTM D638. Three samples were measured, and the average results were obtained. The cured product showed a tensile strength of 4.5 MPa and an elongation at break of 560%.

[0094] Example 3 Aerosil R202 (3 g) and Omya BLH (57 g) were added to CN9002 (17.47 g) and CN981 (17.8 g) and homogenized in a high-speed mixer. AATMP (4.13 g) was added, and the mixture was homogenized in a high-speed mixer. DBN (0.2 g) was pre-dissolved in industrial-grade ethanol (0.4 g), and this mixture was added to the above formulation. After further homogenization, the mixture was pressed into 2 mm thick sheets and cured at 60°C for 1 day and at 23°C for 6 days. Test specimens were prepared from this sheet, and material properties were recorded according to ASTM D638. Three samples were measured, and the average results were obtained. The cured product showed a tensile strength of 2.86 MPa and an elongation at break of 260%.

[0095] Example 4 Monarch 430 (20 g) and Omya BLH (20 g) were added to CN996 (48.94 g) and Dynasylan 1122 (0.3 g) and homogenized in a high-speed mixer. AAEG-215 (10.16 g) was added, and the mixture was homogenized in a high-speed mixer. DBN (0.2 g) was pre-dissolved in industrial-grade ethanol (0.4 g), and this mixture was added to the above formulation. After further homogenization, the mixture was pressed into 2 mm thick sheets and cured at 60°C for 1 day and at 23°C for 6 days. Test specimens were prepared from these sheets, and material properties were recorded according to ASTM D638. Three samples were measured, and the average results were obtained. The cured product showed a tensile strength of 5.97 MPa and an elongation at break of 630%.

[0096] Example 5 Monarch A580 (10 g) and Omya BLH (20 g) were added to CN996 (58.87 g) and homogenized in a high-speed mixer. AATMP (10.53 g) was added, and the mixture was homogenized in a high-speed mixer. DBN (0.2 g) was pre-dissolved in industrial-grade ethanol (0.4 g), and this mixture was added to the above formulation. After further homogenization, the mixture was pressed into 2 mm thick sheets and cured at 60°C for 1 day and at 23°C for 6 days. Test specimens were prepared from this sheet, and material properties were recorded according to ASTM D638. Three samples were measured, and the average results were obtained. The cured product showed a tensile strength of 14.7 MPa and an elongation at break of 155%.

[0097] Comparative Example 1 DBN (0.33 g) was pre-dissolved in industrial-grade ethanol (0.66 g), and this mixture, along with Dynasylan 1122 (0.49 g), was added to CN996 (81.55 g) and homogenized using a high-speed mixer. AAEG-215 (16.95 g) was added to the above formulation. After further homogenization, the mixture was pressed into 2 mm thick sheets and cured at 60°C for 1 day and at 23°C for 6 days. Specimens were prepared from these sheets, and material properties were recorded according to ASTM D638. Three samples were measured, and the average results were obtained. The cured product showed a tensile strength of 0.371 MPa and an elongation at break of 811.7%.

[0098] Comparative Example 2 Monarch 430 (15 g) and Omya BLH (60 g) were added to CN996 (20.49 g) and homogenized in a high-speed mixer. AAEG-215 (4.26 g) was added, and the mixture was homogenized in a high-speed mixer. DBN (0.08 g) was pre-dissolved in industrial-grade ethanol (0.17 g), and this mixture was added to the above formulation. After further homogenization, the mixture was pressed into 2 mm thick sheets and cured at 60°C for 1 day and at 23°C for 6 days. Test specimens were prepared from these sheets, and material properties were recorded according to ASTM D638. Three samples were measured, and the average results were obtained. The cured product showed a tensile strength of 2.39 MPa and an elongation at break of 56.9%.

[0099] It is evident from the above results that the embodiments of the present invention all exhibit an acceptable or excellent combination of tensile strength and elongation at break, while the comparative examples do not achieve such a combination in at least one aspect of the stated properties.

Claims

1. A reactive composition for use as an adhesive, comprising: (a) Polyfunctional acetoacetate compounds, (b) Polyfunctional urethane (meth)acrylate oligomers, (c) Catalyst, and (d) Packing material, The filler is present in an amount of 20% to less than 75% by weight of the total weight of the reactive composition.

2. The reactive composition according to claim 1, wherein the polyfunctional acetoacetate compound has at least two acetoacetoxy groups, preferably two to ten acetoacetoxy groups, and more preferably three to four acetoacetoxy groups.

3. The reactive composition according to claim 1 or 2, wherein the polyfunctional acetoacetate compound is an acetylated polyol obtained from glycerol, trimethylolpropane, isosorbide ethanol, neopentyl glycol, pentaerythritol, dimethylolpropane, dipentaerythritol, propoxylated monosaccharide, trimethylolethane, and combinations thereof.

4. The reactive composition according to any one of claims 1 to 3, wherein the weight-average molecular weight of the polyfunctional urethane (meth)acrylate oligomer is from 500 g / mol to 50,000 g / mol, preferably from 1,000 g / mol to 10,000 g / mol, and more preferably from 1,500 g / mol to 8,000 g / mol.

5. The reactive composition according to any one of claims 1 to 4, wherein the polyfunctional urethane (meth)acrylate oligomer is selected from polyfunctional polyester urethane (meth)acrylate, polyfunctional polyether urethane (meth)acrylate, polyfunctional polyester / polyether urethane (meth)acrylate, and combinations thereof.

6. The reactive composition according to any one of claims 1 to 5, wherein the molar equivalent ratio of acetoacetate groups to (meth)acrylate groups in the reactive adhesive / sealant composition is greater than 1:1, preferably in the range of 2:1 to 1.05:1, and more preferably in the range of 2:1 to 1.1:

1.

7. The reactive composition according to any one of claims 1 to 6, wherein the catalyst is selected from 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), triazabicyclodecene (TBD), tetramethylguanidine (TMG), trioctylphosphine (TOP), triphenylphosphine (TPP), (tetrabutylammonium hydroxide)TBAOH, NaOH, KOH, NaOEt, KOEt, phosphazane, and combinations thereof.

8. The reactive composition according to any one of claims 1 to 7, wherein the filler is selected from carbon black, pyrolytic silica, precipitated silica, calcium carbonate, and combinations thereof.

9. The reactive composition according to any one of claims 1 to 8, wherein the filler is present in an amount of more than 30% to 70% by weight, and preferably 40% to 60% by weight, of the total weight of the reactive composition.

10. The reactive composition according to any one of claims 1 to 7, comprising one or more additives selected from the group consisting of solvents, pigments, plasticizers, leveling agents, foam inhibitors, rheology control agents, antioxidants, tackifiers, adhesion promoters, flame retardants, UV stabilizers, and combinations thereof.

11. A reactive composition for use as an adhesive, wherein, based on the total weight of the reactive composition, the composition comprises: (a) 1% to 20% by weight of polyfunctional acetoacetate compounds, (b) 15% to 65% by weight of polyfunctional urethane (meth)acrylate oligomers, (c) 0.05% to 2% by weight of catalyst, and (d) 20% to less than 75% by weight, preferably 40% to 60% by weight of filler.

12. A two- or multi-part reactive composition for use as an adhesive, comprising: (a) The first part comprising a polyfunctional acetoacetate compound, (b) A second portion comprising polyfunctional urethane (meth)acrylate oligomers, The catalyst is included in the first and / or second part. The first and / or second parts contain filler, and The filler is present in an amount of 20% to less than 75% by weight of the total weight of the reactive composition.

13. The cured product of the reactive composition according to any one of claims 1 to 11 or the two- or multi-part reactive composition according to claim 12.

14. Use of the reactive composition according to any one of claims 1 to 11 or the two- or multi-part reactive composition according to claim 12 for bonding to a substrate made of or having a surface of the following materials: paper, fabric, leather, metal, porcelain, ceramics, glass, wood, or plastic.

15. A method of bonding a windshield in a vehicle, comprising applying a reactive composition according to any one of claims 1 to 11 or a two- or multi-part reactive composition according to claim 12 to bond the windshield to a vehicle frame.

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