DE102010000705A1 - Curable composition, useful e.g. as adhesives, comprises a polyether and/or a polyacrylic acid ester, a tin organic compound and a compound that does not contain tin- and silicon atoms and contains two functions e.g. hydroxy group - Google Patents

Abstract

Curable composition comprises: (a) at least one polyether and/or at least one polyacrylic acid ester with at least one terminal group (I); (b) at least one tin organic compound; and (c) at least one compound that does not contain tin- and silicon atoms and contains at least two functions comprising carboxy-, carbonyl- or hydroxy-group, or nitrogen atoms that are part of a ring system with aromatic character. Curable composition comprises: (a) at least one polyether and/or at least one polyacrylic acid ester with at least one terminal group of formula (A n-R-SiXY1Z) (I); (b) at least one tin organic compound; and (c) at least one compound that does not contain tin- and silicon atoms and contains at least two functions comprising carboxy-, carbonyl- or hydroxy-group, or nitrogen atoms that are part of a ring system with aromatic character. A : divalent linking group; R : divalent optionally a heteroatom containing 1-12C-hydrocarbon residue; X, Y1, Z : 1-8C-alkyl, 1-8C-alkoxy or 1-8C-acyloxy, where at least one of X, Y1, Z is 1-8C-alkyl, 1-8C-alkoxy or 1-8C-acyloxy; and n : 0 or 1. An independent claim is included for producing the curable composition, comprising mixing the components (a), (b) and (c).

Description

The invention relates to delayed-setting compositions based on silyl-terminated polymers, a process for their preparation and their use in adhesives, sealants and coating materials.

One-component, moisture-curing adhesives and sealants have played a significant role in numerous technical applications for many years. In addition to the polyurethane adhesives and sealants with free isocyanate groups and the traditional silicone adhesives and sealants based on dimethylpolysiloxanes, the so-called silane-modified adhesives and sealants have increasingly also been used recently. Compared to the polyurethane adhesives and sealants, the silane-modified adhesives and sealants have the advantage that they are free of isocyanate groups, in particular of monomeric diisocyanates. Furthermore, they are characterized by a broad adhesion spectrum on a variety of substrates without surface pretreatment by primer.

Polymer systems which have reactive silyl groups are therefore known in principle. In the presence of atmospheric moisture, polymers which have silyl groups with hydrolyzable substituents are capable, even at room temperature, of condensing with elimination of the hydrolyzed radicals. Depending on the content of silyl groups with hydrolyzable substituents and the structure of these silyl groups, mainly long-chain polymers (thermoplastics), relatively wide-mesh, three-dimensional networks (elastomers) or highly crosslinked systems (thermosets) are formed. The polymers usually have an organic skeleton which z. B. carries alkoxy or Acyloxysilylgruppen. The organic skeleton may be, for example, polyurethanes, polyesters, polyethers, etc.

In order to allow a rapid curing of the compositions after bonding, curing formulations are usually added to the formulations, which are usually metal organyls, for example based on tin or iron. On the one hand, the rapid curing of the compositions is desirable in order to be able to rapidly produce a stable bond between two substrates. On the other hand, fast-curing systems offer only a short processing phase and thus only short-term correction options immediately after use, which in individual cases overwhelms the users. It is therefore desirable to have a suitable processing phase followed by rapid curing.

DE-OS 1956672 describes multicomponent adhesives based on polyisocyanates and polyhydroxy compounds containing an organotin curing rate catalyst and a time-catalysis modifier selected from the group consisting of β-dicarbonyl compounds, α-hydroxy ketones, fused aromatic β-hydroxy ketones and nitrogen heterocyclic, condensed aromatic β-hydroxy compounds were added. However, such compositions no longer meet the requirements of modern adhesives, for example with regard to the adhesive spectrum or the elastic properties.

EP 0549210 A2 describes thermoformable compositions containing polymers with hydrolyzable silyl groups, through which post cure following thermal deformation is achieved. The polymers are polyolefins in which olefinically unsaturated silanes are copolymerized. In order to prevent embrittlement from thermal deformation, in addition to the silane condensation catalyst, an organic functional compound having at least one amino or carboxy group in addition to at least one hydroxy group is added. The compositions of EP 0549210 A2 give moldings such as cable sheathing and are not particularly suitable because of their low elasticity as adhesives or sealants.

There is therefore a need for adhesives, sealants and coating materials which combine a broad adhesion spectrum and good elasticity values with further advantageous properties. It is therefore an object of the present invention to provide a crosslinkable composition which forms the basis for adhesives, sealants and coating materials having a broad adhesion spectrum and good elasticity values, as well as a user-friendly, extended processing phase and subsequently as short a curing time as possible.

• a) mindestens einen Polyether und/oder mindestens einen Polyacrylsäureester mit mindestens einer Endgruppe der allgemeinen Formel (I) -A_n-R-SiXYZ (I), worin A eine zweibindige Bindegruppe, R ein zweibindiger gegebenenfalls ein Heteroatom enthaltender Kohlenwasserstoffrest mit 1-12 C-Atomen, und X, Y, Z unabhängig voneinander C₁-C₈-Alkyl-, C₁-C₈-Alkoxy- oder C₁-C₈-Acyloxyreste sind, wobei mindestens einer der Reste eine C₁-C₈-Alkoxy- oder C₁-C₈-Acyloxygruppe ist, und n 0 oder 1 ist; sowie
• b) mindestens eine zinnorganische Verbindung,
• c) mindestens eine Verbindung, die frei von Zinn- und Siliziumatomen ist und die mindestens zwei Funktionen aufweist, die jeweils ausgewählt sind aus: Carboxy-, Carbonyl-, Hydroxygruppen sowie Stickstoffatomen, die Bestandteil eines Ringsystems mit aromatischem Charakter sind, umfasst.

The achievement of the object of the invention can be found in the claims. It consists essentially of a curable composition, as components

• a) at least one polyether and / or at least one polyacrylic acid ester having at least one end group of the general formula (I) -A _n -R-SiXYZ (I), where A is a divalent linking group, R is a divalent hydrocarbon radical optionally containing one heteroatom having 1-12 C atoms, and X, Y, Z are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy, wherein at least one of the radicals is a C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy group, and n is 0 or 1; such as
• b) at least one organotin compound,
• c) at least one compound which is free of tin and silicon atoms and which has at least two functions, each of which is selected from: carboxy, carbonyl, hydroxy groups and nitrogen atoms which are part of a ring system having an aromatic character comprises.

Such a composition exhibits excellent adhesive properties on a wide variety of substrates, allows high elasticity bonds after cure, and leaves the user ample time for post-application corrections, with prolonged skin-over-time, but after this accelerated hardened. The bonds produced with such a composition therefore exhibit good strength values after curing, which indicate a stable and resilient bond.

• a) mindestens einen Polyether und/oder mindestens einen Polyacrylsäureester mit mindestens einer Endgruppe der allgemeinen Formel (I) -A_n-R-SiXYZ (I), worin A eine zweibindige Bindegruppe, R ein zweibindiger gegebenenfalls ein Heteroatom enthaltender Kohlenwasserstoffrest mit 1-12 C-Atomen, und X, Y, Z unabhängig voneinander C₁-C₈-Alkyl-, C₁-C₈-Alkoxy- oder C₁-C₈Acyloxyreste sind, wobei mindestens einer der Reste eine C₁-C₈-Alkoxy- oder C₁-C₈-Acyloxygruppe ist, und n 0 oder 1 ist; sowie
• b) mindestens eine zinnorganische Verbindung,
• c) mindestens eine Verbindung, die frei von Zinn- und Siliziumatomen ist und die mindestens zwei Funktionen aufweist, die jeweils ausgewählt sind aus: Carboxy-, Carbonyl-, Hydroxygruppen sowie Stickstoffatomen, die Bestandteil eines Ringsystems mit aromatischem Charakter sind, wobei das Ringsystem mit aromatischem Charakter ein Stickstoffatom als einziges Heteroatom enthält, umfasst.

According to the invention, a curable composition which is used as components

• a) at least one polyether and / or at least one polyacrylic acid ester having at least one end group of the general formula (I) -A _n -R-SiXYZ (I), where A is a divalent linking group, R is a divalent hydrocarbon radical optionally containing one heteroatom having 1-12 C atoms, and X, Y, Z are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy, wherein at least one of the radicals is a C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy group, and n is 0 or 1; such as
• b) at least one organotin compound,
• c) at least one compound which is free of tin and silicon atoms and which has at least two functions which are each selected from: carboxy, carbonyl, hydroxyl groups and nitrogen atoms which are part of a ring system having an aromatic character, wherein the ring system with aromatic character containing a nitrogen atom as a single heteroatom includes.

• a) mindestens einen Polyether und/oder mindestens einen Polyacrylsäureester mit mindestens einer Endgruppe der allgemeinen Formel (I) -A_n-R-SiXYZ (I), worin A eine zweibindige Bindegruppe, R ein zweibindiger gegebenenfalls ein Heteroatom enthaltender Kohlenwasserstoffrest mit 1-12 C-Atomen, und X, Y, Z unabhängig voneinander C₁-C₈-Alkyl-, C₁-C₈-Alkoxy- oder C₁-C₈-Acyloxyreste sind, wobei mindestens einer der Reste eine C₁-C₈-Alkoxy- oder C₁-C₈-Acyloxygruppe ist, und n 0 oder 1 ist; sowie
• b) mindestens eine zinnorganische Verbindung,
• c) mindestens eine Verbindung, die frei von Zinn- und Siliziumatomen ist und die mindestens zwei Funktionen aufweist, von denen eine ausgewählt ist aus Carboxy-, Carbonyl-, Hydroxygruppen und bevorzugt eine Hydroxygruppe ist und die zweite entweder ein Stickstoffatom als Bestandteil eines Ringsystems mit aromatischem Charakter ist, wobei das Ringsystem bevorzugt ein Stickstoffatom als einziges Heteroatom enthält, oder eine Carboxygruppe ist, umfasst.

Particularly preferred is a curable composition, which as components

• a) at least one polyether and / or at least one polyacrylic acid ester having at least one end group of the general formula (I) -A _n -R-SiXYZ (I), where A is a divalent linking group, R is a divalent hydrocarbon radical optionally containing one heteroatom having 1-12 C atoms, and X, Y, Z are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy, wherein at least one of the radicals is a C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy group, and n is 0 or 1; such as
• b) at least one organotin compound,
• c) at least one compound which is free of tin and silicon atoms and which has at least two functions, one of which is selected from carboxy, carbonyl, hydroxy groups and preferred is a hydroxy group and the second one is either a nitrogen atom as part of a ring system of aromatic character, the ring system preferably containing a nitrogen atom as a single heteroatom, or a carboxy group.

A curable composition is understood to mean a substance or a mixture of several substances which is curable by physical or chemical measures. These chemical or physical measures, for example, in the supply of energy in the form of heat, light or other electromagnetic radiation, but also in the most simple contact with atmospheric moisture, water or a reactive component.

A polyether is understood as meaning a polymer whose organic repeating units contain ether functionalities C-O-C in the main chain. Thus, polymers containing pendent ether groups, such as, for example, the cellulose ethers, starch ethers and vinyl ether polymers, are not included among the polyethers. Also polyacetals such as the polyoxymethylene (POM) are generally not counted among the polyethers.

A polyacrylic acid ester is understood as meaning a polymer based on acrylic acid esters, which therefore has as repeat unit the structural motif -CH ₂ -CH (COOR) -, in which R is linear, branched, cyclic and / or functional substituent-containing alkyl radicals, for example Methyl, ethyl, isopropyl, cyclohexyl, 2-ethylhexyl or 2-hydroxyethyl radicals.

The / the polyether and / or polyacrylic acid ester of component a) has / have at least one end group of the general formula I. -A _n -R-SiXYZ (I) on. A divalent or divalent bonding group A is a divalent chemical group which links the polymer skeleton of the alkoxy- and / or acyloxysilane-terminated polymer with the radical R of the end group. The divalent linking group A can be formed, for example, in the preparation of the alkoxy- and / or acyloxysilane-terminated polyether and / or polyacrylate polymer, for example as a urethane group by the reaction of a hydroxyl-functionalized polyether with an isocyanatosilane. In this case, the divalent binding group of structural features occurring in the underlying polymer backbone can be both distinguishable and indistinguishable. The latter is, for example, if it is identical to the points of attachment of the repeat units of the polymer backbone.

n is 0 or 1, d. H. the divalent linking group A links the polymer backbone with the radical R (n = 1) or the polymer backbone is directly linked or linked with the radical R (n = 0). The radical R is a divalent, optionally containing a heteroatom hydrocarbon radical having 1 to 12 carbon atoms. As heteroatom, for example, oxygen (O) or nitrogen (N) may be included. The hydrocarbon radical may be, for example, a straight-chain or branched or cyclic, substituted or unsubstituted alkylene radical. The hydrocarbon radical may be saturated or unsaturated.

X, Y and Z are independently C ₁ -C ₈ -alkyl radicals, C ₁ -C ₈ -alkoxy radicals or C ₁ -C ₈ -acyloxy radicals. At least one of the radicals X, Y, Z must be a hydrolyzable group, that is to say a C ₁ -C ₈ alkoxy radical or a C ₁ -C ₈ acyloxy radical. As hydrolyzable groups, preference is given to alkoxy groups, in particular methoxy, ethoxy, propyloxy and butoxy groups. This is advantageous since no substances irritating the mucous membranes are released during the curing of compositions containing alkoxy groups. The alcohols formed are harmless in the released amounts and evaporate. Therefore, such compositions are particularly suitable for the home improvement sector. However, as hydrolyzable groups, acyloxy groups such as an acetoxy group -O-CO-CH ₃ may also be used.

The alkoxy- and / or acyloxysilane-terminated polyether and / or polyacrylic acid ester of the formula (I) preferably has at least two terminal groups of the general formula (I). Each polymer chain thus contains at least two linkage sites at which the condensation of the polymers can take place with elimination of the hydrolyzed radicals in the presence of atmospheric moisture. In this way, a regular and fast crosslinkability is achieved, so that bonds can be obtained with good strength. In addition, can be on the amount and structure of the hydrolyzable groups -. B. use of di- or Trialkoxysilylgruppen, methoxy groups or longer radicals, etc. - Design of the achievable network as a long-chain system (thermoplastics), relatively wide-meshed three-dimensional network (elastomers) or highly networked system (thermosets) control, so that among other things the elasticity, flexibility and heat resistance of the finished crosslinked compositions can be influenced.

Preferably, X is an alkyl group and Y and Z are each an alkoxy group, or X, Y and Z are each an alkoxy group. In general, polymers which contain di- or trialkoxysilyl groups have highly reactive attachment sites which enable rapid curing, high degrees of crosslinking and thus good final strengths. The particular advantage of dialkoxysilyl groups is that the corresponding compositions after curing are more elastic, softer and more flexible than systems containing trialkoxysilyl groups. They are therefore particularly suitable for use as sealants. In addition, they cease even less alcohol when curing and are therefore of particular interest when the amount of alcohol released is to be reduced. With trialkoxysilyl groups, on the other hand, a higher degree of crosslinking can be achieved, which is particularly advantageous if a harder, stronger mass is desired after curing. In addition, trialkoxysilyl groups are more reactive, ie they crosslink faster and thus reduce the required amount of catalyst, and they have advantages in the "cold flow" - the dimensional stability of a corresponding adhesive under the influence of force and possibly temperature.

Particularly preferably, X, Y and Z are each independently a methyl, an ethyl, a methoxy or an ethoxy group. Methoxy and ethoxy groups as relatively small hydrolyzable groups with low steric demand are very reactive and thus allow rapid curing even with low catalyst use. They are therefore particularly interesting for systems in which a rapid curing is desired, such as adhesives, which should have a high initial adhesion. Particularly preferably, X, Y and Z are a methyl or a methoxy group. Depending on the nature of the alkyl radicals on the oxygen atom, compounds having alkoxysilyl groups have different reactivities in chemical reactions. Within the alkoxy groups, the methoxy group shows the greatest reactivity. It is thus possible to resort to silyl groups of this type if particularly rapid curing is desired. Higher aliphatic radicals such as ethoxy bring about a lower reactivity of the terminal alkoxysilyl group compared to methoxy groups and can advantageously be used for the development of graduated crosslinking rates. Interesting design options also open up combinations of both groups. If, for example, X is chosen to be methoxy and Y is ethoxy within the same alkoxysilyl group, the desired reactivity of the terminal silyl groups can be set particularly finely, if only silyl groups carrying methoxy groups are perceived as too reactive and the ethoxy-bearing silyl groups too sluggish for the intended use.

In addition to methoxy and ethoxy groups, it is of course also possible to use larger radicals than hydrolyzable groups, which naturally have a lower reactivity. This is of particular interest, even if delayed curing is to be achieved via the design of the alkoxy groups.

R is preferably a hydrocarbon radical having 1 to 6 C atoms. The curing rate of the composition can also be influenced by the length of the hydrocarbon radicals which form the link between the polymer skeleton and the silyl radical. In particular, R is a methylene, ethylene or nPropylenrest. Methylene and 1,3-propylene radicals are particularly preferably used. Alkoxysilane-terminated compounds having a methylene group as a link to the polymer backbone - so-called α-silanes - have a particularly high reactivity of the final silyl group, which leads to shortened setting times and thus to a very rapid curing of formulations based on such polymers. In general, an extension of the connecting hydrocarbon chain leads to a reduced reactivity of the polymers. In particular, the γ-silanes - they contain the unbranched propylene radical as a link - have a balance between necessary reactivity (acceptable curing times) and delayed curing (open time, possibility of correction after bonding) on. By consciously combining α- and γ-alkoxysilane-terminated building blocks, the curing rate of the systems can thus be influenced as desired.

A is preferably an amide, carbamate, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group or an oxygen or nitrogen atom. The binding group A can be formed in the preparation of the silyl-terminated polymers by reacting the framework polymer with a reactive compound bearing the -R-SiXYZ sequence. Group A may be both distinguishable and indistinguishable from structural features occurring in the underlying polymer backbone. The latter is, for example, if it is identical to the points of attachment of the repeat units of the polymer backbone. In this case, n would correspond to the value 0. If the binding group A is distinguishable from the linking groups in the polymer backbone, n corresponds to the value 1.

Particularly preferred as a linking group are urethane and urea groups, which can be obtained by reacting certain functional groups of a prepolymer with an organosilane which carries a further functional group. Urethane groups can, for. B. arise when either the polymer backbone contains terminal hydroxyl groups and isocyanatosilanes used as a further component, or conversely, when a polymer having terminal isocyanate groups is reacted with a terminal hydroxy-containing alkoxysilane. Similarly, urea groups can be obtained when a terminal primary or secondary amino group - either on the silane or on the polyether and / or polyacrylic acid ester - is used which reacts with a terminal isocyanate group present in the respective reactant. This means that either an aminosilane with a terminal isocyanate-containing polyether and / or polyacrylic acid ester or a terminally substituted with an amino group polyether and / or polyacrylic acid ester is reacted with an isocyanatosilane. Urethane and urea groups advantageously increase the strength of the polymer chains and the entire crosslinked polymer because they can form hydrogen bonds.

Polymers containing polyether as a backbone have a flexible and elastic structure not only at the end groups but also in the polymer backbone. This can be used to produce compositions which have excellent elastic properties. Polyethers are not only flexible in their backbone but also stable at the same time. For example, they are not attacked or decomposed by water and bacteria. In the context of the present invention, polyethers based on polyethylene oxide and / or polypropylene oxide in component a) are particularly preferably used under availability aspects.

Component a) preferably contains at least one alkoxy- and / or acyloxysilane-terminated polyether which has a molecular weight M _n of 4,000 to 100,000, preferably 8,000 to 50,000, particularly preferably 10,000 to 30,000, in particular 15,000 to 25,000 g / mol. The molecular weight M _n is understood to mean the number average molecular weight of the polymer. For the purposes of the present invention, the number average molecular weight M _n as well as the weight average molecular weight M _{w are} determined by gel permeation chromatography (GPC). Such a method is known to the person skilled in the art. The stated molecular weights are particularly advantageous, since the corresponding compositions have a balanced ratio of viscosity (easy processability), strength and elasticity. This combination is very advantageous in a molecular weight range (M _n ) of 12,000 to 20,000, in particular 14,000 to 18,000, pronounced.

In the context of the present invention, component (a) preferably contains at least one polyether in which the ratio M _w / M _{n is} less than 1.5. The ratio M _w / M _n , which is also referred to as polydispersity, indicates the width of the molecular weight distribution and thus of the different degrees of polymerization of the individual chains in the case of polydisperse polymers. For many polymers and polycondensates, the polydispersity has a value of about 2. Strict monodispersity would be given at a value of 1. The preferred polydispersity in the context of the present invention of less than 1.5 indicates a comparatively narrow molecular weight distribution and thus the specific expression of the molecular weight related properties, such. As the viscosity, towards. Particularly preferably, at least one alkoxy and / or acyloxysilane-terminated polyether of component a) has a polydispersity (M _w / M _n ) of less than 1.3.

The polyether (s) preferably used in component (a) are furthermore preferably distinguished by a low number of double bonds at the ends of the polymer chain. This so-called terminal unsaturation results from an undesirable side reaction in the polymerization of low molecular weight diols with alkylene oxides. As a result, there is a certain proportion of mono-hydroxypolyethers which can only be silylated at one end of the chain and accordingly also cross-link only via one end of the chain. This has detrimental effects on the functionality of the polyethers and the compositions made therefrom. Polyethers with a low number of terminal double bonds can be prepared, for example, by the so-called double-metal cyanide catalysis (DMC catalysis). Component a) preferably contains at least one polyether having a terminal unsaturation of less than 0.07 meq / g, determined by the method ASTM D4671 , having.

The curable composition according to the invention contains as component b) at least one organotin compound. Component b) is added to the composition in particular as a crosslinking catalyst. Examples of suitable tin organyls are the 1,3-dicarbonyl compounds of di- or tetravalent tin, for example the acetylacetonates, such as di (n-butyl) tin (IV) di (acetylacetonate), di (n-octyl) tin (IV) di (acetylacetonate), (n-octyl) (n-butyl) tin (IV) di (acetylacetonate); the dialkyltin (IV) -dicarboxylates, for example di-n-butyltin dilaurate, di-n-butyltin maleate, di-n-butyltin diacetate, di-n-octyltin diacetate or the corresponding dialkoxylates, for example di-n-butyltin dimethoxide; and the tin (II) carboxylates such as stannous octoate or stannous phenolate. Also suitable are the following tin compounds: ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, di (n-butyl) tin (IV) di (methyl maleate), di (n-butyl) tin (IV) di (butyl maleate ), Di (n-octyl) tin (IV) di (methyl maleate), di (n-octyl) tin (IV) di (butyl maleate), di (n-octyl) tin (IV) di (iso-octyl maleate ), Di (n-butyl) tin (IV) sulfide, di (n-butyl) tin (IV) oxide, di (n-octyl) tin (IV) oxide, (n-butyl) ₂ Sn (SCH ₂ COO) , (n-octyl) ₂ Sn (SCH ₂ COO), (n-octyl) ₂ Sn (SCH ₂ CH ₂ COO), (n-octyl) ₂ Sn (SCH ₂ CH ₂ COOCH ₂ CH ₂ OCOCH ₂ S), (n-butyl) ₂ Sn (SCH ₂ COO-iC ₈ H ₁₇ ) ₂ , (n-octyl) ₂ Sn (SCH ₂ COO-iC ₈ H ₁₇ ) ₂ , (n-octyl) ₂ Sn (SCH ₂ COO-) nC ₈ H ₁₇ ) ₂ . Component b) is particularly preferably a dialkyltin (IV) -dicarboxylate, in particular di-n-butyltin dilaurate. The component b) is preferably used in an amount of 0.01 to 10 wt .-%, based on the total weight of the composition. It is also possible to use mixtures of several catalysts in order to combine advantageous effects.

As component c), the composition according to the invention comprises at least one compound which is free of tin and silicon atoms and which has at least two functions, each of which is selected from: carboxy, carbonyl, hydroxyl groups and nitrogen atoms which form part of a ring system having an aromatic character are. By carboxy groups are meant functionalities of the structure -COOH, functionalities of the structure -OH under hydroxy groups and functionalities of the structure C =O under carbonyl groups. The at least two functions or functional groups may in principle be the same or different. Preferably, at least one compound of component c) has at least two different functions, each of which is selected from carboxy, carbonyl, hydroxy and nitrogen atoms which are part of a ring system having an aromatic character. The abovementioned carboxy, carbonyl and hydroxy groups of component c) are considered in the context of the present invention as isolated functional groups and are not present as part of more complex functional groups. For example, a compound having only one carboxy group is not considered to be a component c) although the carboxy group contains both a carbonyl and a hydroxy group. Likewise, for example, carbonyl groups that are part of ester groups (-COOR) are considered as carbonyl groups in the sense of component c). In the case of nitrogen atoms as part of an aromatic ring system, only the nitrogen atoms themselves are considered to be the functional group and not the entire aromatic system. It may therefore be located at another point of the ring system with aromatic character quite a further functional group of component c), for example an OH group.

Suitable compounds of component c) are, for example, β-dicarbonyl compounds such as 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro- 2,4-pentanedione, 2,4-hexanedione, 2,4-pentanedione, 5-methyl-2,4-hexanedione, 2,4-octanedione, 5,5-dimethyl-2,4-hexanedione, 3-ethyl 2,4-pentanedione, 2,4-decanedione, 2,2-dimethyl-3,5-nonanedione, 3-methyl-2,4-pentanedione, 2,4-tridecanedione, 1-cyclohexyl-1,3-butanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, 1- (4-biphenyl) -1,3-butanedione, 1-phenyl-1,3- pentanedione, 3-benzyl-2,4-pentanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1-phenyl-2-butyl-1,3-butanedione, 1-phenyl-3-3 ( 2-methoxyphenyl) -1,3-propanedione, 1- (4-nitrophenyl) -1,3-butanedione, 1- (2-furyl) -1,3-butanedione, 1- (tetrahydro-2-furyl) -1 , 3-butanedione, dimedone and dibenzoylmethane.

A further group as component c) of suitable compounds form α-hydroxy ketones such as benzoin, acetoin and α-hydroxy-acetophenone and α-hydroxy carboxylic acids such as mandelic acid, lactic acid, citric acid, malic acid, ascorbic acid and tartaric acid, with lactic acid being particularly preferred , Further, condensed aromatic β-hydroxy ketones such as naphthazarin, 1-hydroxy-9-fluorenone or 1-hydroxyanthraquinone are suitable.

Nitrogen atoms which are part of a ring system having an aromatic character are understood as meaning nitrogen atoms which are present in addition to carbon atoms as a ring-forming atom in at least monocyclic structures which have aromaticity, ie have an arrangement of π-electrons corresponding to the Hückel rule. In the context of the present invention, in this context at least monosubstituted nitrogen-containing heteroaromatics and among these in particular condensed systems are suitable as component c), for example 8-hydroxyquinolines, 2-hydroxyquinolines, 7-hydroxy-3-H-indoles, 8-hydroxyquinoxalines, 8-hydroxyquinazolines, 8-hydroxycinnolines, 4-hydroxyphenanthridines, 4- Hydroxyacridines and 1-hydroxyphenazines, each of which may have further substituents, for example halogen atoms or alkyl groups.

The compositions according to the invention thus have at least one organotin compound and at least one compound of type c). Such a combination causes a delayed curing of the composition according to the invention. This gives the consumer the opportunity to make corrections even after the application and the compression of the substrates to be bonded, for example, to move the substrates against each other until reaching the desired positions. The curable composition according to the invention particularly preferably comprises, as component c), compounds which are capable of forming complexes of two or more ligands, in particular of chelate complexes, with the compound (s) of component b).

Preferably, at least one of the functions of at least one compound of component c) has at least one oxygen atom and at least one other function has at least one nitrogen atom which is part of a ring system having an aromatic character, or at least two functions of a compound of component c) each have at least an oxygen atom, wherein at least one carbon atom bonded directly to this oxygen atom has a different oxidation state than at least one carbon atom of the second function bonded directly to this oxygen atom. Particularly suitable in this sense, for example, β-hydroxy ketones or α-hydroxycarboxylic acids.

Particularly preferably, component c) comprises at least one N-heteroaromatic compound or an α-hydroxy carboxylic acid, in particular 8-hydroxyquinoline or lactic acid. The preferred molar ratio (mol / mol) of the total amount of compound (s) of component c) to the total amount of compound (s) of component b) is 1:10 to 10: 1, particularly preferably 1: 5 to 5: 1, in particular 1: 4 to 4: 1 and most preferably 1: 3 to 3: 1. The proportion by weight of the sum of components b) and c) in the composition according to the invention is preferably up to 5% by weight, in particular up to 3% by weight and very particularly preferably up to 2% by weight, in each case based on the total weight the composition.

The compositions according to the invention which are suitable as adhesives, sealants or coating materials, in addition to the abovementioned components a), b) and c), optionally also contain other auxiliaries and additives which give them, for example, improved elastic properties, improved resilience and low residual tack to lend. These auxiliaries and additives include adhesion promoters, plasticizers and fillers. In addition, the compositions may contain, as further additives, stabilizers, antioxidants, reactive diluents, drying agents, UV stabilizers, anti-aging agents, rheological aids, color pigments or color pastes, fungicides, flameproofing agents and / or, to a lesser extent, solvents.

By a plasticizer is meant a substance which reduces the viscosity of the compositions, thereby facilitating processability and, moreover, improving the flexibility and extensibility of the compositions.

The plasticizer is preferably selected from a fatty acid ester, a dicarboxylic acid ester, an ester OH groups or epoxidized fatty acids, a fat, a glycolic acid ester, a phthalic acid ester, a benzoic acid ester, a phosphoric acid ester, a sulfonic acid ester, a trimellitic acid ester, an epoxidized plasticizer, a polyether Plasticizer, a polystyrene, a hydrocarbon plasticizer and a chlorinated paraffin, and mixtures of two or more thereof. By the specific selection of one of these plasticizers or a specific combination, further advantageous properties of the composition according to the invention, for. B. gelling the polymers, cold elasticity or cold resistance or antistatic properties can be realized.

For example, from the group of phthalic acid esters dioctyl phthalate, dibutyl phthalate, diisoundecyl phthalate, diisononyl phthalate or butyl benzyl phthalate, of the adipates dioctyl adipate, diisodecyl adipate, furthermore diisodecyl succinate, dibutyl sebacate or butyl oleate. Of the polyether plasticizers, end-capped polyethylene glycols are preferably used, for example polyethylene or polypropylene glycol di-C _1-4 -alkyl ethers, in particular the dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof. Also suitable as plasticizers are, for example, esters of abietic acid, butyric acid esters, acetic acid esters, propionic acid esters, thiobutyric acid esters, citric acid esters and esters based on nitrocellulose and polyvinyl acetate, and mixtures of two or more thereof. Also suitable, for example, are the asymmetric esters of adipic acid monooctyl ester 2-ethylhexanol (Edenol DOA, Cognis Germany GmbH, Dusseldorf). In addition, suitable plasticizers are the pure or mixed ethers of monofunctional, linear or branched C _4-16 alcohols or mixtures of two or more different ethers of such alcohols, for example dioctyl ether (available as Cetiol OE, from Cognis Deutschland GmbH, Dusseldorf). Likewise suitable as plasticizers in the context of the present invention are diurethanes which can be prepared, for example, by reacting diols having OH end groups with monofunctional isocyanates, by selecting the stoichiometry such that essentially all free OH groups react. Optionally, excess isocyanate can then be removed from the reaction mixture, for example, by distillation. Another method for the preparation of diurethanes is the reaction of monofunctional alcohols with diisocyanates, where possible all of the NCO groups react.

A viscosity of the composition according to the invention, which is too high for certain applications, can also be reduced in a simple and expedient manner by using a reactive diluent, without there being any demixing phenomena (eg plasticizer migration) in the hardened mass. Preferably, the reactive diluent has at least one functional group which, for example, reacts after application with moisture or atmospheric oxygen. Examples of such groups are silyl groups, isocyanate groups, vinyl unsaturated groups and polyunsaturated systems. As reactive diluents it is possible to use all compounds which are miscible with the composition according to the invention with reduction in viscosity and have at least one group reactive with the binder, alone or as a combination of several compounds. The viscosity of the reactive diluent is preferably less than 20,000 mPas, particularly preferably about 0.1-6,000 mPas, very particularly preferably 1-1,000 mPas (Brookfield RVT, 23 ° C., spindle 7, 10 rpm).

As Reaktiwerdünner can be z. For example, the following substances are used: polyalkylene glycols reacted with isocyanatosilanes (eg Synalox 100-50B, DOW), alkyltrimethoxysilane, alkyltriethoxysilane, such as methyltrimethoxysilane, methyltriethoxysilane and vinyltrimethoxysilane (XL 10, Wacker), phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane, vinyldimethoxymethylsilane ( XL 12, Wacker), vinyltriethoxysilane (GF 56, Wacker), vinyltriacetoxysilane (GF 62, Wacker), isooctyltrimethoxysilane (III trimethoxy), isooctyltriethoxysilane (10% triethoxy, Wacker), N-trimethoxysilylmethyl-0-methylcarbamate (XL 63, Wacker), N-dimethoxy (methyl) silylmethyl-O-methyl-carbamate (XL 65, Wacker), hexadecyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane and partial hydrolysates of these compounds. Further, the following polymers are also available from Kaneka Corp. Also suitable as reactive diluents are polymers which can be prepared from an organic skeleton by grafting with a vinyl silane or by reacting polyol, polyisocyanate and alkoxysilane.

A polyol is understood as meaning a compound which contains one or more OH groups in the molecule. The OH groups can be both primary and secondary. Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol and higher glycols, as well as other polyfunctional alcohols. The polyols may additionally contain other functional groups such. As esters, carbonates, amides. To prepare a reactive diluent by reacting polyol with polyisocyanate and alkoxysilane, the corresponding polyol component is reacted in each case with an isocyanate which is at least difunctional. In principle, any isocyanate having at least two isocyanate groups is suitable as the at least difunctional isocyanate, but as a rule compounds having two to four isocyanate groups, in particular two isocyanate groups, are preferred within the scope of the present invention. Among the alkoxysilyl groups, the di- and trialkoxysilyl groups are preferred.

Suitable polyisocyanates for the preparation of a reactive diluent are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1, 4-diisocyanate, bis (2-isocyanatoethyl) fumarate, and mixtures of two or more thereof, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2, 6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2, 4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate (MDI) or their partially or fully hydrogenated cycloalkyl derivatives, for example fully hydrogenated MDI (H12-MDI), alkyl-substituted diphenylmethane diisocyanates, for example mono-, di-, tri- or tetraalkyldiphenylmethane diisocyanate, and their partially or completely hydrogenated cycloalkyl derivatives, 4,4'-diisocyanatophenylperfluoroethane, phthalic acid bis-isocyanatoethyl ester, 1-chloromethylphenyl-2,4- or 2,6-diisocyanate, 1-bromomethylphenyl 2,4- or 2,6-diisocyanate, 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates, as obtained by reacting 2 mol of diisocyanate with 1 mol of thiodiglycol or Dihydroxydihexylsulfid are available, the di- and triisocyanates of di- and trimer fatty acids, or mixtures of two or more of said diisocyanates.

Likewise, as polyisocyanates, it is possible to use trihydric or higher isocyanates, as obtainable, for example, by oligomerization of diisocyanates, in particular by oligomerization of the abovementioned isocyanates. Examples of such trihydric and higher polyisocyanates are the triisocyanurates of HDI or IPDI or mixtures thereof or their mixed triisocyanurates and polyphenylmethylene polyisocyanate, as obtainable by phosgenation of aniline-formaldehyde condensation products.

To reduce the viscosity of the composition according to the invention, it is also possible to use solvents in addition to or instead of a reactive diluent. Suitable solvents are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, ethers, esters, ester alcohols, keto alcohols, keto ethers, keto esters and ether esters. Preferably, however, alcohols are used, since in this case the storage stability increases. C ₁ -C ₁₀ alcohols, especially methanol, ethanol, i-propanol, isoamyl alcohol and hexanol are particularly preferred.

The composition of the invention may further comprise a coupling agent. An adhesion promoter is understood as meaning a substance which improves the adhesive properties of adhesive layers on surfaces. Conventional adhesion promoters (tackifiers) known to the person skilled in the art can be used alone or as a combination of several compounds. Suitable examples are resins, terpene oligomers, coumarone / indene resins, aliphatic, petrochemical resins and modified phenolic resins. In the context of the present invention, for example, hydrocarbon resins are suitable, such as those obtained by polymerization of terpenes, mainly .alpha. Or .beta.-pinene, dipentene or limonene. The polymerization of these monomers is usually cationic with initiation with Friedel-Crafts catalysts. The terpene resins also include copolymers of terpenes and other monomers, for example styrene, α-methylstyrene, isoprene and the like. The resins mentioned are used, for example, as adhesion promoters for pressure-sensitive adhesives and coating materials. Also suitable are the terpene-phenolic resins prepared by acid catalyzed addition of phenols to terpene or rosin. Terpene-phenolic resins are soluble in most organic solvents and oils and are miscible with other resins, waxes and rubbers. Likewise suitable in the context of the present invention as adhesion promoters in the abovementioned sense are the rosins and their derivatives, for example their esters or alcohols. Silane coupling agents, in particular aminosilanes, are particularly suitable.

In a specific embodiment of the curable composition according to the invention, the composition comprises a silane of the general formula (II) R'R''NR-SiXYZ (II) as a bonding agent, wherein
R 'and R "independently of one another are hydrogen or C ₁ -C ₈ -alkyl radicals,
R is a divalent hydrocarbon radical optionally containing one heteroatom having 1-12 C atoms, and
X, Y, Z are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy, wherein at least one of the radicals is a C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy group. Such compounds naturally have a high affinity for the binding polymer components of the curable composition according to the invention, but also for a wide range of polar and non-polar surfaces and therefore contribute to the formation of a particularly stable adhesion between the adhesive composition and the respective substrates to be bonded. The linking group R may, for example, be a straight-chain or branched or cyclic, substituted or unsubstituted alkylene radical. Optionally, the heteroatom contained therein is nitrogen (N) or oxygen (O). If X, Y and / or Z are an acyloxy group, this can be done, for example, by For example, be the acetoxy group -OCO-CH ₃ .

Suitable fillers for the composition according to the invention are, for example, chalk, limestone, precipitated and / or fumed silica, zeolites, bentonites, magnesium carbonate, kieselguhr, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals. Furthermore, organic fillers can be used, in particular carbon black, graphite, wood fibers, wood flour, sawdust, pulp, cotton, pulp, wood chips, chaff, chaff, ground walnut shells and other fiber short cuts. Furthermore, short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber or even polyethylene fibers can be added. Aluminum powder is also suitable as a filler. In addition, as fillers are hollow spheres with a mineral Case or a plastic cover. These may be, for example, glass bubbles, which are commercially available under the trade names Glass Bubbles ^® .

Hollow balls based on plastic, z. B. Expancel ^® or Dualite ^® , for example, in the EP 0 520 426 B1 described. These are composed of inorganic or organic substances, each having a diameter of 1 mm or less, preferably 500 μm or less. For some applications, fillers are preferred which impart thixotropy to the formulations. Such fillers are also described as rheological aids, eg. As hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC. So that they can be pressed out well from a suitable metering device (eg tube), such preparations have a viscosity of 3,000 to 15,000, preferably 4,000 to 8,000 mPas or even 5,000 to 6,000 mPas. The fillers are preferably used in an amount of 1 to 80 wt .-%, based on the total weight of the composition. A single filler or a combination of multiple fillers may be used.

In a preferred embodiment of the composition according to the invention, the filler is a highly disperse silica having a BET surface area of from 10 to 90 m ² / g, in particular from 35 to 65 m ² / g. When used, such a silica does not significantly increase the viscosity of the composition of the present invention, but does contribute to enhancing the cured formulation. About this gain z. B. the initial strengths, tensile shear strengths and the adhesion of the adhesives, sealants or coating materials in which the composition of the invention is used, improved.

Particular preference is given to using a highly disperse silica having a BET surface area of 45 to 55 m ² / g, in particular having a BET surface area of about 50 m ² / g. Such silicas have the additional advantage of a 30 to 50% shortened incorporation time compared to silicic acids with a higher BET surface area. Another advantage lies in the fact that said highly-dispersed silicic acid can be incorporated into silane-terminated adhesives, sealants or coating materials in a considerably higher concentration without adversely affecting the transparency and the flow properties of the adhesives, sealants or coating materials. Particular preference is also given to an embodiment of the composition according to the invention in which the filler is a highly disperse silica having an average particle size d ₅₀ of less than 25 μm, preferably from 5 to 20 μm, measured by laser diffraction. Such a filler is particularly well suited when highly transparent, clear compositions are needed for particularly demanding applications. It is also conceivable to use pyrogenic and / or precipitated silicas having a higher BET surface area, advantageously 100-250 m ² / g, in particular 110-170 m ² / g, as filler. The incorporation of such silicas, however, takes a comparatively long time and is therefore more cost-intensive. In addition, significant amounts of air are introduced into the product, which in turn must be removed cumbersome and tedious. On the other hand, the effect of enhancing the cured composition due to the higher BET surface area can be achieved with a lower silica weight fraction. In this way, further substances can be introduced in order to improve the preparation according to the invention with regard to other requirements.

In the event that a basic filler is to be used instead of acidic fillers, calcium carbonates (chalks) are suitable, for example, whereby cubic, non-cubic, amorphous and other modifications can be used. Preferably, the crayons used are surface-treated or coated. The coating agents used are preferably fatty acids, fatty acid soaps and fatty acid esters, for example lauric acid, palmitic acid or stearic acid, sodium or potassium salts of such acids or their alkyl esters. In addition, however, other surface-active substances such as sulfate esters of long-chain alcohols or alkylbenzenesulfonic acids or their sodium or potassium salts or else coupling reagents based on silanes or titanates are also suitable. The surface treatment of the chalks is often associated with an improvement in the processability and the adhesive strength and also the weather resistance of the compositions. The coating composition is usually used in an amount of from 0.1 to 20% by weight, preferably from 1 to 5% by weight, based on the total weight of the crude crayon.

Depending on the desired property profile, precipitated or ground chalks can be used. Ground chalks can be made, for example, from natural lime, limestone or marble by mechanical grinding, using dry or wet methods. Depending on the milling process, fractions with different average particle size are obtained. Advantageous specific surface values (BET) are between 1.5 m ² / g and 50 m ² / g.

Furthermore, the composition of the invention may contain antioxidants. Preferably, the proportion of antioxidants in the composition of the invention is up to about 7 wt .-%, in particular up to about 5 wt .-%, based on the total weight of the composition. The composition of the invention may further contain UV stabilizers. The proportion of UV stabilizers in the composition according to the invention is preferably up to about 2% by weight, in particular about 1% by weight. Particularly suitable UV stabilizers are the so-called hindered amine light stabilizers (HALS). It is preferred in the context of the present invention, when a UV stabilizer is used, which carries a silyl group and is incorporated in the final product during curing or curing. Particularly suitable for this purpose are the products Lowilite 75, Lowilite 77 (Great Lakes, USA). It is also possible to add benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus and / or sulfur.

It often makes sense to further stabilize the compositions according to the invention against penetrating moisture, in order to increase shelf life even more. Such an improvement in shelf life can be achieved, for example, by the use of desiccants. Suitable drying agents are all compounds which react with water to form an inert group with respect to the reactive groups present in the composition, and thereby undergo the smallest possible changes in their molecular weight. Furthermore, the reactivity of the desiccants to moisture penetrated into the composition must be higher than the reactivity of the end groups of the present invention silyl group-bearing polymer. Suitable drying agents are, for example, isocyanates.

Silanes are also advantageously used as desiccants, for example vinyl silanes, such as 3-vinylpropyltriethoxysilane, oxime silanes, such as methyl-O, O ', O''- butan-2-one-trioximosilane or O, O', O '', O '''. Butan-2-one tetraoximosilane (CAS Nos. 022984-54-9 and 034206-40-1) or benzamidosilanes such as bis (N-methylbenzamido) methylethoxysilane (CAS No. 16230-35-6) or carbamatosilanes such as carbamatomethyltrimethoxysilane. But the use of methyl, ethyl or vinyltrimethoxysilane, tetramethyl or -ethylethoxysilane is possible. Vinyl trimethoxysilane and tetraethoxysilane are particularly preferred in terms of efficiency and cost. Also suitable as a desiccant are the abovementioned reactive diluents, provided they have a molecular weight (M _n ) of less than about 5,000 g / mol and end groups whose reactivity to moisture penetration is at least as great, preferably greater, than the reactivity of the reactive Groups of the silyl group-carrying polymer according to the invention. Finally, it is also possible to use alkyl orthoformates or orthoacetates as drying agents, for example methyl or ethyl orthoformate, methyl or ethyl orthoacetate. The composition of the invention typically contains from about 0.01 to about 10 weight percent desiccant.

The composition of the invention preferably contains 100 parts by weight Component a), 0.5-25 parts by weight Adhesion promoters, 0.01-10 parts by weight Component b), 0.001-100 parts by weight Component c), and optionally 0-125 parts by weight plasticizers, 0-125 parts by weight Filler, 0-25 parts by weight Desiccant or water catcher, 0-10 parts by weight other additives such as pigments, stabilizers, UV absorbers, anti-aging agents, antioxidants, rheological aids, thinners or reactive diluents and / or solvents, as well as fungicides and flame retardants. Compositions based on these proportions open up the possibility of obtaining readily processable adhesives, sealants or coating materials which, in addition to very good elasticity values, have good strength and adhesion. At the same time, the properties of the composition can be precisely tailored to the respective field of application by a specific weighting of the components.

The viscosity of the curable composition according to the invention is preferably less than 1,000,000 mPas (measured using a Brookfield Viscometer Type RVDVII +, Spindle No. 7, 10 rpm at 23 ° C). Particularly preferably, the viscosity of the composition according to the invention is less than 500,000 mPas. In particular, the viscosity of the composition is less than 250,000 mPas. These viscosities allow good processability of the compositions.

• a) ein Polyether und/oder mindestens ein Polyacrylsäureester mit mindestens einer Endgruppe der allgemeinen Formel (I) -A_n-R-SiXYZ (I), worin A eine zweibindige Bindegruppe, R ein zweibindiger gegebenenfalls ein Heteroatom enthaltender Kohlenwasserstoffrest mit 1-12 C-Atomen, und X, Y, Z unabhängig voneinander C₁-C₈-Alkyl-, C₁-C₈-Alkoxy- oder C₁-C₈-Acyloxyreste sind, wobei mindestens einer der Reste eine C₁-C₈-Alkoxy- oder C₁-C₈-Acyloxygruppe ist, und n 0 oder 1 ist;
• b) eine zinnorganische Verbindung;
• c) eine Verbindung, die frei von Zinn- und Siliziumatomen ist und die mindestens zwei Funktionen aufweist, die jeweils ausgewählt sind aus: Carboxy-, Carbonyl-, Hydroxygruppen sowie Stickstoffatomen, die Bestandteil eines Ringsystems mit aromatischem Charakter sind, sowie gegebenenfalls ein Haftvermittler miteinander gemischt werden.

Another object of the present invention is a process for the preparation of a curable composition according to the invention, which is characterized in that at least

• a) a polyether and / or at least one polyacrylic acid ester having at least one end group of the general formula (I) -A _n -R-SiXYZ (I), where A is a divalent linking group, R is a divalent hydrocarbon radical optionally containing one heteroatom having 1-12 C atoms, and X, Y, Z are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy, wherein at least one of the radicals is a C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy group, and n is 0 or 1;
• b) an organotin compound;
• c) a compound which is free of tin and silicon atoms and which has at least two functions, each of which are selected from: carboxy, carbonyl, hydroxy groups and nitrogen atoms which are part of a ring system having an aromatic character, and optionally a coupling agent with each other be mixed.

Another object of the present invention is the use of a curable composition according to the invention or prepared according to the inventive curable composition as adhesive, sealant or coating material, in particular as an adhesive for bonding plastics, metals, glass, ceramics, wood, wood materials, paper , Paper materials, rubber and textiles.

In principle, in the present invention, all features listed in the context of the present text, in particular those described as preferred and / or specifically designated embodiments, ranges, constituents and other features of the composition according to the invention, the inventive method and the use of the invention in all possible and not mutually exclusive exclusionary combinations, combinations of preferred and / or specially designated features being also considered to be preferred and / or specific.

In the following, the invention will be explained in more detail by means of embodiments, wherein the selection of the examples does not represent a limitation of the scope of the subject invention.

Examples:

1. Preparation of a Silane-terminated Polyether of Component a)

328 g (28 mmol) of polypropylene glycol 12000 (OHZ = 9.6) are dried in a 500 ml reactor at 80 ° C in a vacuum. Under nitrogen atmosphere, 0.07 g of bismuth (III) octanoate (BorchiKat 24) is added at 80 ° C., followed by the addition of 14 g (67 mmol) of isocyanatopropyltrimethoxysilane (% NCO = 19.9). After stirring for one hour at 80 ° C, the resulting polymer is cooled and treated with 7.1 g of vinyltrimethoxysilane and 5.3 g of a mixture of 70 wt .-% bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebazat and 30 wt .-% of methyl-1,2,2,6,6-pentamethyl-4-piperidylsebazat (Tinuvin 765). The product is stored moisture-tight under a nitrogen atmosphere in a glass jar before being processed into a curable composition.

2. Compositions and properties

Tab. 1: Compositions and properties of silicic acid formulations Example no. 1 (See) 2 3 Composition (parts by weight) Polymer from 1. 83.0 83.0 83.0 Silica (Aerosil OX 50) 10.0 10.0 10.0 Aminopropyltrimethoxysilane (Geniosil GF 96) 5.0 5.0 5.0 Vinyltrimethoxysilane (Geniosil XL 10) 2.0 2.0 2.0 dibutyltindilaurate 0.10 0.20 0.20 lactic acid 0.05 salicylic acid 0.1 properties Skin Over Time (min) 9 18 13 Tensile shear strengths to BSP / BSP after storage under standard conditions for 0.5 h N / mm ² 12:13 1.16 0.4 1.0 h N / mm ² 0.7 1:53 0.9 2.0 h N / mm ² 1.98 2:44 2.2 7 d N / mm ² 4.63 4.71 4.6 BSP = beech plywood

The examples show that the skin over time of the inventive compositions despite a double content of curing catalyst (dibutyltin dilaurate) compared to the composition of Example 1 is significantly delayed. Tab. 2: Compositions and properties of chalky formulations Example no. 4 (Cf.) 5 6 7 Composition (parts by weight) Polymer from 1. 28.0 28.0 28.0 28.0 phthalate 12.5 12.5 12.5 12.5 Calcium carbonate (Omyabond 302) 57.0 57.0 57.0 57.0 Aminopropyltrimethoxysilane (Geniosil GF 96) 1.0 1.0 1.0 1.0 Vinyltrimethoxysilane (Geniosil XL 10) 1.4 1.4 1.4 1.4 dibutyltindilaurate 0.2 0.20 0.20 0.20 8-hydroxyquinoline 0,015 0,044 0.131 properties Skin Over Time (min) 5 6 10 50 Tensile shear strengths to BSP / BSP in N / mm ² after storage under standard conditions for 10 min 0.59 0.6 0.16 0.2 30 min 1.74 1.54 0.67 0.4 1 h 2.42 2.3 1.5 0.7 2 h 2.66 2.6 2.2 1 3 h 2.97 2.89 2.5 1.3 4 h 3.4 3.5 2.8 1.9 6 h 3.6 3.6 3.2 2.5 8 h 3.7 3.6 3.5 2.9

The examples show that the adhesive compounds prepared with compositions according to the invention have a significantly prolonged skin over time, but then accelerate accelerated and achieve very good strength values in a short time, which are at the level of a non-retarded curing composition.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 1956672 A [0005]
• EP 0549210 A2 [0006, 0006]
• EP 0520426 B1 [0050]

Cited non-patent literature

• ASTM D4671 [0028]

Claims (10)

A curable composition comprising as components a) at least one polyether and / or at least one polyacrylic acid ester having at least one end group of the general formula (I) -A _n -R-SiXYZ (I), where A is a divalent linking group, R is a divalent hydrocarbon radical optionally containing one heteroatom having 1 - 12 C atoms, and X, Y, Z are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ -Acyloxyreste, said at least one of a C ₁ - C ₈ -alkoxy or C ₁ -C ₈ acyloxy group, and n is 0 or 1; and b) at least one organotin compound, c) at least one compound which is free of tin and silicon atoms and which has at least two functions which are each selected from: carboxy, carbonyl, hydroxyl groups and nitrogen atoms which are part of a ring system with aromatic character. A curable composition according to claim 1, characterized in that at least one compound of component c) has at least 2 different functions, each of which are selected from carboxy, carbonyl, hydroxy and nitrogen atoms which are part of a ring system having an aromatic character. Curable composition according to at least one of the preceding claims, characterized in that component c) comprises at least one N-heteroaromatic compound or an α-hydroxy carboxylic acid. A curable composition according to at least one of the preceding claims, characterized in that the molar ratio (mol / mol) of the total amount of compound (s) of component c) to the total amount of compound (s) of component b) is from 1:10 to 10: 1 , Curable composition according to at least one of the preceding claims, characterized in that component a) contains at least one polyether having a molecular weight M of 4,000 to 100,000 g / mol. Curable composition according to at least one of the preceding claims, characterized in that component a) contains at least one polyether having a terminal unsaturation of less than 0.07 meq / g, determined by the method ASTM D4671. Curable composition according to at least one of the preceding claims, characterized in that the composition is a silane of the general formula (II) R'R''NR-SiXYZ (II) in which R 'and R "independently of one another are hydrogen or C ₁ -C ₈ -alkyl radicals, R is a divalent hydrocarbon radical optionally containing one heteroatom and having _{1 to} 12 carbon atoms, and X, Y, Z independently of one another are C ₁ - C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy, wherein at least one of the radicals is a C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy group. Curable composition according to at least one of the preceding claims, characterized in that it contains 100 parts by weight of component a), 0.5-25 parts by weight of adhesion promoter, 0.01-10 parts by weight of component b), 0.001-100 parts by weight of component c) and optionally 0- 125 parts by weight of plasticizer, 0-125 parts by weight of filler, 0-25 parts by weight desiccant or water scavenger, 0-10 parts by weight further additives such as pigments, stabilizers, UV absorbers, anti-aging agents, antioxidants, rheological aids, thinners or reactive diluents and / or solvents, as well as fungicides and flame retardants. Process for the preparation of a curable composition according to at least one of Claims 1 to 8, characterized in that at least a) a polyether and / or at least one polyacrylic acid ester having at least one end group of the general formula (I) -A _n -R-SiXYZ (I), where A is a divalent linking group, R is a divalent hydrocarbon radical optionally containing one heteroatom having 1-12 C atoms, and X, Y, Z are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy, wherein at least one of the radicals is a C ₁ -C ₈ alkoxy or C ₁ -C ₈ acyloxy group, and n is 0 or 1; b) an organotin compound; c) a compound which is free of tin and silicon atoms and which has at least two functions, each of which are selected from: carboxy, carbonyl, hydroxy groups and nitrogen atoms which are part of a ring system having an aromatic character, are mixed together. Use of a curable composition according to any one of claims 1 to 8 or a curable composition prepared according to a method according to claim 9 as an adhesive, sealant or coating material.