Composition based on a silane-functionalized polymer with improved topcoatability

Abstract

The present invention relates to a moisture-curable composition comprising at least one organic polymer P containing reactive silane groups; 1.0 to 25.0% by weight, preferably 2.0 to 20% by weight, and particularly 2.5 to 10% by weight, of a dimethyl or diethyl ester of an aliphatic C3-C5 dicarboxylic acid, based on the total weight of the composition; and at least one curing catalyst for the alkoxysilane groups. This moisture-curable composition is particularly suitable as an elastic adhesive, coating, filler, or sealant, and exhibits excellent overcoatability, especially with automotive topcoats or similar paints.

Description

[Technical Field]

[0001] The present invention relates to curable compositions based on organosilane-functionalized polymers, and to the use thereof as adhesives, sealants, fillers, or coatings. [Background technology]

[0002] Curable compositions based on polymers containing reactive silane groups play an important role in many industrial and construction applications, for example, as adhesives, sealants, or coatings. Polymers containing reactive silane groups are either polydiorganosiloxanes (commonly called "silicones" or "silicone rubbers") or organic polymers containing reactive silane groups (also known as "silane-functional polymers," "silane-modified polymers" (SMPs), or "silane-terminated polymers" (STPs)). Compositions containing these polymers are cured via crosslinking reactions of the reactive silane groups on the polymer (hydrolysis under the influence of moisture, condensation of silanol groups into siloxane bonds).

[0003] Due to their diverse mechanical properties in their cured state and excellent adhesion to various substrates, compositions based on substrates and organosilane-terminated polymers are widely used in repair applications. Their tensile strength, elasticity, Shore A hardness, and many other related properties can be adjusted over a wide range by appropriately formulating the composition, and in many cases, their adhesive performance is fully realized without requiring extensive pretreatment of the substrate. Therefore, such compositions are extremely suitable for repair operations, such as the restoration of a car body after a collision, because they form durable adhesive bonds on painted or bare metal and other materials used in automobile manufacturing.

[0004] One problem with compositions based on silane-functional polymers is that their topcoat performance is somewhat limited, especially when used with hard, hydrophobic paints, varnishes, or lacquers, which are currently used as topcoats in, for example, automotive paint shops.

[0005] After repairing a damaged painted object, such as the body of a damaged car, it is necessary to reapply the same paint that was applied to the rest of the object to the repaired area in order to make the repaired damage less noticeable. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, with modern durable paints, varnishes, and lacquers, the topcoatability of compositions based on silane-functional polymers is a problem. When using common silane-functional polymer-based compositions, the paint, varnish, or lacquer tends to flake off after some time, especially when scratched or otherwise damaged, leaving visible paint defects that are not only unsightly but can also accelerate rusting if the painted substrate is metal. Furthermore, it has been observed that components of common silane-functional polymer-based compositions, such as plasticizers, often react with or migrate into the dried paint applied over them, thereby causing visible discoloration on the dried paint, varnish, or lacquer covering the cured silane-functional polymer-based composition.

[0007] Therefore, an object of the present invention is to provide a curable composition based on a polymer containing an organically reactive silane group that can be easily overcoated and has durability such that the paint, varnish, or lacquer applied thereon does not peel or show signs of discoloration. This is also applicable to paints, varnishes, or lacquers used today in automotive paint shops, particularly hydrophobic, demanding, and high-hardness paints, varnishes, or lacquers. [Means for solving the problem]

[0008] The present invention achieves these objectives using the features of independent claim 1.

[0009] When a moisture-curable composition based on a polymer containing an organic reactive silane group is mixed with 1.0% to 25.0% by weight, preferably 2.0% to 20% by weight, and particularly 2.5% to 10% by weight, of a dimethyl or diethyl ester of an aliphatic C3-C5 dicarboxylic acid, and at least one curing catalyst for alkoxysilane groups, based on the entire composition, remarkably, significantly improved topcoatability is obtained, especially when used with hydrophobic, demanding, high-hardness paints, varnishes, or lacquers used today in automotive paint shops.

[0010] Further aspects of the present invention are the subject of further independent claims. Particularly preferred embodiments of the present invention are the subject of dependent claims. [Modes for carrying out the invention]

[0011] In a first embodiment, the present invention relates to a moisture-curing composition comprising the following: - An organic polymer P containing at least one reactive silane group; - Based on the entire composition, 1.0% to 25.0% by weight, preferably 2.0% to 20% by weight, and particularly 2.5% to 10% by weight, of dimethyl or diethyl esters of aliphatic C3-C5 dicarboxylic acids; and - At least one curing catalyst for alkoxysilane groups.

[0012] In this specification, the term "reactive silane group" refers to a silyl group bonded to an organic group or a polyorganosiloxane group and having 1 to 3, particularly 2 or 3, hydrolyzable substituents or hydroxyl groups on its silicon atom. Particularly useful hydrolyzable substituents are alkoxy groups. Those silane groups are also called "alkoxysilane groups". The reactive silane group may be in a partially or fully hydrolyzed form, for example, silanol.

[0013] The terms "hydroxysilane", "isocyanatosilane", "aminosilane", and "mercaptosilane" refer to organoalkoxysilanes having 1 or more hydroxyl, isocyanato, amino, or mercapto groups in addition to a silane group on an organic group.

[0014] "Amino-functional compound" refers to a compound containing an amino group.

[0015] "Primary amino group" refers to an NH2 group bonded to one organic group, "secondary amino group" refers to an NH group bonded to two organic groups (which may together form part of a ring), and "tertiary amino group" refers to a N group bonded to three organic groups (two or three of which may together form part of one or more rings). Thus, "primary aminosilane" is an aminosilane containing a primary amino group, and "secondary aminosilane" is an aminosilane containing a secondary amino group. The latter also includes compounds having both primary and secondary amino groups.

[0016] The "polyoxyalkylene group" contains an ether group and refers to a linear or branched hydrocarbyl group containing two or more consecutive repeating units of the (O-R) type (where R is a linear or branched alkylene group obtained, for example, by polyaddition of ethylene oxide or 1,2-propylene oxide to a starter molecule having two active hydrogen atoms).

[0017] Substance names starting with "poly", such as polyols or polyisocyanates, formally refer to substances containing functional groups having two or more of those names in one molecule.

[0018] The term "organic polymer" includes a group of macromolecules that are chemically homogeneous but different in terms of degree of polymerization, molar mass, and chain length, formed by a polymerization reaction (polymerization, polyaddition, polycondensation), with most of the polymer backbone being carbon atoms, as well as reaction products of such a group of macromolecules. Polymers having a polyorganosiloxane main chain (generally called "silicones") are not organic polymers in the context of this specification.

[0019] The term "polyether containing a reactive silane group" further includes organic polymers that contain a silane group and may further contain urethane groups, urea groups, or thiourethane groups in addition to polyether units. Such polyethers containing a reactive silane group may also be called "polyurethanes containing a reactive silane group".

[0020] In this specification, the term "molecular weight" should be understood to mean the molar mass (in grams / mol) of a molecule or a part of a molecule (sometimes called a "radical"). In this specification, the term "radical" is formally used to mean the remaining part of a molecule bonded to a certain atom by a covalent bond, while "bond" is a "cut" that describes the rest of the molecule to which it is bonded. The term "average molecular weight" refers to the number average M of an oligomeric or polymeric mixture of molecules or groups. n This should be understood as meaning that this is typically measured by gel permeation chromatography (GPC) using polystyrene as a standard.

[0021] "Weight percent" (or "percentage by weight") and its abbreviation "wt.-%" refer to the weight percentage of a compound in the entire composition unless otherwise defined. The terms "weight" and "mass" are used interchangeably herein and refer to mass as a property of a physical object, generally measured in kilograms (kg).

[0022] "Storage-stable" or "storable" refers to a substance or composition that can be stored at room temperature in a suitable container for an extended period, typically at least three to six months or more, without any change in its usability or performance, particularly in terms of viscosity and crosslinking ratio, to the extent that it is still suitable for use as a result of storage.

[0023] "Room temperature" refers to a temperature of approximately 23°C.

[0024] All industrial standards (norms) referenced herein refer to their respective editions in force as of the filing date of the first filing of the present invention, unless otherwise defined.

[0025] The composition of the present invention requires, firstly, at least one organic polymer P containing a reactive silane group.

[0026] The amount of polymer P in the composition is generally 10 to 60% by weight, preferably 10 to 40% by weight, and more preferably 15 to 30% by weight, based on the total composition. Within this range, good mechanical properties can be obtained without significantly increasing the cost of the composition.

[0027] The organic polymer P containing reactive silane groups is particularly a polyurethane, polyolefin, polyester, polycarbonate, polyamide, poly(meth)acrylate, or polyether, or a mixture of these polymers, each supporting one, preferably two or more silane groups. These silane groups may be pendanted in the chain or at the terminal, and are bonded to the organic polymer via carbon atoms.

[0028] More preferably, the organic polymer P containing the reactive silane group is a polyolefin containing a reactive silane group, a polyurethane containing a reactive silane group, a polyether containing a reactive silane group, or a mixture of these polymers.

[0029] The most preferable organic polymer containing the reactive silane group is a polyether containing the reactive silane group.

[0030] The silane group present in the organic polymer containing the reactive silane group is preferably an alkoxysilane group, particularly an alkoxysilane group of formula (VII): [ka] [In the formula, R 14 This is a monovalent hydrocarbyl group having 1 to 5 carbon atoms, in a linear or branched configuration, particularly methyl, ethyl, or isopropyl; R15 This is a linear or branched monovalent hydrocarbyl group having 1 to 8 carbon atoms, particularly methyl or ethyl; and x is a numerical value of 0, 1, or 2, preferably 0 or 1, and especially 0.

[0031] R 14 However, methyl or ethyl is more preferable.

[0032] For specific purposes, its R 14 The group is preferably an ethyl group, because in this case, ethanol, which is ecologically and toxicologically harmless, is released during the curing process of the composition.

[0033] Particularly preferred are trimethoxysilane groups, dimethoxymethylsilane groups, or triethoxysilane groups.

[0034] In this context, the methoxysilane group has the advantage of being particularly reactive, while the ethoxysilane group has the advantage of being toxicologically advantageous and having particularly high storage stability.

[0035] The organic polymer containing the reactive silane group has, on average, preferably 1.3 to 4, particularly 1.5 to 3, and more preferably 1.7 to 2.8 silane groups per molecule. It is preferable that these silane groups are located at the terminals.

[0036] The organic polymer containing the reactive silane group has an average molecular weight of preferably 1,000 to 30,000 g / mol, and more particularly 2,000 to 20,000 g / mol, as measured relative to a polystyrene standard by GPC. The organic polymer containing the reactive silane group has a silane equivalent of preferably 300 to 25,000 g / eq, and more particularly 500 to 15,000 g / eq.

[0037] The organic polymer containing the reactive silane group may be solid or liquid at room temperature. It is preferable that it be liquid at room temperature.

[0038] Most preferably, the organic polymer containing the reactive silane group is a liquid at room temperature, and the silane group is particularly a dialkoxysilane group and / or a trialkoxysilane group, more preferably a trimethoxysilane group or a triethoxysilane group.

[0039] Processes for preparing polymers containing organically reactive silane groups are known to those skilled in the art.

[0040] In a preferred process, an organic polymer containing an organic reactive silane group can be obtained by optionally reacting an organic polymer containing an allyl group with a hydrosilane, for example, by chain elongation using a diisocyanate.

[0041] In a more preferred process, a polyether containing a reactive silane group can be obtained by copolymerizing an alkylene oxide and an epoxy silane, optionally using, for example, chain elongation with a diisocyanate.

[0042] In a further preferred process, a polymer containing an organically reactive silane group can be obtained by optionally using chain elongation with a diisocyanate and reacting the organic polyol with isocyanatosilane.

[0043] In a further preferred process, a polyether containing a reactive silane group can be obtained by reacting an NCO-terminated urethane polymer, obtained by the reaction of an isocyanate group-containing organic polymer, particularly a polyol, with a hyperstoichiometric amount of polyisocyanate, with an aminosilane, hydroxysilane, or mercaptosilane. The reactive silane-containing polyether obtained from this process is particularly preferred. This process makes it possible to use many inexpensive starting materials that are readily available on the market, and by means of obtaining various polymer properties, such as high ductility, high strength, low modulus of elasticity, low glass transition temperature, or high weather resistance.

[0044] More preferably, the organic polymer containing the reactive silane group can be obtained by reacting an NCO-terminated urethane polyether with an aminosilane or hydroxysilane. Suitable NCO-terminated urethane polymers can be obtained by reacting a polyol, particularly a polyether polyol, particularly a polyoxyalkylenediol or polyoxyalkylentriol, preferably a polyoxypropylenediol or polyoxypropylenetriol, with a hyperstoichiometric amount of polyisocyanate, particularly a diisocyanate. Furthermore, other polyols, such as poly(meth)acrylate polyols, polyhydrocarbon polyols, particularly polybutadiene polyols, polyhydroxy-functional oils and fats, polycarbonate polyols, polyester polyols, and polyhydroxy-functional acrylonitrile / butadiene copolymers are also suitable. In addition, small amounts of low molecular weight dihydric or polyhydric alcohols, such as diols, glycols, and sugar alcohols, can be used as additives.

[0045] Preferably, the reaction between the polyisocyanate and the polyol is carried out in the absence of moisture (humidity) at a temperature of 50°C to 160°C, in the presence of a suitably selected catalyst, by weighing and adding the polyisocyanate so that its isocyanate groups are present in a stoichiometric excess relative to the hydroxyl groups of the polyol. More specifically, the excess amount of polyisocyanate is selected such that, even after all the hydroxyl groups have reacted, the resulting urethane polymer retains a free isocyanate group content of 0.1% to 5% by weight, preferably 0.2% to 4% by weight, and more preferably 0.3% to 3% by weight, based on the total polymer.

[0046] Preferred diisocyanates are selected from the group consisting of: hexamethylene 1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (=isophorone diisocyanate, i.e., IPDI), various desired mixtures of trilen 2,4- and 2,6-diisocyanates and their isomers (TDI), and various desired mixtures of diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanates and their isomers (MDI). Particularly preferred are MDI, IPDI, or TDI. In some embodiments, IPDI is most preferred. This yields a polyether containing a reactive silane group with particularly good lightfastness.

[0047] Particularly preferred as polyether polyols are polyoxyalkylenediols or polyoxyalkylentriols having a degree of unsaturation lower than 0.02 meq / g, especially lower than 0.01 meq / g, and an average molecular weight in the range of 400 to 25,000 g / mol, especially 1,000 to 20,000 g / mol.

[0048] It is also possible to partially use other polyols, particularly polyacrylate polyols, and low molecular weight diols or triols, along with polyether polyols.

[0049] Suitable aminosilanes for reaction with NCO-terminated urethane polyethers are primary and secondary aminosilanes. Suitable examples include: 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, primary aminosilanes, for example, adducts formed from 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and a Michael acceptor, for example, acrylonitrile, (meth)acrylic acid ester, (meth)acrylamide, maleic acid or fumaric acid diester, citraconic acid diester, or itaconic acid diester, particularly dimethyl or diethyl N-(3-trimethoxysilylpropyl)aminosuccinate. Similarly preferred are aminosilane analogs in which the silicon atom is represented by an ethoxy group or an isopropoxy group instead of a methoxy group.

[0050] Hydroxysilanes suitable for reaction with NCO-terminated urethane polyethers can be obtained, in particular, by adding an aminosilane to a lactone, a cyclic carbonate, or a lactide.

[0051] Suitable aminosilanes for this purpose include, in particular: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3-methylbutyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltriethoxysilane, 2-aminoethyltrimethoxysilane, or 2-aminoethyltriethoxysilane. Particularly preferred are: 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, or 4-amino-3,3-dimethylbutyltriethoxysilane.

[0052] Preferred lactones are, in particular, γ-valerolactone, γ-octaractone, δ-decalactone, and ε-decalactone, and especially γ-valerolactone.

[0053] Suitable cyclic carbonates include, in particular, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, or 4-(phenoxymethyl)-1,3-dioxolan-2-one.

[0054] Preferred lactides are, in particular, the following: 1,4-dioxane-2,5-dione (lactide formed from 2-hydroxyacetic acid, also called "glycolide"), 3,6-dimethyl-1,4-dioxane-2,5-dione (lactide formed from lactic acid, also called "lactide"), and 3,6-diphenyl-1,4-dioxane-2,5-dione (lactide formed from mandelic acid).

[0055] Preferred hydroxysilanes obtained by this method include: N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide, N-(3-triethoxysilylpropyl)-4-hydroxypentanamide, N-(3-triethoxysilylpropyl)-4-hydroxyoctanamide, N-(3-triethoxysilylpropyl)-5-hydroxydecanamide, and N-(3-triethoxysilylpropyl)-2-hydroxypropylcarbamate.

[0056] In addition to these, suitable hydroxysilanes can also be obtained by adding aminosilane to an epoxide or by adding an amine to an epoxysilane.

[0057] Suitable hydroxysilanes obtained by this method are: 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexane-1-ol, 2-morpholino-4(5)-(2-triethoxysilyl-ethyl)cyclohexane-1-ol, or 1-morpholino-3-(3-(triethoxysilyl)propoxy)propane-2-ol.

[0058] Further preferred polyethers containing reactive silane groups include commercially available products such as: MS Polymer (trademark) (manufactured by Kaneka Corporation; particularly products of S203H, S303H, S227, S810, MA903, and S943); MS Polymer (trademark) or Silyl (trademark) (manufactured by Kaneka Corporation; particularly products of SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, and MAX951); Excestar (registered trademark) (manufactured by Asahi Glass Co., Ltd.; particularly products of S2410, S2420, S3430, and S3630); and SPUR+. *(manufactured by Momentive Performance Materials; particularly products 1010LM, 1015LM, 1050MM); Vorasil (trademark) (manufactured by Dow Chemical Co.; particularly products 602 and 604); Desmoseal (registered trademark) (manufactured by Bayer MaterialScience AG; particularly products S XP2458, S XP2636, S XP2749, S XP2774, and S XP2821), TEGOPAC (registered trademark) (manufactured by Evonik Industries AG; particularly products Seal 100, Bond 150, Bond 250); Polymer ST (manufactured by Hanse Chemie AG / Evonik Industries AG, particularly products 47, 48, 61, 61LV, 77, 80, 81); Geniosil (registered trademark) STP (manufactured by Wacker Chemie AG; particularly products E10, E15, E30, E35, WP1, and WP2).

[0059] Particularly preferred polymers containing an organo-reactive silane group have end groups of formula (VIII): [Chemical formula] [wherein, R 16 is a linear or branched divalent hydrocarbyl group having 1 to 12 carbon atoms and optionally having cyclic and / or aromatic groups and optionally having one or more heteroatoms, particularly one or more nitrogen atoms; T is a divalent group selected from -O-, -S-, -N(R 17 )-, -O-CO-N(R 17 )-, -N(R 17 )-CO-O-, and -N(R 17 )-CO-N(R 17 )-, but here, R 17 is hydrogen or a linear or branched hydrocarbyl group having 1 to 20 carbon atoms and optionally having a cyclic moiety and optionally having an alkoxysilane, ether, or carboxylic acid ester group; and R 14 , R 15 , and x have the definitions given earlier.

[0060] Preferably, R 16 However, this is 1,3-propylene or 1,4-butylene, where the butylene may be substituted with one or two methyl groups.

[0061] Comfortable, R 16 However, it is 1,3-propylene.

[0062] In some preferred embodiments of the moisture-curable composition of the present invention, the polymer P contains a methoxysilyl group. The methoxysilyl group is particularly highly reactive, and therefore has the advantage that the composition cures rapidly and / or with a low amount of catalyst.

[0063] In other preferred embodiments, the reactive silane group is ethoxysilane, propoxysilane, or a higher alkoxysilane group, preferably an ethoxysilane group. These embodiments result in a reduction in the level of methanol in the VOCs during or after the curing of the composition.

[0064] In some or other preferred embodiments of the moisture-curable composition of the present invention, the moisture-curable composition does not contain any compound that separates and releases methanol when hydrolyzed. Instead, it is preferable that the composition contains only ethanol-fissible compounds (i.e., ethoxysilane-functional compounds). This has the advantage that the composition is not particularly toxic, yet still exhibits sufficient curing behavior.

[0065] The moisture-curable composition of the present invention contains, based on the entire composition, 1.0% to 25.0% by weight, preferably 2.0% to 20% by weight, and particularly 2.5% to 10% by weight, of a dimethyl or diethyl ester of an aliphatic C3-C5 dicarboxylic acid.

[0066] Surprisingly, it was found that dimethyl or diethyl esters of aliphatic C3-C5 dicarboxylic acids, particularly dimethyl glutarate, contribute to the effect of the present invention, namely the improved coatability of the composition.

[0067] Dimethyl or diethyl esters of aliphatic C3-C5 dicarboxylic acids are available on the market either in pure form or, more commonly, as so-called dibasic ester mixtures. Most commonly, they are dimethyl esters, but other esters, such as diethyl esters or esters of higher alcohols, are also available.

[0068] These typically include, based on the total mixture, 0.5–30% by weight of dimethyl succinate, 50–99% by weight of dimethyl glutarate, and 0.5–25% by weight of dimethyl adipate, or other alcohols in place of methanol, such as ethanol esters.

[0069] In this invention, only diesters of methanol or ethanol are suitable. Esters of higher alcohols, such as isobutanol esters, are not suitable for the compositions in this invention because they lead to problems with deactivation and storage stability.

[0070] Dimethyl esters are the most preferred. They allow for the best stability and topcoat effect of the composition.

[0071] The most preferred dimethyl ester is dimethyl glutarate (also known as dimethyl pentanediate).

[0072] In the composition of the present invention, it is preferable that the mixture of dimethyl or diethyl esters of aliphatic C3-C5 dicarboxylic acids used contains at least 50% by weight, particularly at least 75% by weight, preferably at least 90% by weight, and most preferably at least 95% by weight of dimethyl glutarate, based on the total mixture.

[0073] In a preferred embodiment, the curable composition contains less than 5% by weight of other aliphatic dicarboxylic acid diesters, based on the total amount of aliphatic dicarboxylic acid diesters, including dimethyl glutarate, contained in the composition.

[0074] A preferred source of dimethyl glutarate for the compositions of the present invention is a dibasic ester having a high dimethyl glutarate content. For example, Estasol DMG, a mixture of dimethyl succinate, dimethyl glutarate, and dimethyl adipate (Estasol® DMG, manufactured by Chemoxy) containing 99% by weight of dimethyl glutarate, is highly suitable for the purposes of the present invention.

[0075] It is even more preferable if the moisture-curable composition contains 0.1% to 5% by weight, preferably 0.25% to 2.5% by weight, of the organosilane OS of formula (I), based on the entire composition: R a -Si(OCH3)3(I) [In the formula, R a [These are aliphatic, alicyclic, or aromatic C4-C12 alkyl groups, preferably C6-C10 alkyl groups (optionally including ether oxygen or a secondary amino group)].

[0076] The use of organosilane OS in the compositions of the present invention has the advantage of achieving particularly good topcoatability, surpassing that of compositions using dimethyl or diethyl esters of aliphatic C3-C5 dicarboxylic acids, especially dimethyl glutarate, alone.

[0077] Preferred organosilane OSs include: n-butyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, octyltrimethoxysilane, and N-(n-butyl)-3-aminopropyltrimethoxysilane.

[0078] In a particularly preferred embodiment, the organosilane OS is N-(n-butyl)-3-aminopropyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, or any mixture thereof.

[0079] The composition preferably contains 2.5% to 10% by weight of dimethyl glutarate and 0.25% to 2.5% by weight of the organosilane OS, particularly octyltrimethoxysilane and / or N-(n-butyl)-3-aminopropyltrimethoxysilane.

[0080] Preferably, the moisture-curable composition in the present invention further contains 0.5 to 2.5% by weight of an organosilane other than that of formula (I) listed above, based on the entire composition.

[0081] The composition of the present invention may contain 0 to 2.5% by weight of at least one monomeric or oligomeric organosilane based on the whole composition. Preferably, the composition of the present invention contains 0.5 to 2% by weight of a further monomeric or oligomeric organosilane based on the whole composition.

[0082] One advantage of using oligomeric alkoxysilanes is that, compared to pure monomeric silanes, using them in larger quantities makes it possible to achieve lower VOC levels.

[0083] An example of a suitable monomeric amino-functionalized alkoxysilane is shown in formula (II): [ka] [In the formula, R 2 This is a monovalent alkyl group having 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, most preferably a methyl group; R 3 This is a monovalent, linear, cyclic, or branched alkyl or aralkyl group having 1 to 20 carbon atoms and containing a heteroatom optionally selected from O, N, and S; R 4 This is a monovalent, linear, branched, or cyclic alkyl or aralkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, most preferably a methyl group; R 5 This is a monovalent, linear, branched, or cyclic alkyl or aralkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms; The subscript i is an integer having a value of 0 or 1, preferably 0; The subscript k is an integer with a value of 2 or 3, except when i=1, then k=2; The subscript p is an integer with values ​​between 1 and 6.

[0084] Suitable oligomeric silanes are shown in formulas (III) and (IV), where formula (III) represents a linear oligomer and formula (IV) represents a cyclic oligomer. Branched oligomers can also be used, at least as part of an oligomer mixture.

[0085] A linear oligomer suitable for use as an oligomeric silane is shown in formula (III): [ka] [In the formula, R 1 It independently represents the following: - An alkoxy group having 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, more preferably a methoxy group, - R as defined earlier 3 , or - R as defined earlier 4 ;and The subscript n is an integer with values ​​between 1 and 30.

[0086] A cyclic oligomer suitable for use as an oligomeric silane is shown in formula (IV): [ka] [In the formula, R 1 This has the same meaning as mentioned above; and The subscript j is an integer with values ​​between 3 and 30.

[0087] Preferred monomeric or oligomeric amino-functional alkoxysilanes include: 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)-propyl]ethylenediamine, and oligomers obtained by condensing the above aminosilanes and oligomerizing them optionally with alkylalkoxysilanes, particularly methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, and octyltrimethoxysilane.

[0088] Preferably, the monomeric, oligomeric, or analogous compounds thereof contain an ethoxy group instead of a methoxy group.

[0089] When these silanes are used in the compositions of the present invention, they have the advantage of improving both the adhesion of the composition to various substrates and the curing speed of the composition without impairing its mechanical properties.

[0090] Furthermore, preferred organosilanes other than those of formula (I) are epoxy-functional or thiol-functional organosilanes. These silanes improve adhesion to various substrates.

[0091] These compositions may further contain at least one plasticizer in an amount of 0 to 40% by weight, preferably 5 to 25% by weight, and more preferably 7 to 15% by weight, based on the composition as a whole.

[0092] These plasticizers may be any plasticizers commonly used in compositions based on silane-functionalized polymers. Examples of such substances include: carboxylic acid esters, for example, phthalate esters, particularly dioctyl phthalate, bis(2-ethylhexyl) phthalate, bis(3-propylheptyl) phthalate, diisononyl phthalate, or diisodecyl phthalate; diesters of ortho-cyclohexane-dicarboxylic acid, particularly diisononyl 1,2-cyclohexanedicarboxylic acid; adipate esters, particularly dioctyl adipicate, bis(2-ethylhexyl) adipicate; azelaic acid esters, particularly bis(2-ethylhexyl) azelaic acid; sebacate esters, particularly bis(2-ethylhexyl) sebacate or diisononyl sebacate; glycol ethers, glycol esters, organophosphate esters or sulfonic acid esters; sulfonamides; polybutenes; or methyl or ethyl esters of fatty acids derived from natural oils and fats (also known as "biodiesel").

[0093] Even more preferable are polymeric plasticizers, which have the advantages of a lower tendency to migrate into the surrounding environment and a lower contribution to VOC levels.

[0094] The term "polymeric plasticizer" as used herein refers to polymeric additives that are liquid at room temperature and do not contain hydrolyzable silane groups. In contrast to conventional plasticizers such as phthalates, polymeric plasticizers generally have higher molecular weights.

[0095] The polymeric plasticizer has an average molecular weight M of 500 to 12,000 g / mol, particularly 1,000 to 10,000 g / mol, and more preferably 2,500 to 5,000 g / mol. n It is preferable that it has [this feature].

[0096] Suitable polymeric plasticizers include polyols, for example, those suitable for producing the organic polymer P described herein, provided that they are liquid at room temperature. Suitable polyols suitable as polymeric plasticizers include polyether polyols, polyester polyols, polyhydrocarbon polyols, polybutadiene polyols, and poly(meth)acrylate polyols. Particularly preferred are polyether polyols, especially those with an average molecular weight M of 500 to 12,000 g / mol, especially 1,000 to 10,000 g / mol, and more preferably 2,500 to 5,000 g / mol. n It possesses the following characteristics.

[0097] Such polyols are particularly suitable for combination with organic polymers P.

[0098] A major advantage of using polyether polyols as polymeric plasticizers is their exceptionally rapid adhesion development, particularly their excellent adhesion performance.

[0099] A particularly preferred embodiment of the polymeric plasticizer has, for example, terminally capped hydroxyl groups converted to ester groups.

[0100] The composition further includes a curing catalyst for curing the alkoxysilane, and in particular for crosslinking a polymer containing a silane group. Preferred catalysts are, in particular, metal-organic compounds and / or basic nitrogen or phosphorus compounds.

[0101] Suitable metal-organic compounds are, in particular, compounds of tin, titanium, zirconium, aluminum, or zinc, especially diorganosin(IV) compounds, for example, especially dibutyltin(IV) diacetate, dibutyltin(IV) dilaurate, dibutyltin(IV) dineodecanoate, or dibutyltin(IV) bis(acetylacetonate), and dioctyltin(IV) dilaurate, and furthermore, especially complexes of titanium(IV), zirconium(IV), aluminum(III), or zinc(II) with alkoxy, carboxylate, 1,3-diketonate, 1,3-ketoesterate, or 1,3-ketoamide ligands.

[0102] Suitable basic nitrogen or phosphorus compounds include, in particular, imidazoles, pyridines, phosphazene bases, or preferably amines, hexahydrotriazines, biguanides, guanidines, or further amidines.

[0103] In addition, the composition may contain an acid, particularly a carboxylic acid, as a co-catalyst. Preferred are: aliphatic carboxylic acids, such as formic acid, lauric acid, stearic acid, isostearic acid, oleic acid, 2-ethyl-2,5-dimethylcaproic acid, 2-ethylhexanoic acid, neodecanoic acid, mixtures of fatty acids from the hydrolysis of natural oils and fats, or di- and polycarboxylic acids, particularly poly(meth)acrylic acid.

[0104] In preferred embodiments, the composition is substantially free of organosin compounds. Organosin-free compositions are advantageous in terms of health and environmental protection. More specifically, the tin content of the curable composition is less than 0.1% by weight, and particularly less than 0.05% by weight, in some preferred embodiments. These embodiments are also beneficial to consumers, particularly due to the low levels of potentially harmful organosin compounds.

[0105] Suitable basic nitrogen or phosphorus compounds include, in particular, imidazoles, pyridines, phosphazene bases, secondary or tertiary amines, hexahydrotriazines, biguanides, guanidines, or amidines.

[0106] Suitable nitrogen-containing compounds as catalysts include, in particular: amines, especially N-ethyl-diisopropylamine, N,N,N',N'-tetramethylalkylenediamine, 1,4-diazabicyclo[2.2.2]octane; amidines, for example, especially 1,8-diazabicyclo[5.4.0]undes-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 6-dibutylamino-1,8-diazabicyclo-[5. 4.0] Undes-7-ene; Guanidines, for example, particularly tetramethylguanidine, 2-guanidino-benzimidazole, acetylacetone-guanidine, 3-di-o-tolyl-guanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine; and imidazoles, particularly N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole, and N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0107] The moisture-curable composition according to claims 1 to 7, characterized in that the curing catalyst for the alkoxysilane group is a metal organocatalyst, an amine compound, or a mixture thereof.

[0108] The composition may contain further components, in particular the following auxiliary agents and additives: - Adhesion promoters and / or crosslinking agents, particularly further aminosilanes, mercaptosilanes, epoxysilanes, (meth)acryloylsilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, oligomers of these silanes, adducts formed from primary aminosilanes and epoxysilanes, or (meth)acryloylsilanes, or anhydridosilanes, amino-functional alkylsilsesquioxanes, 3-glycidoxypropyltrimethoxysilanes, 3-glycidoxypropyltriethoxysilanes, or 3-ureidopropyltrimethoxysilanes, or oligomers of these silanes; - Desiccants or drying agents, particularly tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or organoalkoxysilanes having a functional group at the α-position relative to the silane group, particularly N-(methyldimethoxysilylmethyl)-O-methylcarbamate, (methacryloyloxymethyl)silane, methoxymethylsilane, orthoformate esters, calcium oxide, or molecular sieves, particularly vinyltrimethoxysilane or vinyltriethoxysilane; - Additional plasticizers, in particular reactive plasticizers in the form of monofunctional polysiloxanes or monofunctional organic polymers, i.e., those that are silane-reactive at only one end; - Solvent; - Inorganic or organic fillers, in particular optionally coated with fatty acids, especially stearic acid, such as natural, ground, or precipitated calcium carbonate, barite, talc, quartz powder, silica sand, dolomite, wollastonite, kaolin, calcined kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica including fine silica from a pyrolysis process, industrially produced carbon black, graphite, metal powders such as aluminum, copper, iron, silver, or steel, PVC powder, or hollow spherical objects; - Fibers, particularly glass fibers, carbon fibers, metal fibers, ceramic fibers, or polymer fibers, such as polyamide fibers or polyethylene fibers; - dye; - Pigments, especially titanium dioxide or iron oxide; - Rheological modifiers, particularly thickeners or thixotropic additives, particularly layered silicates such as bentonite, castor oil derivatives, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silica, cellulose ethers, or hydrophobically modified polyoxyethylenes; - Stabilizers against oxidation, heat, light, or UV irradiation; - Natural resins, oils and fats, such as rosin, shellac, linseed oil, castor oil, or soybean oil; - Preferably, non-reactive polymers that are solid at room temperature, such as homopolymers or copolymers of unsaturated monomers selected from the group including ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate, or alkyl (meth)acrylates, particularly polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene-vinyl acetate copolymer (EVA), or atactic poly-α-olefin (APAO); - Flame retardant substances, particularly the fillers listed above, aluminum hydroxide and magnesium hydroxide, or, particularly, organic phosphate esters, such as triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, isodecyldiphenyl phosphate, tris(1,3-dichloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroisopropyl) phosphate, tris(chloropropyl) phosphate, isopropylated triphenyl phosphate, isopropylated mono-, bis-, or tris(isopropylphenyl) phosphates at various levels, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or ammonium polyphosphate; - Surfactants, particularly wetting agents, leveling agents, deaerating agents, or defoamers; - Biocides, especially algaecides, fungicides, or substances that inhibit the growth of fungi; Furthermore, other substances commonly used in curable compositions. Certain components are preferably chemically or physically dried before being incorporated into the composition.

[0109] In preferred embodiments of the moisture-curing composition of the present invention, the composition further comprises a plasticizer, a filler, a thixotropic additive, a stabilizer, and / or a pigment.

[0110] The composition preferably contains, based on the whole composition, at least one desiccant or drying agent, most preferably vinyltrimethoxysilane, in an amount of 0.5 to 2.5% by weight, preferably 1 to 2% by weight. This range is advantageous for achieving optimal storage stability and skin formation time without making the cured product too hard and / or too brittle.

[0111] In a preferred embodiment, the composition includes at least one dehydrating agent and at least one adhesion promoter.

[0112] The composition is preferably manufactured and stored in a manner that eliminates moisture. Typically, it has storage stability if moisture (humidity) is eliminated in appropriate packaging or arrangement, for example, more specifically in bottles, canisters, pouches, buckets, tubs, or cartridges.

[0113] The composition may take the form of a one-component composition or a multi-component, particularly two-component, composition.

[0114] In this specification, "one component" refers to a composition in which all of its constituent components are stored in the same container in the form of a mixture and which can be cured using moisture.

[0115] In this specification, "two-component" refers to a composition in which the constituent components exist as two separate components, which are stored in separate containers. The two components are mixed together immediately before or during application of the composition, thereby selectively curing the mixed composition under the action of moisture (humidity).

[0116] Various second, or optionally additional components are mixed with the first component before or during application, particularly by means of a static mixer or a dynamic mixer.

[0117] The composition is applied (coated) in particular at ambient temperature, preferably within a temperature range of 0°C to 45°C, and especially within a temperature range of 5°C to 35°C, and cured under these conditions.

[0118] If appropriate during application, the crosslinking reaction of silane groups is initiated under the influence of moisture. Existing silane groups can condense with existing silanol groups to give siloxane groups (Si-O-Si groups). Existing silane groups can also be hydrolyzed upon contact with moisture to give silanol groups (Si-OH groups), which then undergo a subsequent condensation reaction to form siloxane groups (Si-O-Si groups). As a result of these reactions, the composition permanently hardens. Amidine of formula (I) or their reaction products accelerate this hardening.

[0119] If water is required for curing, this can come from the atmosphere (air humidity), or otherwise, the composition can be brought into contact with a water-containing component, for example by painting, using a smoothing agent, or by spraying. Alternatively, water or a water-containing component can be added to the composition at the time of application, for example, in the form of a water-containing or water-releasing liquid or paste. A paste is particularly preferred if the composition itself is in the form of a paste.

[0120] In curing by means of air humidity, the composition hardens from the outside inward, and a skin is initially formed on the surface of the composition. The "skin time" or "skin formation time" is an indicator of the curing rate of the composition. The curing rate is generally determined by various factors, such as the availability of water (e.g., relative air humidity) and temperature.

[0121] The composition is suitable for a wide range of applications, including: particularly as a paint, varnish, or primer; as a resin for manufacturing fiber composite materials; as rigid foams, flexible foams, molded articles, elastomers, fibers, films, or membranes; as potting compounds, sealants, adhesives, coatings, or paints for construction and industrial applications, such as seam seals, cavity seals, electrical insulation compounds, sprinkling compounds, joint sealants, and welds. Alternatively, it can be used as crimp seam sealant, assembly adhesive, body structure adhesive, glazing adhesive, sandwich element adhesive, lamination adhesive, window and facade film adhesive, laminate adhesive, packaging adhesive, wood adhesive, parquet adhesive, fixing adhesive, floor covering, floor coating, balcony coating, roof coating, concrete protective coating, parking lot coating, sealing, pipe coating, corrosion-resistant coating, textile coating, seismic damping element, sealing element, or spacing compound.

[0122] The composition is particularly suitable as an adhesive and / or sealant, especially for sealing joints and for elastic adhesive bonding in construction and industrial applications, and especially as an elastic coating with crack-bridging properties for protection and / or sealing of roofs, floors, balconies, parking lot floors, or concrete pipes.

[0123] Therefore, preferably, the composition is an adhesive, sealant, or coating.

[0124] The composition is most suitable for repairing or restoring painted, varnished, and / or lacquered substrates, particularly metals, coated metals, or painted, lacquered, and / or varnished metals.

[0125] This type of composition typically includes plasticizers, fillers, adhesion promoters and / or crosslinking agents, and dehydrating agents, as well as optionally further aids and additives.

[0126] For use as an adhesive or sealant, the composition is preferably of a paste-like viscosity having structural viscosity. Such a paste-like sealant or adhesive is applied to a substrate, in particular, by hand, by compressed air, or by battery-powered application from a standard cartridge, or by transport pump or extruder, or optionally by application robot, from a vat or hobock bucket.

[0127] For use as a coating, the composition preferably has the viscosity of a liquid at room temperature and possesses self-leveling properties. It may also have weak thixotropy, allowing it to be applied to slanted or vertical surfaces without immediately running off. It is applied, in particular, by means of rollers or brushes, or by pouring and leveling with, for example, a roller, scraper, or notched trowel.

[0128] In a preferred embodiment of the moisture-curable composition, the composition is sprayable. This means that its viscosity is quite low, and therefore the composition is sprayable. Surprisingly, the use of dimethyl glutarate helps to achieve such low viscosity.

[0129] When applying the composition, it is preferable to apply it to at least one type of substrate.

[0130] Suitable substrates include, in particular, the following: - Glass, glass ceramics, concrete, mortar, brick, tile, gypsum, and natural rocks such as limestone, granite, or marble; - Metals and alloys, such as aluminum, iron, steel, and non-ferrous metals, and furthermore, surface-finished metals and alloys, such as galvanized or chromium-plated metals, or surface-coated metals, such as aluminum coated with Kynar® or Duranar®; - Leather, textiles, paper, wood, resins, for example, wood-based materials bonded with phenolic resins, melamine resins or epoxy resins, resin-textile composite materials, and further polymer composite materials; - Plastics such as polyvinyl chloride (rigid and flexible PVC), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), polyester, poly(methyl methacrylate) (PMMA), epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyolefin (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymer (EPM) and ethylene / propylene / diene terpolymer (EPDM), and furthermore, fiber-reinforced plastics such as carbon fiber-reinforced plastic (CFP), glass fiber-reinforced plastic (GFP), and sheet molding compound (SMC), where these plastics may be surface-treated by plasma, corona, or flame means; - Coated substrates, such as powder-coated metals or alloys; - Paint, lacquer, or varnish, especially automotive topcoats.

[0131] If necessary, these substrates may be pre-treated before applying the composition, particularly by chemical and / or physical cleaning methods, or by applying an adhesion promoter, adhesion promoter solution, or primer.

[0132] Generally, surface pretreatment is not required before applying the composition. The composition exhibits excellent adhesion to a wide variety of materials that are unprimed, unpretreated, and even uncleaned.

[0133] Another aspect of the present invention is therefore a method for repairing a damaged, painted, varnished and / or lacquered object, comprising the following steps: (a) Optionally, remove paint, varnish, and / or lacquer from the damaged portion of the object; (b) Mechanically repairing or restoring the damaged portion of an object by using the moisture-curing composition described above to bond, seal, fill, or coat the damaged portion; (c) Curing the applied moisture-curing composition with air humidity or added water; (d) Reapplying paint, varnish, and / or lacquer over the repaired or restored portion of the object and over the cured composition thereof.

[0134] In step (d), it is preferable to reapply the paint, varnish, and / or lacquer by spraying.

[0135] In a preferred embodiment of the process described above, the damaged object to be painted, varnished, and / or lacquered is the body of a vehicle, particularly an automobile.

[0136] The compositions disclosed herein generally possess, in particular, excellent mechanical properties related to high tensile strength, high elongation at break, and high resistance to tear propagation, as well as moderate to high Shore A hardness and low extrusion force, thus providing easy coating, excellent storage stability during storage, and especially high topcoatability. This makes them particularly suitable as general-purpose elastic adhesives, sealants, fillers, and coatings in repair and restoration processes, especially on painted, lacquered, or varnished objects.

[0137] It is possible to bond or seal two identical substrates or two different substrates, particularly the aforementioned substrates.

[0138] After curing the composition using water, particularly water in the form of air humidity, and / or at least one suitable crosslinking agent, a cured composition is obtained.

[0139] The compositions of the present invention have exceptionally high topcoatability, particularly when used with paints, lacquers, and / or varnishes used as automotive topcoats, during or after curing. Furthermore, they typically have storage stability of at least 12 months in an unopened container.

[0140] Another aspect of the present invention is the use of the adhesive compositions described herein for adhesive bonding, coating, or sealing substrates.

[0141] By using the composition, articles can be obtained that are joined, sealed, or coated with the composition. These articles are particularly: building structures, particularly structures constructed by structural or civil engineering; industrially produced goods or consumer goods, particularly windows, household appliances, or transportation systems, for example, more specifically, passenger cars, buses, trucks, railway vehicles, ships, aircraft, or helicopters. Alternatively, the articles may be components that can be mounted thereon.

[0142] Another aspect of the present invention is a substrate that is adhesively sealed, coated, filled, or bonded with an adhesive composition described herein. [Examples]

[0143] The following descriptions are examples intended to illustrate the invention as described in detail. It will be understood that the invention is not limited to these described examples.

[0144] The term "standard climate conditions" refers to a temperature of 23±1°C and a relative humidity of 50±5%.

[0145] Test method: Tensile strength and elongation at break were determined for a 2 mm thick cured film that was stored for 7 days under standard climate conditions after curing, according to DIN EN 53504 (tensile speed: 200 mm / min).

[0146] Tear propagation resistance was determined for a 2 mm thick film after curing for 7 days under standard climatic conditions, according to DIN 53515.

[0147] To determine the extrusion force, the composition was divided into internally coated aluminum cartridges (outer diameter 46.9 mm, inner diameter 46.2 mm, length 215 mm, metric ISO thread M15 × 1.5 mm) and airtightly sealed with a polyethylene stopper (diameter 46.1 mm) (manufactured by Novelis Germany GmbH). After conditioning at 23°C for 24 hours (or heating aging at 60°C for 14 days, followed by acclimatization at 23°C for 4 hours), the cartridges were opened and their contents were extruded using an extruder. For this purpose, a nozzle with an inner diameter opening of 2 mm was screwed onto the cartridge threads. Using an extruder (Zwick / Roell Z005), the force required to extrude the composition at an extrusion speed of 60 mm / min was measured. The reported values ​​are the average force measured after extruding distances of 22 mm, 24 mm, 26 mm, and 28 mm. The measurement was stopped after an extrusion distance of 30 mm.

[0148] Shore A hardness was determined according to DIN 53505, using test specimens with a layer thickness of 6 mm after curing for 7 days under standard climatic conditions.

[0149] To determine the skin formation time (the time until a tack-free surface is achieved, "tack-free time"), a small amount of the test adhesive composition (either stored at 23°C for 24 hours before the test, or simulated aging at 60°C for 7 days in a sealed container, followed by acclimatization at 23°C for 4 hours) was applied to a 3mm thick layer on a cardboard sheet under conditions of 23°C and 50% relative humidity. The surface of the curing adhesive was then lightly tapped using an LDPE pipette, and the time taken was measured. The tack-free time is the first time when no adhesive residue remains on the pipette.

[0150] Adhesion testing using a grid was performed according to the following procedure: An aluminum plate was thoroughly cleaned with heptane and pre-treated with Sika® Aktivator-205 (manufactured by Sika Schweiz) to ensure that all compositions adhered properly to it during the test protocol. Wooden spacers (3.5 mm thick) were placed on the aluminum sheet, and the composition was applied to the aluminum surface between the spacers. After removing excess composition with a spatula, a smooth 3.5 mm layer of fresh composition was formed on the aluminum plate. After curing at 23°C and 50% relative humidity for 24 hours, each automotive paint was sprayed onto the cured composition according to the instructions for use of each paint. After the paints were dried, a clear coat (according to the paint manufacturer's instructions) was applied by spraying. The entire multi-layered paint, including the clear coat, was then completely dried in an oven at 60°C for 40 minutes.

[0151] Subsequently, a cross-cutting procedure was initiated on the paint covering the cured composition. This was done by using a thin knife to make six horizontal and six vertical cuts across the entire surface of the paint, with a distance of 1 mm between each cut. This created a 6x6 grid of lines perpendicular to each other at a 90-degree angle. This procedure was performed on paint layers with a thickness of 61–120 micrometers, according to ISO 2409 (2007). Then, pressure-sensitive tape was pressed firmly onto the cut areas. Within five minutes of applying the tape, its free end was grasped and it was quickly peeled off at an angle of approximately 45–60 degrees.

[0152] The adhesion of the paint to the sealant beads was strictly evaluated according to the description in ISO 2409 (2007): GT0: The cut edges are perfectly smooth, and the grid squares are not peeling at all. GT1: Small pieces of coating peeled off at the intersection of the cuts. Less than 5% of the cross-cuts were affected. GT2: Coating delamination along the edges of the cuts and / or at the intersections. A cross-cut area greater than 5% but less than 15% is affected. GT3: Coating peels off in large ribbon-like strips, partially or entirely, along the edges of the cut, and / or partially or entirely, in different parts of a square. A cross-cut area larger than 15% but less than 35% is affected. GT4: Along the edges of the cut, the coating peels off in large ribbon-like patches, and / or several squares peel off partially or completely. A cross-cut area larger than 35% and smaller than 65% is affected. GT5: Classification: A degree of separation that cannot be fully classified in GT4.

[0153] The results of this measurement are shown in Tables 4 and 5 as % adhesion, where classification GT0 is represented as 100%. In Table 4 or 5, for example, a value of 85% corresponds to classification GT2.

[0154] [Table 1]

[0155] Preparation of polymer P containing reactive silane groups: Polymer STP: After removing moisture (humidity), 1000 g of Acclaim® 12200 polyol (polyoxypropylene diol with low levels of unsaturation, manufactured by Covestro; OH value, 11.0 mg KOH / g), 43.6 g of isophorone diisocyanate (IPDI; Vestanet® IPDI, manufactured by Evonik), 126.4 g of diisodecyl phthalate (DIDP), and 0.12 g of dibutyltin dilaurate (DBTDL) were heated to 90°C with continuous stirring, and maintained at this temperature until the content of free isocyanate groups, determined by titration, reached a stable value of 0.63% by weight. Next, 63.0 g of N-(3-trimethoxysilylpropyl)-aminosuccinate diethyl (an adduct formed from 3-aminopropyltrimethoxysilane and diethyl maleate; prepared according to U.S. Patent No. 5,364,955) was mixed in, and the mixture was stirred at 90°C by FT-IR spectroscopy until no free isocyanates were detected. The resulting polyether containing trimethoxysilane groups with a silane equivalent of approximately 6880 g / eq (calculated from the amount used) was cooled to room temperature, moisture was removed, and it was stored.

[0156] Preparation of thixotropic additives: First, 1000 g of diisodecyl phthalate (Palatinol® Z, manufactured by BASF SE (Germany)) and 160 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44 MCL, manufactured by Bayer MaterialScience AG (Germany)) were charged into a vacuum mixer and gently heated. Next, 90 g of monobutylamine was gradually added dropwise while vigorously stirring. The resulting white paste was continued to stir under reduced pressure and cooled for a further 1 hour. The resulting thixotropic additive contained 20% by weight of the thixotropic agent in 80% by weight of diisodecyl phthalate and was used in the formulation without further processing.

[0157] Compositions based on polymers containing reactive silane groups: In Tables 2-9, reference examples (not related to the present invention) are indicated with "Ref.". The compounds used are those specified in Table 1.

[0158] Compositions C1-C17: A series of example compositions were prepared by mixing the components shown in Tables 2, 3, 6, and 8 in a vacuum mixer under a nitrogen atmosphere. First, polymer P, plasticizer, and dialkyl ester (e.g., DMG, if used), thixotropy additive, and VTMO (if used) were thoroughly mixed over 5 minutes. Next, the dried filler was added while kneading at 60°C for 15 minutes. Heating was stopped, silane OS (if used), and further silanes and catalysts were added, and the composition was then processed under vacuum for 10 minutes to obtain a homogeneous paste. The paste was then filled into an aluminum spreading piston cartridge with an internal coating, sealed, and stored under standard climatic conditions for at least 24 hours before the test protocol was applied.

[0159] [Table 2]

[0160] [Table 3]

[0161] These results clearly demonstrate that the compositions of the present invention exhibit significantly improved topcoatability in all automotive paints tested. The mechanical properties of the compositions of the present invention are not affected by the compositional adjustments of the present invention. Furthermore, the embodiments of the present invention exhibit significantly lower extrusion forces compared to the reference example, which is advantageous in terms of the ease of application (coating) and sprayability (aerosolability) of the compositions.

[0162] The test results are shown in Tables 4 and 5:

[0163] [Table 4]

[0164] [Table 5]

[0165] Further experiments were conducted to investigate the effects of changing the carboxylic acid ester. These compositions C9 to C12 are shown in Table 6.

[0166] Table 7 shows some of the measurement results for the compositions in these examples.

[0167] Table 7 shows that the diisobutyl ester of aliphatic C3-C5 dicarboxylic acid (Experiment C10) exhibits significant inactivation of the hardening mechanism after heat storage in a sealed container (aging simulation). This can be observed from the significantly longer tack-free time after heat storage. Another ester not according to the present invention (Experiment C11) shows a much higher extrusion force value, which is even higher after heat storage.

[0168] [Table 6]

[0169] [Table 7]

[0170] Tables 8 and 9 show additional experiments to further investigate the effects of different dimethyl esters of dicarboxylic acids and their mixtures. These compositions C13–C17 are shown in Table 8.

[0171] Table 9 shows some of the measurement results for the compositions of these examples.

[0172] Table 9 shows that increasing the amount of dimethyl glutarate (compared to dimethyl adipicate) increases tensile strength and elongation at break, while decreasing the extrusion force. There is no significant effect on tack-free time, Shore A, and coatability. Experiment C17, using dimethyl succinate, shows lower elongation and a slightly higher extrusion force compared to samples containing a significant amount of dimethyl glutarate.

[0173] [Table 8]

[0174] [Table 9] This disclosure includes the following embodiments of the invention: <Aspect 1> A moisture-curing composition containing the following: - At least one organic polymer P containing a reactive silane group; - Based on the entire composition, 1.0% to 25.0% by weight, preferably 2.0% to 20% by weight, and particularly 2.5% to 10% by weight, of dimethyl or diethyl esters of aliphatic C3-C5 dicarboxylic acids; and - At least one curing catalyst for an alkoxysilane group. <Aspect 2> The moisture-curable composition according to embodiment 1, characterized in that the organic polymer P containing a reactive silane group is polyurethane, polyolefin, polyester, polycarbonate, polyamide, poly(meth)acrylate, or polyether, or a mixture thereof. <Aspect 3> The moisture-curable composition according to embodiment 1 or 2, characterized in that the composition further comprises 0.1% to 5% by weight, preferably 0.25% to 2.5% by weight, of the organosilane OS of the following formula (I), based on the entire composition: R a -Si(OCH 3 ) 3 (I) (In the formula, R a (These are aliphatic, alicyclic, or aromatic C4-C12 alkyl groups that optionally contain an ether oxygen or a secondary amino group.) <Aspect 4> The moisture-curable composition according to embodiment 3, characterized in that the organosilane OS is N-(n-butyl)-3-aminopropyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, or a mixture thereof. <Aspect 5> The moisture-curable composition according to embodiment 3 or 4, characterized in that the composition comprises 2.5% to 10% by weight of a dimethyl or diethyl ester of an aliphatic C3-C5 dicarboxylic acid, particularly dimethyl glutarate, and 0.25% to 2.5% by weight of the organosilane OS. <Aspect 6> A moisture-curable composition according to any one of embodiments 1 to 5, characterized in that the composition further comprises 0.5 to 2.5% by weight of an organosilane not conforming to formula (I) as described in embodiment 3, based on the entire composition. <Aspect 7> The moisture-curable composition according to any one of embodiments 1 to 6, characterized in that the composition further comprises at least one further additive selected from the group consisting of plasticizers and diluents, fillers, thixotropic additives, stabilizers, drying agents, and pigments. <Aspect 8> A moisture-curable composition according to any one of embodiments 1 to 7, characterized in that the curing catalyst for the alkoxysilane group is a metal organocatalyst, an amine compound, or a mixture thereof. <Pattern 9> A moisture-curable composition according to any one of embodiments 1 to 8, characterized in that the dimethyl or diethyl ester of the aliphatic C3-C5 dicarboxylic acid contains at least 50% by weight, preferably at least 75% by weight, and particularly at least 90% by weight of dimethyl glutarate, based on the total amount of aliphatic C3-C5 dicarboxylic acid esters contained in the composition. <Aspect 10> A moisture-curable composition according to any one of embodiments 1 to 9, characterized in that the organic polymer P is contained in the composition in an amount of 10% to 60% by weight based on the entire composition. <Aspect 11> A moisture-curable composition according to any one of embodiments 1 to 10, characterized in that it is sprayable. <Aspect 12> A method for repairing damaged, painted, varnished, and / or lacquered objects, including the following steps: (a) optionally remove the paint, varnish, and / or lacquer from the damaged portion of the object; (b) Mechanically repairing or restoring the damaged portion of the object by using a moisture-curing composition according to any one of embodiments 1 to 11 to bond, seal, fill, or coat the damaged portion; (c) Curing the applied moisture-curing composition with air humidity or added water; (d) Reapplying paint, varnish, and / or lacquer over the repaired or restored portion of the object and over the cured composition. <Aspect 13> The process according to embodiment 12, characterized in that in step (d), the paint, varnish, and / or lacquer is reapplied by spraying. <Aspect 14> The method according to embodiment 12 or 13, characterized in that the damaged, painted, varnished and / or lacquered object is the body of a vehicle, particularly the body of an automobile. <Aspect 15> Use of the moisture-curing composition according to any one of embodiments 1 to 11, for use in bonding, coating, filling, or sealing a substrate.

Claims

1. below: - At least one organic polymer P containing a reactive silane group; - Based on the entire composition, 1.0% to 25.0% by weight of dimethyl or diethyl esters of aliphatic C3-C5 dicarboxylic acids; and - At least one curing catalyst for alkoxysilane groups In a moisture-curing composition containing, The organic polymer P containing a reactive silane group is in the form of polyurethane, polyether, or a mixture thereof. The dimethyl or diethyl ester of the aliphatic C3-C5 dicarboxylic acid contains at least 90% by weight of dimethyl glutarate, based on the total amount of aliphatic C3-C5 dicarboxylic acid esters contained in the composition. A moisture-curing composition characterized by the following features.

2. The moisture-curing composition according to claim 1, characterized in that the composition further comprises 0.1% to 5% by weight of organosilane OS of the following formula (I), based on the entire composition: R ａ -Si(OCH ３ ) ３ (I) (In the formula, R ａ (This is an aliphatic or alicyclic C4-C12 alkyl group optionally containing an ether oxygen or a secondary amino group, or an aromatic group optionally containing an ether oxygen or a secondary amino group).

3. The moisture-curable composition according to claim 2, characterized in that the composition comprises 2.5% to 10% by weight of a dimethyl or diethyl ester of an aliphatic C3-C5 dicarboxylic acid and 0.25% to 2.5% by weight of the organosilane OS.

4. The composition contains, based on the entire composition, 0.5 to 2.5% by weight of formula (I) R ａ -Si(OCH ３ ) ３ (I) (In the formula, R ａ The moisture-curable composition according to any one of claims 1 to 3, further comprising an organosilane that does not conform to (optionally being an aliphatic or alicyclic C4-C12 alkyl group containing an ether oxygen or a secondary amino group, or an optionally C6-C12 aromatic group containing an ether oxygen or a secondary amino group).

5. The moisture-curable composition according to any one of claims 1 to 4, characterized in that the composition further comprises at least one further additive selected from the group consisting of plasticizers, diluents, fillers, thixotropic additives, stabilizers, drying agents, and pigments.

6. The moisture-curing composition according to any one of claims 1 to 5, characterized in that the organic polymer P is contained in the composition in an amount of 10% to 60% by weight based on the entire composition.

7. A method for repairing damaged, painted, varnished, and / or lacquered objects, including the following steps: (a) optionally removing the paint, varnish, and / or lacquer from the damaged portion of the object; (b) Mechanically repair or restore the damaged portion of the object by using the moisture-curing composition according to any one of claims 1 to 6 to bond, seal, fill, or coat the damaged portion; (c) Curing the applied moisture-curable composition with air humidity or added water; (d) Reapplying paint, varnish, and / or lacquer over the repaired or restored portion of the object and over the cured composition.

8. The method according to claim 7, characterized in that in step (d), the paint, varnish, and / or lacquer is reapplied by spraying.

9. The method according to claim 7 or 8, characterized in that the damaged painted, varnished and / or lacquered object is the body of a vehicle.

10. Use of the moisture-curing composition according to any one of claims 1 to 6, for use in bonding, coating, filling, or sealing a substrate.

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