DE102008032580A1 - Curable compositions - Google Patents

Abstract

The invention relates to a transparent, curable composition having a viscosity of less than 60,000 mPa.s (measured with a Brookfield viscometer type RVDVII +, spindle no. 7, 10 rpm at 23 ° C.), c) a prepolymer component P comprising a1) an alkoxy- and / or acyloxysilane-terminated polymer having at least one end group of the general formula (I) -An-R-SiXYZ (I), where A is a divalent linking group, R is a divalent hydrocarbon radical having 1-12 C atoms optionally containing a heteroatom and X, Y, Z are independently C1-C8 alkyl, C1-C8 alkoxy or C1-C8 acyloxy, at least one of which is C1-C8 alkoxy or C1-C8 acyloxy, and n 0 or 1; a2) a bonding agent; a3) a catalyst and a4) a plasticizer; and d) comprises a filler F and characterized in that the prepolymer component P has a refractive index (measured with an Abbe refractometer at 20 ° C) which does not deviate more than 0.01 from the refractive index of the filler F.

Description

The This invention relates to curable compositions having a Viscosity smaller than 60,000 mPas, their production and Use in adhesives, sealants or coating materials.

Polymer Systems, which have reactive silyl groups are known. In the presence of humidity are polymers that over Have silyl groups with hydrolyzable substituents, already at room temperature, with elimination of the hydrolyzed Remainders to condense with each other. Depending on the content of silyl groups with hydrolyzable substituents and the structure of these silyl groups mainly long-chain polymers (thermoplastics) form, relatively wide-mesh, three-dimensional networks (elastomers) or highly crosslinked systems (thermosets).

The Polymers generally have an organic backbone on, at the ends z. B. carries alkoxy or Acyloxysilylgruppen. For example, the organic backbone may be to polyurethanes, polyesters, polyethers, etc. act.

Around To achieve bonds with good strength, the polymers usually added fillers. Because of the higher Strength of the fillers compared to the polymers result in higher bond strengths. The disadvantage is however, that the added fillers have a haze cause the compositions and thus any existing Reverse transparency of the original compositions. Furthermore, the added fillers cause an increased Viscosity, which often at the expense of processability and applicability goes.

It There is therefore a need for the most transparent possible compositions with good processability and applicability. It also exists the desire that such compositions have good strength and have sufficient binding to substrates.

task The present invention is therefore transparent, curable To provide compositions which have good strength and have good adhesion and at the same time work well and apply.

• a) eine Prepolymerkomponente P, umfassend
• a1) ein alkoxy- und/oder acyloxysilanterminiertes Polymer 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;
• a2) einen Haftvermittler;
• a3) einen Katalysator; und
• a4) einen Weichmacher; und
• b) einen Füllstoff F; umfasst; und die dadurch gekennzeichnet ist, dass die Prepolymerkomponente P einen Brechungsindex (gemessen mit einem Abbe Refraktometer bei 20°C) aufweist, der nicht mehr als 0,01 von dem Brechungsindex des Füllstoffs F abweicht.

The invention relates to a transparent, curable composition having a viscosity of less than 60,000 mPas (measured with a Brookfield viscometer type RVDVII +, spindle no. 7, 10 rpm at 23 ° C), the

• a) a prepolymer component P comprising
• a1) an alkoxy- and / or acyloxysilane-terminated polymer having at least one end group of the general formula (I) -A _n -R-SiXYZ (I) wherein A denotes a divalent linking group, R denotes a divalent hydrocarbon radical optionally containing one heteroatom with 1-12 C atoms, and X, Y, Z, independently of one another, denote C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy or C ₁ - C _{8 are} 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;
• a2) a bonding agent;
• a3) a catalyst; and
• a4) a plasticizer; and
• b) a filler F; includes; and characterized in that the prepolymer component P has a refractive index (measured with an Abbe refractometer at 20 ° C) which does not deviate more than 0.01 from the refractive index of the filler F.

The curable compositions according to the invention are distinguished, in particular, by being transparent. Furthermore, they have a low yield point and show good processability and applicability. This is particularly advantageous when larger areas are to be treated with adhesives, sealants or coating materials, as is the case for example with surface coatings or large-area adhesions. As an example, the large-area gluing of veneer (wood) is mentioned. The compositions according to the invention can easily pass, so that a large-area application is possible. By running the compositions, uneven floors can be flat if very level. Furthermore, it is advantageous that the curable compositions are pourable, so that they can be poured from a bottle or an open container, for example, on a bottom surface, so that they can be applied much faster and easier than highly viscous compositions, for example, from a tube be applied. The transparency of the curable composition is retained even after curing. Therefore, it is also very easy to bond transparent workpieces, such as glass or transparent plastics. However, the transparency of the composition is also advantageous in the processing of non-transparent materials, since, for example, in the case of (unclean) processing, the composition which forms after bleaching does not stand out unpleasantly since it is transparent.

Further are the curable invention Compositions by good cohesive properties, in particular good strength and good tear strength, as well as good Adhesive properties, d. H. a good and firm bond to different Substrates, off.

Under A curable composition is a substance or a mixture of several substances by physical or chemical measures is curable. It can 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 easiest to contact with humidity, water or consist of a reactive component.

The prepolymer component P comprises a1) an alkoxy- and / or acyloxysilane-terminated polymer, a2) an adhesion promoter, a3) a catalyst and a4) a plasticizer. As second component b) a filler F is contained in the curable composition. The silane-terminated polymer P has 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 polymer, e.g. B. as a urethane group by the reaction of a hydroxy-functionalized polyether with an isocyanatosilane. In this case, the divalent binding group of structural features occurring in the underlying polymer skeleton 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 binding group A is linked the polymer backbone with the radical R (n = 1) or the Polymer skeleton is directly connected to the radical R or linked (n = 0).

Of the Radical R is a divalent hydrocarbon radical optionally containing a heteroatom with 1 to 12 carbon atoms. For example, as a heteroatom Oxygen (O) or nitrogen (N) may be included. In the hydrocarbon radical For example, it can be a straight-chain or branched one or cyclic, substituted or unsubstituted alkylene radical act. The hydrocarbon radical can be saturated or unsaturated be.

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, ie a C ₁ -C ₈ -alkoxy group or -rest or a C ₁ -C ₈ -acyloxy group or -rest. 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 prepolymer component P has a refractive index n which does not deviate more than 0.01 from the refractive index of the filler F. This means that the refractive index of the prepolymer component P is within plus or minus 0.01 of the refractive index of the filler F. The refractive index or the refractive index or the refractive index are measured with an Abbe refractometer at 20 ° C. Above a refractive index deviation of 0.01, the compositions begin to become cloudy and do not show the excellent transparency of the composition according to the invention.

To a preferred embodiment of the invention Composition differs the refractive index of the prepolymer component P is not more than 0.005 of the refractive index of the filler F from.

at Such a low deviation of the refractive index show the Compositions have a crystal clear transparency, are colorless and thus excellent for particularly demanding applications suitable.

To a further preferred embodiment of the invention Composition is the refractive index of the plasticizer in the range from 1.39 to 1.55. Within this range of refractive indices preferably also the values of the usable further constituents the prepolymer component and the fillers, so that transparent Systems can be obtained. The span of the refractive indices is at the same time big enough to have a good variability to ensure the selection of plasticizers. Especially it is advantageous if the refractive index of the plasticizer in Range from 1.43 to 1.50. Within these limits corresponds the refractive index optimally with the values of the other prepolymer components and the applicable fillers such that compositions arise with a particularly clear transparency.

in the Frame of a further preferred embodiment of the invention Composition is the refractive index of the prepolymer component P in the range of 1.43 to 1.48. It was found that this span enough scope for both variations of the Composition within the prepolymer component as well the combination with different fillers and more Leaves components on as wide as possible Base transparent compositions with excellent performance properties to be able to produce. Optimum transparency results when the refractive index of the prepolymer component in the preferred range is from 1.45 to 1.46.

In a further preferred embodiment of the invention Composition has the alkoxy and / or acyloxysilanterminierte Polymer at least two end groups of the general formula (I). Each polymer chain thus contains at least two linking sites, in which, with elimination of the hydrolyzed radicals in the presence Humidity of the condensation of the polymers can take place. On This way will be a regular and fast Crosslinkability achieved so that bonds with good strengths can be obtained. In addition, lets about the amount and structure of the hydrolyzable Groups - eg. B. use of di- or trialkoxysilyl groups, Methoxy groups or longer radicals etc. - the embodiment of the achievable network as a long-chain system (thermoplastics), relatively wide-meshed three-dimensional network (elastomers) or highly cross-linked system (thermosets) control, so that under Elasticity, flexibility and other things the heat resistance of the finished crosslinked compositions can be influenced.

In In a preferred embodiment, X is an alkyl group and Y and Z are an alkoxy group, or X, Y and Z are an alkoxy group. Generally, polymers have di- or trialkoxysilyl groups contain highly reactive linkages, the fast curing, high degree of crosslinking and thus enabling good final strength. Another advantage Such alkoxy-containing polymers can be seen therein that during curing under the influence of moisture Alcohols are formed, which are harmless in the released amounts are and evaporate. Therefore, such compositions are suitable especially for the home improvement sector. The special Advantage of Dialkoxysilylgruppen - the former variant at the beginning of this paragraph - is that the corresponding Compositions after curing elastic, softer and more flexible than trialkoxysilyl group-containing systems. They are therefore particularly suitable for use as sealants suitable. In addition, they split during curing even less alcohol and are therefore particularly interesting, when the amount of alcohol released is to be reduced.

With Trialkoxysilyl groups, however, can be a higher Achieve degree of crosslinking, which is particularly advantageous if after the curing of a harder, firmer mass desired becomes. In addition, trialkoxysilyl groups are more reactive, network faster and thus reduce the required Amount of catalyst, and they have advantages when "cold Flow "- the dimensional stability of a corresponding Adhesive under the influence of force and possibly temperature - on.

Particularly preferred is an embodiment in which X, Y and Z are each independently one 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.

Especially an embodiment is preferred in which X, Y and Z a Methyl or methoxy group. Compounds with alkoxysilyl groups have different depending on the nature of the alkyl radicals on the oxygen atom Reactivities in chemical reactions. It shows within the alkoxy groups, the methoxy group is the largest Reactivity. So silyl groups can be used be if a particularly fast curing desired becomes. Higher aliphatic radicals such as ethoxy cause a already lower reactivity compared to methoxy groups the terminal alkoxysilyl group and may be advantageous for the development of graduated crosslinking speeds be used.

interesting Design possibilities also open up combinations both groups. If z. B. for X methoxy and for Y ethoxy selected within the same alkoxysilyl group, can produce the desired reactivity of the shooter Silyl groups are particularly finely adjusted, if only Methoxy-bearing silyl groups as too reactive and the ethoxy groups carrying silyl groups for use as too sluggish be felt.

Next Of course, methoxy and ethoxy groups can be used also larger radicals than hydrolyzable groups are used, the nature of a lower Have reactivity. This is especially interesting if delayed curing is desired is, for example, in adhesives, even after the application still a shift of the glued surfaces against each other to find the final positions should.

In a further preferred embodiment of the invention Composition R is a hydrocarbon radical having 1 to 6 carbon atoms. about the length of the hydrocarbon radicals that make up the link between Form polymer skeleton and silyl radical, the curing rate can the composition are influenced, creating a further design opportunity for the composition according to the invention is opened.

Especially R is a methylene, ethylene or propylene radical. Especially preferred Methylene and 1,3-propylene radicals are used. alkoxysilane Compounds with a methylene group as a link to the polymer backbone - so-called α-silanes - have a particularly high reactivity of the final silyl group on what shortened setting times and thus to a very fast curing of formulations based such polymers.

As a general rule leads to an extension of the connecting hydrocarbon chain to a reduced reactivity of the polymers. Especially the γ-silanes - they contain the unbranched Propylene radical as a link - have a balance between required reactivity (acceptable curing times) and delayed curing (open time, possibility for correction after gluing).

By a deliberate combination of α- and γ-alkoxysilane-terminated Building blocks can increase the curing rate of the systems be influenced as desired.

In a further preferred embodiment of the invention Composition A is 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 backbone polymer with a reactive compound, which carries the -R-SiXYZ sequence is reacted. The group A can occur from in the underlying polymer backbone Structural features both distinguishable and indistinguishable be. The latter is for example, if they are with the nodes identical to the repeat units of the polymer backbone is. In this case, n would equal 0. If the binding group is A from the linking groups in the polymer backbone distinguishable, n corresponds to the value 1.

Several methods are described in the art for linking a reactive silyl group to a polymer backbone. Mention may be the polymerization of unsaturated monomers with such z. B. alkoxysilyl groups. A suitable monomer of the latter variety would be, for example, vinyltrimethoxysilane. Another method is the grafting of unsaturated monomers such. B. Vinyltrimethoxysilane on thermoplastics, such as polyethylene. Also widely used is the hydrosilylation, the addition of H-silanes such as methyldimethoxysilane to carbon-carbon double bonds under noble metal catalysis. By this method, the residue containing the terminal silyl group is linked directly, ie without a further linking group, to the polymeric backbone (n = 0 in formula I).

Especially preferred as a linking group are urethane and urea groups, the by reaction of certain functional groups of a prepolymer with an organosilane, which is another functional group carries, can be obtained. urethane can z. B. arise when either the polymer backbone contains terminal hydroxy groups and as another component Isocyanatosilane be used, or if conversely a polymer, which has terminal isocyanate groups, with a terminal hydroxy-containing alkoxysilane is reacted. Similarly, urea groups can be obtained be if a terminal primary or secondary Amino group - either on silane or on the polymer - used becomes, which with an existing in the respective reaction partner terminal Isocyanate group reacts. That means either an aminosilane with a terminal isocyanate group-containing polymer or terminal substituted with an amino group polymer with a Isocyanatosilane is reacted. Urethane and urea groups advantageously increase the strength of the polymer chains and of the entire crosslinked polymer because they are hydrogen bonds can train.

in the Frame of a further preferred embodiment of the invention Composition has the alkoxy and / or acyloxysilanterminierte Polymer has a backbone that is selected from the group polyurethanes, polyethers, polyesters, polyacrylates, Poly (meth) acrylates, polyacrylamides, poly (meth) acrylamides, polyvinyl esters, Polyolefins, alkyd resins, phenolic resins, vinyl polymers, styrene-butadiene copolymers, and copolymers of one or more of the aforementioned basic skeletons. By the selection and the specific arrangement of the for the backbone used classes of polymers can essential properties of the invention Composition - such. Viscosity and elasticity, but also the resistance to environmental influences - determined become.

Especially be preferred for the construction of the skeleton Polyurethanes and polyesters and polyether used. The use of polyurethanes and polyesters opens up manifold Possible applications, because with both polymer classes depending on choice and stoichiometric ratios the starting materials very different mechanical properties can be realized. Polyester can over it are decomposed by water and bacteria and are therefore for applications where biodegradability important, interesting. Polymers containing polyether as a backbone contain not only at the end groups, but also in the polymer backbone a flexible and elastic structure. This allows compositions produce excellent elastic properties. Polyethers are not only flexible in their basic structure, but at the same time constantly. This is how they become, for example not attacked or decomposed by water and bacteria. As part of The present invention will be discussed in terms of availability particularly preferred polyethers based on polyethylene oxide and / or polypropylene oxide used.

In a further preferred embodiment of the composition according to the invention, the alkoxy- and / or acyloxysilane-terminated polymer has a molecular weight M _n of 4,000 to 100,000, preferably 8,000 to 50,000, more 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. This, as well as the weight-average molecular weight M _w , can be determined by gel permeation chromatography (GPC). Such a method is known to the person skilled in the art.

The given molecular weights are particularly advantageous since the appropriate balance of appropriate compositions of viscosity (easy processability), strength and Have elasticity. Very advantageous is this combination in a molecular weight range of 12,000 to 20,000, in particular from 14,000 to 18,000, pronounced.

Preferably, in the context of the present invention, 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. The viscosity, out. The alkoxy- and / or acyloxysilane-terminated polymer particularly preferably has a polydispersity (M _w / M _n ) of less than 1.3.

The compositions according to the invention which act as adhesives, Sealing or coating materials are suitable, in addition to the above-mentioned silylated polymer compounds, further auxiliary and additives that give them improved elastic properties, improved resilience, long enough Processing time, fast curing speed and give little residual tack. To these auxiliaries and additives include adhesion promoters, catalysts and plasticizers as well Fillers. In addition, the Compositions as further additives stabilizers, antioxidants, Reactive diluents, drying agents, UV stabilizers, anti-aging agents, rheological aids, color pigments or color pastes, fungicides, Flame retardant and / or possibly also to a small extent Solvent included.

Under a plasticizer is understood to mean a substance which determines the viscosity reduces the compositions and thus the processability facilitates flexibility and beyond Elongation of the compositions improved.

In a preferred embodiment of the invention Composition is the plasticizer selected from a Fatty acid ester, a dicarboxylic acid ester, a Esters of 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 one Paraffin, and mixtures of two or more thereof. These plasticizers combine their own function particularly advantageous - relief processability, flexibility and flexibility Elongation of the compositions - with a suitable expression of the refractive index, to the desire according to compositions with excellent transparency become. Through the targeted selection of one of these plasticizers or a specific combination may have further advantageous properties the composition of the invention, for. Gelling ability the polymers, cold elasticity or cold resistance or antistatic properties can be realized.

For example are suitable from the group of phthalates dioctyl phthalate, Dibutyl phthalate, diisoundecyl phthalate, diisononyl phthalate or butylbenzyl 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 ester, acetic acid ester, propionic acid ester, Thiobutyric acid esters, citric acid esters as well Nitrocellulose and polyvinyl acetate-based esters, and mixtures from two or more of them. For example, the asymmetric ones are also suitable Esters of adipic acid monooctyl ester with 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).

Also in the context of the present invention are suitable as plasticizers Diurethane, which, for example, by reaction of diols can be prepared with OH end groups with monofunctional isocyanates, by choosing the stoichiometry such that essentially all of the free OH groups abreact. If necessary, excess Isocyanate can then be, for example, by distillation be removed from the reaction mixture. Another method for Preparation of diurethanes consists in the implementation of monofunctional Alcohols with diisocyanates, where possible all Abreact NCO groups.

A for certain applications too high viscosity of the adhesive or sealant according to the invention can also by using a reactive diluent to simple and appropriate manner, without that there are signs of segregation (eg plasticizer migration) comes in the hardened mass.

Preferably the reactive diluent has at least one functional Group on, after the application z. B. with moisture or Atmospheric oxygen reacts.

Examples for such groups are silyl groups, isocyanate groups, vinylic unsaturated groups and polyunsaturated Systems.

When Reactive thinner you can get all the compounds with the Composition of the invention with reduction the viscosity are miscible and over at least have a binder reactive group alone or as a combination of several compounds.

The Viscosity of the reactive diluent is preferably less than 20,000 mPas, more preferably about 0.1-6,000 mPas, most preferably 1-1000 mPas (Brookfield RVT, 23 ° C, spindle 7, 10 rpm).

When Reactive diluents can be z. B. use the following substances: 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 (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (10 trimethoxy), isooctyltriethoxysilane (IO triethoxy, Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (XL63, Wacker), N-dimethoxy (methyl) silylmethyl-O-methyl-carbamate (XL65, Wacker), hexadecyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane and partial hydrolysates of these compounds.

Further are also the following polymers from Kaneka Corp. as a reactive diluent Can be used: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.

Farther Suitable reactive diluents are polymers which consist of a organic backbone by grafting with a vinyl silane or by reaction of polyol, polyisocyanate and alkoxysilane produced are.

Under a polyol is understood to be a compound in the molecule contains one or more OH groups. The OH groups can both primary and secondary.

To The suitable aliphatic alcohols include, for example Ethylene glycol, propylene glycol and higher glycols, as well other polyfunctional alcohols. The polyols can additionally other functional groups such. As esters, carbonates, amides.

to Preparation of a reactive diluent by reaction of Polyol with polyisocyanate and alkoxysilane will be the corresponding Polyol component each with an at least difunctional isocyanate implemented. As at least difunctional isocyanate is basically each isocyanate having at least two isocyanate groups in question, in However, the rule in the context of the present invention compounds with two to four isocyanate groups, especially with two isocyanate groups prefers.

Under The alkoxysilyl groups preferred are the di- and trialkoxysilyl groups.

Suitable polyisocyanates for preparing 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 '' - Diphenylmethandiisocyanat or 4,4'-diphenylmethane diisocyanate (MDI) or their partially or fully hydrogenated cycloalkyl derivatives, for example fully hydrogenated it is 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-bischloromethyl ether-4,4 "-diphenyl diisocyanate, sulfur-containing diisocyanates, as obtained by reacting 2 mol Diisocyanate with 1 mole of thiodiglycol or Dihydroxydihexylsulfid are available, the di- and Trii socyanates of di- and trimer fatty acids, or mixtures of two or more of said diisocyanates.

As well can be used as polyisocyanates trihydric or higher isocyanates, as exemplified by oligomerization of diisocyanates, in particular by oligomerization of the above-mentioned isocyanates, available. Examples of such trihydric and higher polyisocyanates are the triisocyanurates of HDI or IPDI or mixtures thereof or their mixed triisocyanurates as well as polyphenylmethylene polyisocyanate, as by phosgenation of aniline-formaldehyde condensation products is.

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 according to the invention also comprises a bonding agent. Under a bonding agent is a substance understood that the adhesion properties of adhesive layers Improved surfaces. It can usual, Adhesion promoters known to the person skilled in the art (tackifiers) alone or as Combination of several compounds are used. Are suitable For example, resins, terpene oligomers, coumarone / indene resins, aliphatic, petrochemical resins and modified phenolic resins. Are suitable in the context of the present invention, for example, hydrocarbon resins, as produced by polymerization of terpenes, mainly α- od. β-pinene, dipentene or limonene are obtained. The Polymerization of these monomers is usually cationic below Initiation with Friedel-Crafts catalysts. To the terpene resins are also copolymers of terpenes and other monomers, for example Styrene, α-methylstyrene, isoprene and the like. The resins mentioned find, for example, as adhesion promoters for Pressure sensitive adhesives and coating materials use. Also suitable are the terpene-phenolic resins, which are acid-catalyzed Addition of phenols to terpene or rosin can be made. Terpene phenolic resins are available in most organic solvents and oils soluble and with other resins, waxes and Rubber miscible. Also in the context of the present invention suitable as adhesion promoters in the sense mentioned above are the rosin resins and their derivatives, for example their esters or alcohols. Especially Silane coupling agents, in particular aminosilanes, are particularly suitable.

In a further preferred embodiment of the curable composition according to the invention, the prepolymer component P 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 .

The prepolymer component P of the curable composition of the invention comprises as a further constituent a catalyst. As crosslinking catalysts for controlling the curing rate of the curable compositions of the invention, for example, organometallic compounds such as iron or tin compounds are suitable, in particular the 1,3-dicarbonyl compounds of iron such. Example, iron (III) acetylacetonate or di- or tetravalent tin such as dibutyltin bisacetylacetonate, the dialkyltin (IV) dicarboxylates -. As dibutyltin dilaurate, dibutyltin maleate or Dibu tyltin diacetate - or the corresponding dialkoxylates, e.g. B. dibutyltin dimethoxide. Especially with the organotin compounds are well-tried and easily accessible catalysts with excellent activity. However, some tin organyls have come under criticism due to physiological and environmental concerns. Therefore, in another preferred embodiment, the composition according to the invention is tin-free. Nevertheless, the compositions according to the invention can be cured well and quickly using alternative catalysts without any loss of quality.

Boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide or mixed boron halides can alternatively be used as curing catalysts. Particularly preferred are boron trifluoride complexes such as. B. boron trifluoride diethyl etherate ( CAS-No. [109-63-7] ), which are easier to handle as liquids than the gaseous boron halides.

Further is 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) as a catalyst for the composition of the invention suitable.

About that In addition, titanium, aluminum and zirconium compounds or mixtures of one or more catalysts used from one or more of the groups just mentioned. On the one hand, the use of tin compounds can also be achieved in this way On the other hand, a better adhesion can be avoided to normally poorly adherent organic surfaces such as B. reach acrylates. Among the titanium, aluminum and Zirconium catalysts, the titanium catalysts are preferably used, because they give you the best cure results.

Titanium catalysts are compounds which have hydroxyl groups and / or substituted or unsubstituted alkoxy groups, ie titanium alkoxides of the general formula Ti (OR ^z ) ₄ , wherein R ^{z is} an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms and the 4 alkoxy groups OR ^{z are the} same or different. Furthermore, one or more of the radicals -OR ^{z can be} replaced by acyloxy groups -OCOR ^z .

As well are suitable as titanium catalysts titanium alkoxides in which a or more alkoxy groups are replaced by halogen atoms.

As titanium catalysts z. B. the following mixed or non-mixed-substituted titanium alkoxides are used:
Tetramethoxy titanium, tetraethoxy titanium, tetraallyloxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra (2-butoxy) titanium, tetra (t-butoxy) titanium, tetrapentoxy (titanium), tetracyclopentoxy titanium, tetrahexoxy titanium, tetracyclohexoxy titanium, Tetrabenzoxytitanium, tetraoctoxytitanium, tetrakis (2-ethylhexoxy) -titanium, tetradecoxytitanium, tetradodecoxytitanium, tetrastearoxytitanium, tetrabutoxytitanium dimer, tetrakis (8-hydroxyoctoxy) titanium, titanium diisopropoxy-bis (2-ethyl-1,3-hexanediolate), titanium bis ( 2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolate), tetrakis (2-chloroethoxy) titanium, tetrakis (2-bromoethoxy) titanium, tetrakis (2-methoxyethoxy) titanium, tetrakis (2-ethoxyethoxy) titanium, butoxy Trimethoxy titanium, dibutoxy dimethoxy titanium, butoxy triethoxy titanium, dibutoxy diethoxy titanium, butoxy triisopropoxy titanium, dibutoxy diisopropoxy titanium, tetraphenoxybutane, tetrakis (o-chlorophenoxy) titanium, tetrakis (m-nitrophenoxy) titanium, tetrakis (p-methylphenoxy) titanium, tetrakis (trimethylsiloxy) titanium.

Further titanium acylates can be used: triisopropoxytitanium, Triisopropoxytitanium methacrylate, diisopropoxytitanium dimethacrylate, isopropoxytrintrimethacrylate, Triisopropoxy titanium hexanoate, triisopropoxytitanium stearate and the like.

When halogenated titanium catalysts may, for. As the following compounds be used: triisopropoxytitanium chloride, diisopropoxytitanium dichloride, Isopropoxy titanium trichloride, triisopropoxy titanium bromide, triisopropoxy titanium fluoride, Triethoxytitanium chloride, tributoxytitanium chloride.

Furthermore, titanium chelate complexes can be used:
Dimethoxytitabis (ethylacetoacetate), dimethoxytitanium bis (acetylacetonate), diethoxytitanium bis (ethylacetoacetate), diethoxytitanium bis (acetylacetonate), diisopropoxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (methylacetoacetate), diisopropoxytitanium bis (t-butylacetoacetate), diisopropoxytitanium bis (methyl-3-oxo-4,4-dimethylhexanoate ), Diisopropoxy titanium bis (ethyl 3-oxo-4,4,4-trifluorobutanoate), diisopropoxy titanium bis (acetylacetonate), diisopropoxy titanium bis (2,2,6,6-tetramethyl-3,5-heptanedionate), di (n-butoxy) titanium bis (ethylacetoacetate), di (n-butoxy) tianbis (acetylacetonate), diisobutoxytitanium bis (ethylacetoacetate), diisobutoxytitanium bis (acetylacetonate), di (t-butoxy) titanium bis (ethylacetoacetate), di (t-butoxy) titanium bis (acetylacetonate), di (2 ethylhexoxy) titanium bis (ethylacetoacetate), di (2-ethylhexoxy) titanium bis (acetylacetonate), bis (1-methoxy-2-propoxy) titanium bis (ethylacetoacetate), Bis (3-oxo-2-butoxy) titanium bis (ethylacetoacetate), bis (3-diethylaminopropoxy) titanium bis (ethylacetoacetate), triisopropoxytitanium (ethylacetoacetate), triisopropoxytitanium (diethylmalonate), triisopropoxytitanium (allylacetoacetate), triisopropoxytitanium (methacryloxyethylacetoacetate), 1,2 Dioxyethanitanebis (ethylacetoacetate), 1,3-dioxpropane titanium bis (ethylacetoacetate), 2,4-dioxypentanetitanium bis (ethylacetoacetate), 2,4-dimethyl-2,4-dioxypentanetitan bis (ethylacetoacetate), diisopropoxytitanium bis (triethanolaminate), tetrakis (ethylacetoacetato) titanium, Tetrakis (acetylacetonato) titanium, bis (trimethylsiloxy) titanium bis (ethylacetoacetate), bis (trimethylsiloxy) titanium bis (acetylacetonate).

Prefers The following titanium chelate complexes are used since they are commercial are available and have a high catalytic activity Diethoxytitanbis (ethylacetoacetate), Diethoxytitanbis (acetylacetonate), Diisopropoxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (acetylacetonate), Dibutoxytitanium bis (ethylacetoacetate) and dibutoxytitanium bis (acetylacetonate). Particularly preferred are diethoxytitanium bis (ethylacetoacetate), diisopropoxytitanium (ethylacetoacetate) and dibutoxytitanium bis (ethylacetoacetate), most preferably is diisopropoxy titanium bis (ethyl acetoacetate).

Further It is also possible to use the following titanium catalysts: Isopropoxytitanium tris (dioctylphosphate), isopropoxytitanium tris (dodecylbenzylsulfonate), Dihydroxytitanbislactat.

Aluminum catalysts can also be used as curing catalysts, for. B. aluminum alkoxides Al (OR ^z ) ₃ , wherein R ^{z is} an organic group, preferably a substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms and the three radicals R ^{z are} identical or different.

Also in the case of the aluminum alkoxides, one or more of the alkoxy radicals may be replaced by acyloxy radicals -OC (O) R ^z .

Further Aluminum alkoxides can be used in which a or more alkoxy radicals are replaced by halogen atoms.

From The aluminum catalysts described are the pure aluminum alcoholates in terms of their stability to moisture and the hardenability of the mixtures to which they added are favored. In addition, aluminum chelate complexes prefers.

As aluminum alkoxides, for example, the following compounds can be used:
Trimethoxyaluminum, triethoxyaluminum, triallyloxyaluminum, tri (n-propoxy) aluminum, triisopropoxyaluminum, tri (n-butoxy) aluminum, triisobutoxyaluminum, tri (sec-butoxy) aluminum, tri (t-butoxy) aluminum, tri (n-pentoxy) aluminum, Tricyclopentoxyaluminum, trihexoxyaluminum, tricyclohexoxyaluminum, tribenzoxyaluminum, trioctoxyaluminum, tris (2-ethylhexoxy) aluminum, tridecoxyaluminum, tridodecoxyaluminum, tristearoxyaluminum, dimeric tributoxyaluminum, tris (8-hydroxyoctoxy) aluminum, isopropoxyaluminum bis (2-ethyl-1,3-hexanediolate), diisopropoxyaluminum ( 2-ethyl-1,3-hexanediolate), (2-ethylhexoxy) aluminum bis (2-ethyl-1,3-hexanediolate), bis (2-ethylhexyloxy) aluminum (2-ethyl-1,3-hexanediolate), tris ( 2-chloroethoxy) aluminum, tris (2-bromoethoxy) aluminum, tris (2-methoxyethoxy) aluminum, tris (2-ethoxyethoxy) aluminum, butoxydimethoxyaluminum, methoxydibutoxyaluminum, butoxydiethoxyaluminum, ethoxydibutoxyaluminum, butoxydiisopropoxyaluminum, isopropoxydibutoxyaluminum, triphene oxyaluminum, tris (o-chlorophenoxy) aluminum, tris (m-nitrophenoxy) aluminum, tris (p-methylphenoxy) aluminum.

For example, aluminum acylates can also be used:
Diisopropoxyaluminum acrylate, diisopropoxyaluminum methacrylate, isopropoxyaluminum dimethacrylate, diisopropoxaluminum hexanoate, diisopropoxyaluminum stearate.

Further aluminum halide compounds can be used, z. Diisopropoxyaluminum chloride, isopropoxyaluminum dichloride, diisopropoxyaluminum bromide, Diisopropoxyaluminum fluoride, diethoxyaluminum chloride, dibutoxyaluminum chloride.

Aluminum chelate complexes can also be used as catalysts, for example
Methoxyaluminum bis (ethylacetoacetate), methoxyaluminum bis (acetylacetonate), ethoxyaluminum bis (ethylacetoacetate), ethoxyaluminum bis (acetylacetonate), isopropoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (methylacetoacetate), isopropoxyaluminum bis (t-butylacetoacetate), dimethoxyaluminum (ethylacetoacetate), dimethoxyaluminum (acetylacetonate), diethoxyaluminum (ethylacetoacetate ), Diethoxyaluminum (acetylacetonate), diisopropoxyaluminum (ethylacetoacetate), diisopropoxyaluminum (methylacetoacetate), diisopropoxyaluminum (t-butylacetoacetate), isopropoxyaluminum bis (methyl-3-oxo-4,4-dimethylhexanoate), isopropoxyaluminum bis (ethyl-3-oxo-4,4 , 4-trifluoropentanoate), isopropoxyaluminum bis (acetylacetonate), isop ropoxyaluminum bis (2,2,6,6-tetramethyl-3,5-heptanedionate), n-butoxyaluminum bis (ethylacetoacetate), n-butoxyaluminum bis (acetylacetonate), isobutoxyaluminum bis (ethylacetoacetate), isobutoxyaluminum bis (acetylacetonate), t-butoxyaluminum bis (ethylacetoacetate), t-butoxyaluminum bis (acetylacetonate), 2-ethylhexoxyaluminum bis (ethylacetoacetate), 2-ethylhexoxyaluminum bis (acetylacetonate), 1,2-dioxyethanaluminum (ethylacetoacetate), 1,3-dioxypropanaluminum (ethylacetoacetate), 2,4-doxypentanaluminim (ethylacetoacetate), 2, 4-dimethyl-2,4-dioxypentanaluminim (ethylacetoacetate), iopropoxyaluminum bis (triethanolaminate), aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum (acetylacetonate) bis (ethylacetoacetate). The following aluminum chelate complexes are preferably used as catalysts since they are commercially available and have high catalytic activities: ethoxyaluminum bis (ethylacetoacetate), ethoxyaluminum bis (acetylacetonate), isopropoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (acetylacetonate), butoxyaluminum bis (ethylacetoacetate), butoxyaluminum bis (acetylacetonate) , Dimethoxyaluminum ethylacetoacetate, dimethoxyaluminum acetylacetonate, diethoxyaluminum ethylacetoacetate, diethoxyaluminum acetylacetonate, diisopropoxyaluminum ethylacetoacetate, diisopropoxyaluminum methylacetoacetate and diisopropoxyaluminum (t-butylacetoacetate).

Especially preferred are ethoxyaluminum bis (ethylacetoacetate), isopropoxyaluminum bis (ethylacetoacetate), Butoxyaluminum bis (ethylacetoacetate), dimethoxyaluminum ethylacetoacetate, Diethoxyaluminum ethylacetoacetate and diisopropoxyaluminum ethylacetoacetate.

All particularly preferred are isopropoxyaluminum bis (ethylacetoacetate) and diisopropoxyaluminum ethylacetoacetate.

Further can z. B. also used the following aluminum catalysts bis (dioctylphosphato) isopropoxyaluminum, bis (dodecylbenzylsulfonato) isopropoxyaluminum, Hydroxyaluminum.

Suitable zirconium catalysts are:
Tetramethoxyzirconium, tetraethoxyzirconium, tetraallyloxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetraisobutoxyzirconium, tetra (2-butoxy) zirconium, tetra (t-butoxy) zirconium, tetrapentoxy (zirconium), tetracyclopentoxyzirconium, tetrahexoxyzirconium, tetracyclohexoxyzircon, Tetrabenzoxyzirconium, tetraoctoxyzirconium, tetrakis (2-ethylhexoxy) zirconium, tetradecoxyzirconium, tetradodecoxyzirconium, tetrastearoxyzirconium, tetrabutoyzirconium dimer, tetrakis (8-hydroxyoctoxy) zirconium, zirconium diisopropoxy-bis (2-ethyl-1,3-hexanediolate), zirconium bis ( 2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolate), tetrakis (2-chloroethoxy) zirconium, tetrakis (2-bromoethoxy) zirconium, tetrakis (2-methoxyethoxy) zirconium, tetrakis (2-ethoxyethoxy) zirconium, butoxy Trimethoxyzirconium, dibutoxydimethoxyzirconium, butoxytriethoxyzirconium, dibutoxydiethoxyzirconium, butoxitriisopropoxyzirconium, dibutoxydiisopropoxyzirconium, tetraphenoxybutane, tetrakis (o-chlorophenoxy) zirconium, tetrakis (m-nitrophenoxy) zirconium, tetrakis (p-methylphenoxy) zirconium, tetrakis (trimethyls iloxy) zirconium, diisopropoxyzirconium bis (ethyl acetoacetate), diisopropoxyzirconium bis (acetylacetonate), Dibutoxyzirkonbis (ethylacetoacetate), Dibutoxyzirkonbis (acetylacetonate), Triisopropoxyzirkonethylacetoacetat, Triisopropoxyzirkonacetylacetonat, tris (n-butoxy) zirkonethylacetoacetat, tris (n-butoxy) zirconium, isopropoxyzirconium (ethylacetoacetate), isopropoxyzirconium (acetylacetonate), n-butoxyzircontris (ethylacetoacetate), n-butoxyzircontris (acetylacetonate), n-butoxyzircon (acetylacetonate) bis (ethylacetoacetate).

Prefers for example, diethoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (ethylacetoacetate), Dibutoxyzirconium bis (ethylacetoacetate), triispropoxyzirconium (ethylacetoacetate), Tris (n-butoxy) zirconium (ethylacetoacetate), isopropoxyzircontris (ethylacetoacetate), n-butoxyzircontris (ethylacetoacetate) and n-butoxyzircon (acetylacetonate) bis (ethylacetoacetate) one. Very particular preference is given to diisopropoxyzirconium bis (ethylacetoacetate); Triispropoxyzirconium (ethylacetoacetate) and isopropoxyzircontris (ethylacetoacetate) used.

Furthermore zirconacylates can be used, for example:
Triisopropoxyzirconium, triisopropoxyzirconium methacrylate, diisopropoxyzirconium dimethacrylate, isopropoxyzircontrimethacrylate, triisopropoxyzirconium hexanoate, triisopropoxyzirconstearate and the like.

When halogenated zirconium catalysts can be the following compounds use: triisopropoxyzirconium chloride, diisopropoxyzirconium dichloride, Isopropoxyzirconium trichloride, triisopropoxyzirconium bromide, triisopropoxyzirconfluoride, Triethoxyzirconium chloride, tributoxyzirconium chloride.

In addition, zirconium chelate complexes can also be used:
Dimethoxyzirconium bis (ethyl acetoacetate), dimethoxyzirconium bis (acetylacetonate), diethoxyzirconium bis (ethylacetoacetate), diethoxyzirconium bis (acetylacetonate), diisopropoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (me thylacetoacetate), diisopropoxyzirconium bis (t-butyl acetoacetate), diisopropoxyzirconium bis (methyl 3-oxo-4,4-dimethylhexanoate), diisopropoxyzirconium bis (ethyl 3-oxo-4,4,4-trifluorobutanoate), diisopropoxyzirconium bis (acetylacetonate), diisopropoxyzirconium (2 , 2,6,6-tetramethyl-3,5-heptanedionate), di (n-butoxy) zirconium bis (ethylacetoacetate), di (n-butoxy) zirconium bis (acetylacetonate), diisobutoxyzirconium bis (ethylacetoacetate), diisobutoxyzirconium bis (acetylacetonate), di ( t-butoxy) zirconium bis (ethylacetoacetate), di (t-butoxy) zirconium bis (acetylacetonate), di (2-ethylhexoxy) zirconium bis (ethylacetoacetate), di (2-ethylhexoxy) zirconium bis (acetylacetonate), bis (1-methoxy-2-) propoxy) zirconium bis (ethylacetoacetate), bis (3-oxo-2-butoxy) zirconium bis (ethylacetoacetate), bis (3-diethylaminopropoxy) zirconium bis (ethylacetoacetate), triisopropoxyzirconium (ethylacetoacetate), triisopropoxyzirconium (diethylmalonate), triisopropoxyzircon (allylacetoacetate), triisopropoxyzircon (methacryloxyethylacetoacetate), 1,2-dioxyethane-biskon (ethylacetoacetate), 1,3-dioxypropanecarboxylic (e thylacetoacetate), 2,4-dioxypentanzirconium (ethylacetoacetate), 2,4-dimethyl-2,4-dioxypentanzirconium (ethylacetoacetate), diisopropoxyzirconium bis (triethanolaminate), tetrakis (ethylacetoacetato) zirconium, tetrakis (acetylacetonato) zirconium, bis (trimethylsiloxy) zirconium ( ethylacetoacetate), bis (trimethylsiloxy) zirconium bis (acetylacetonate).

The following zirconium chelate complexes are preferably used since they are commercially available and have a high catalytic activity:
Diethoxyzirconium bis (ethyl acetoacetate), diethoxyzirconium bis (acetylacetonate), diisopropoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (acetylacetonate), dibutoxyzirconium bis (ethylacetoacetate), and dibutoxyzirconium bis (acetylacetonate). Diethoxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium (ethylacetoacetate) and dibutoxyzirconebis (ethylacetoacetate) are most preferred is diisopropoxyzirconium bis (ethylacetoacetate).

Further It is also possible to use the following zirconium catalysts: isopropoxyzircontris (dioctyl phosphate), Isopropoxyzircontris (dodecylbenzylsulfonate), dihydroxyzirconium bislactate.

Furthermore For example, carboxylic acid salts can be used as curing catalysts of metals or a mixture of several such salts are selected, these being selected from the carboxylates the following metals: calcium, vanadium, iron, titanium, potassium, barium, Manganese, nickel, cobalt and / or zirconium. Of the carboxylates are the calcium, vanadium, iron, titanium, potassium, barium, manganese and zirconium carboxylates, because they have high activity exhibit.

Especially preferred are calcium, vanadium, iron, titanium and zirconium carboxylates.

All especially preferred are iron and titanium carboxylates.

You can z. For example, use the following compounds:
Iron (II) (2-ethylhexanoate), iron (III) (2-ethylhexanoate), titanium (IV) (2-ethylhexanoate), vanadium (III) (2-ethylhexanoate), calcium (II) (2-ethylhexanoate) potassium 2-ethylhexanoate, barium (II) (2-ethylhexanoate), manganese (II) (2-ethylhexanoate), nickel (II) (2-ethylhexanoate), cobalt (II) (2-ethylhexanoate), zirconium (IV) ( 2-ethylhexanoate), iron (II) neodecanoate, ferric neodecanoate, titanium (IV) neodecanoate, vanadium (III) neodecanoate, calcium (II) neodecanoate, potassium neodecanoate, barium (II) neodecanoate, zirconium (IV) neodecanoate, iron (II) oleate, iron (III) oleate, titanium tetraoleate, vanadium (III) oleate, calcium (II) oleate, potassium oleate, barium (II) oleate, manganese (II) oleate, nickel (II) oleate, cobalt (II) oleate , Zirconium (IV) oleate, iron (II) naphthenate, iron (III) naphthenate, titanium (IV) naphthenate, vanadium (III) naphthenate, calcium dinaphthenate, potassium naphthenate, barium dinaphthenate, manganese naphthenate, nickel dinaphthenate, cobalt dinaphthenate, zirconium (IV) naphthenate.

In With regard to the catalytic activity, iron (II) 2-ethylhexanoate, Iron (III) 2-ethylhexanoate, titanium (IV) 2-ethylhexanoate, iron (II) neodecanoate, Iron (III) neodecanoate, titanium (IV) neodecanoate, iron (II) oleate, iron (III) oleate, Titanium (IV) oleate, iron (II) naphthenate, iron (III) naphthenate and titanium (IV) naphthenate preferred, and iron (III) 2-ethylhexanoate, iron (III) neodecanoate, Iron (III) oleate and iron (III) naphthenate are particularly preferred.

In view of the non-occurrence of discoloration, preferred are: titanium (IV) 2-ethylhexanoate, calcium (II) 2-ethylhexanoate, potassium 2-ethylhexanoate, barium (II) 2-ethylhexanoate, zirconium (IV) 2-ethylhexanoate, titanium ( IV) neodecanoate, calcium (II) neodecanoate, potassium neodecanoate, barium (II) neodecanoate, zirconium (IV) neodecanoate, titanium (IV) oleate, calcium (II) oleate, potassium oleate, barium (II) oleate, zirconium (IV) oleate, Titanium (IV) naphthenate, calcium (II) naphthenate, potassium naphthenate, barium (II) naphthenate and zirconium (IV) naphthenate. The calcium carboxylates, vanadium carboxylates, iron carboxylates, titanium carboxylates, potassium carboxylates, barium carboxylates, manganese carboxylates, nickel carboxylates, cobalt carboxylates and zirconium carboxylates may be used singly or as a mixture of several catalysts from one or more of the mentioned groups. Except one can use these metal carboxylates in conjunction with Zinncarboxylaten, lead carboxylates Bismutcarboxylaten and Cercarboxylaten.

Of the Catalyst is in an amount of 0.01 to about 10 wt .-%, based on the total weight of the composition used.

It It is also possible to use mixtures of several catalysts to combine beneficial effects.

When Fillers for the invention Composition are, for example, chalk, lime, precipitated and / or fumed silica, zeolites, bentonites, magnesium carbonate, Diatomaceous earth, clay, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, Quartz, flint, mica, glass powder and other ground minerals. Furthermore, organic fillers can also be used especially carbon black, graphite, wood fibers, wood flour, Sawdust, pulp, cotton, pulp, wood chips, Chaff, chaff, ground walnut shells and other fiber cuts. Furthermore, short fibers such as glass fiber, glass filament, Polyacrylonitrile, carbon fiber, Kevlar fiber or polyethylene fibers be added. Aluminum powder is also a filler suitable.

In addition, suitable fillers are hollow spheres with a mineral shell or a plastic shell. 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 added in an amount of 1 to 80 wt .-%, based on the total weight of the composition used. It can be a single filler or a combination of multiple fillers 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. A further 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 the transparency and the flow properties of the adhesives, sealants or coating materials being impaired.

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. Let that way introduce additional substances to improve the preparation according to the invention in terms of other requirements.

Further For example, the composition of the invention may be antioxidants contain. Preferably, the proportion of antioxidants on the composition of the invention up to about 7 wt .-%, in particular up to about 5 wt .-%.

The composition of the invention can about it In addition, UV stabilizers included. Preferably the proportion of UV stabilizers on the inventive Composition up to about 2 wt .-%, in particular about 1 wt .-%. Particularly suitable as UV stabilizers are the so-called hindered Amine Light Stabilizer (HALS). It is within the scope of the present Invention preferred when a UV stabilizer is used, the carries a silyl group and when crosslinking or curing is incorporated into the final product. For this purpose are particularly suitable the products Lowilite 75, Lowilite 77 (Great Lakes, USA). Further also benzotriazoles, benzophenones, benzoates, cyanoacrylates, Acrylates, hindered phenols, phosphorus and / or sulfur be added.

Often it makes sense, the compositions of the invention continue to stabilize against invading moisture, Shelf-life even more to increase.

A such improvement in shelf life can be for example, by using desiccants. When Desiccants are all compounds that are watery Formation of a present in the composition Reactive groups react inert group, and this possible undergo slight changes in their molecular weight. Furthermore, the reactivity of the desiccant must be opposite in the composition of penetrated moisture higher be as the reactivity of the end groups of the composition present inventive silyl groups bearing Polymer.

When Desiccants 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 No. 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 that they have a molecular weight (M _n ) of less than about 5,000 g / mol and have 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.

After all As drying agents, alkyl orthoformates or orthoacetates may also be used be used, for example methyl or ethyl orthoformate, Methyl or ethyl orthoacetate,

The Contains inventive composition usually about 0.01 to about 10 wt .-% desiccant.

In a further preferred embodiment of the composition according to the invention contains these
100 parts by weight of the alkoxy- and / or acyloxysilane-terminated polymer,
0.5-25 parts by weight of a primer,
0.01-10 parts by weight of a catalyst,
5-125 parts by weight of the plasticizer,
5-125 parts by weight of the filler,
0-25 parts by weight of a desiccant or water scavenger, and optionally
0-10 parts by weight of other additives, such as pigments, stabilizers, UV absorbers, anti-aging agents, antioxidants, rheological aids, thinners or reactive diluents and / or solvents, and fungicides and flame retardants.

Compositions based on these proportions open up the possibility of producing good results obtainable adhesives, sealants or coating materials which 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.

In a further preferred embodiment of the invention Composition is the viscosity of the composition 5,000 to 55,000 mPas (measured with a Brookfield viscometer type RVDVII +, spindle # 7, 10 rpm at 23 ° C). Especially preferred is the viscosity of the composition of the invention less than 50,000 mPas. In particular, the viscosity is the composition 9,000 to 40,000 mPas. Very particularly preferred the viscosity is 10,000 to 30,000, in particular 12,000 to 22,000 mPas. These viscosities allow a good processability of the compositions.

• a) eine Prepolymerkomponente P, umfassend
• a1) ein alkoxy- und/oder acyloxysilanterminiertes Polymer mit mindestens einer Endgruppe der allgemeinen Formel (I) -An-R-SiXYZ (I), worinA 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; und
• a2) einen Haftvermittler;
• a3) einen Katalysator; und
• a4) einen Weichmacher; und
• b) ein Füllstoff F

miteinander gemischt werden. Die einzelnen Komponenten sind dabei wie vorstehend ausgeführt definiert.Another object of the invention is a process for the preparation of a transparent, curable composition according to the invention, which is characterized in that

• a) a prepolymer component P comprising
• a1) an alkoxy- and / or acyloxysilane-terminated polymer having at least one end group of the general formula (I) -An-R-SiXYZ (I) wherein A denotes a divalent linking group, R denotes a divalent hydrocarbon radical optionally containing one heteroatom with 1-12 C atoms, and X, Y, Z, independently of one another, denote C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy or C ₁ - C _{8 are} 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; and
• a2) a bonding agent;
• a3) a catalyst; and
• a4) a plasticizer; and
• b) a filler F

be mixed with each other. The individual components are defined as stated above.

at the rest R may be, for example, a straight-chain or branched or cyclic, substituted or unsubstituted Alkylene radical, optionally as a heteroatom oxygen (O) or nitrogen Contains (N), act.

If X, Y and / or Z are an acyloxy group, this may be, for. B. the acetoxy group be.

In a further preferred embodiment of the invention Process becomes plasticizer to the curable composition added until the prepolymer component P has a refractive index (measured with an Abbe refractometer at 20 ° C), which is not more than 0.01, in particular not more than 0.005, of the refractive index of the filler F deviates. The invention Procedure can also be carried out in such a way that plasticizer is added to the curable composition, until the curable composition becomes transparent. Independently which criterion is used in this process with careful dosage of the plasticizer used exactly that amount which is necessary in addition to the curable composition the outstanding use characteristics also one from the consumer perceived as extremely beneficial transparency to rent.

Another object of the invention is the use of a curable composition or a composition according to the invention prepared by the method according to the invention described above as an adhesive, sealant or coating material. Preference is given to the use as an adhesive for bonding plastics, metals, glass, ceramics, wood, wood-based materials, paper, paper materials, rubber and textiles. In such applications, the composition of the invention can be well processed and applied due to its low viscosity and allows good adhesion and strength after curing. As a special application advantage is the transparency - even after curing - to call, which allows an application for their part transparent materials such as glass or transparent plastics and thereby causes no aesthetic disadvantages. In addition, also from joints o. Ä. Emerging remnants of the composition, as they may result from the (unclean) processing, just because of the transparency of the composition is not uncomfortable. Furthermore, a simplified assessment of the bond is made possible, in particular by the transparent bonding of transparent Ma materials enclosed air bubbles can be detected very easily.

in the The invention will be described below with reference to exemplary embodiments explained in more detail.

Examples:

Preparation of Polymer 1:

282 g (15 mmol) of polypropylene glycol 18000 (OHZ = 6.0) were in a 500 ml three-necked flask dried at 100 ° C in a vacuum. Under Nitrogen atmosphere at 80 ° C 0.06 g of dibutyltin laurate added and then with 7.2 g (32 mmol) of isocyanatopropyltrimethoxysilane (% NCO = 18.4). After stirring for one hour at 80 ° C, the resulting polymer was cooled and mixed with 6 g of vinyltrimethoxysilane. The product became moisture-proof stored under nitrogen atmosphere in a glass jar.

Preparation of Polymer 2:

155.1 g (19 mmol) of polypropylene glycol 8000 (OHN = 14.0) were in a 500 ml three-necked flask dried at 100 ° C in a vacuum. Under Nitrogen atmosphere at 80 ° C 0.06 g of dibutyltin laurate added and then with 15.3 g (87 mmol) TDI (% NCO = 47.8). After stirring for one hour at 80 ° C, the resulting polymer with 103.4 g (105 mmol) PolyTHF 1000 (OHZ = 114) and for an additional hour stirred at 80 ° C. It was with a mixture from 10.2 g (45 mmol) of isocyanatopropyltrimethoxysilane (% NCO = 18.3) and 5.5 g (34 mmol) of isocyanatomethyldimethoxymethylsilane (% NCO = 25.7) and stirred for a further hour at 80 ° C. The polymer was cooled and treated with 6 g of vinyltrimethoxysilane added. The product became moisture-proof under a nitrogen atmosphere stored in a glass jar.

Polymer 3:

Kaneka MS Polymer S203H from Kaneka - to the best of our knowledge the Applicant at both ends of the chain methyldimethoxysilyl-terminated Polypropylene glycol in which the silyl groups by hydrosilylation terminal double bonds were introduced.

Polymer 4:

In a 2 l reactor, 85 g of poly-THF (M _n 1000) were introduced and with 100 ppm of a DMC catalyst according to the teaching of US 4472560 Mistake.

Subsequently was evacuated, charged at 110 ° C with 1915 g of propylene oxide and after the addition stirred for half an hour. The Product has an OHV of 10 and a viscosity of 6000 mPas.

300 g (25 mmol) of this block copolymer were placed in a 500 ml three-necked flask dried at 80 ° C in a vacuum. Under nitrogen atmosphere At 80 ° C, 0.1 g of bismuth carboxylate (Borchi Kat 24, FA. Borchers). To this was first 4.3 g (25 mmol) Isocyanatomethyldimethoxymethylsilan (Geniosil XL42) and then 7.7 g (35 mmol) of 3-isocyanatopropyltrimethoxysilane (Geniosil GF 40) was added and stirred at 80 ° C for one hour. The resulting prepolymer mixture was cooled and mixed with 7.0 g Geniosil XL 63. The product became moisture-proof stored under nitrogen atmosphere in a glass jar.

Production of adhesive formulations:

The Production took place in a Speedmixer, z. SpeedMixer DAC 400 FVZ (company Hauschild Engineering).

there First, the liquid components were mixed (without Crosslinking catalyst), then the filler is added and then the catalyst mixed in.

The Results are summarized in Table 1 (in parts by weight). Transparency: ++ = colorless, perfectly clear and transparent; + = transparent with slight haze; - = milky / opaque

Determination of tensile shear strength:

Test specimens of different materials were by means of the composition according to the invention gen 1 to 7 (Table 1) or the composition of Comparative Example 4 as a triple determination, each with a test specimen of wood, z. B. three-ply beech lumber, glued and stored for 7 days. The bond area was 2.5 cm × 2.0 cm.

Of the Adhesive application was one-sided. By means of a toothed spatula Excess glue was removed. To For 7 days, the tensile shear strength was measured by means of a material testing device Zwick (type Zwick Z010) determined.

The measured values are given in N / mm ² in Table 2 and show the suitability of the compositions according to the invention as adhesives which have good strength and good adhesion.

Determination of viscosity:

The Viscosities were measured by means of a Brookfield viscometer Type RVDVII +, spindle no. 7, 10 rpm at 23 ° C determined. The Compositions of Comparative Examples 1 to 3 show high viscosities and no longer meet the requirement that they are process well and apply.

Determination of refractive index:

The refractive index was determined by means of an Abbe refractometer at 20 ° C. Table 1 raw material 1 2 3 4 5 6 7 Polymer 1 100 100 100 100 100 100 100 Polymer 2 Polymer 3 Polymer 4 methyl palmitate 18.5 9.3 18.5 Adipic acid, 2-ethylhexyl 22.2 Diisoundecyphthalat 21 24.1 33.3 42.6 C _10-21 Alkylsulfonsäurephenylester 24.1 20.4 42.6 aminopropyltrimethoxysilane 6.2 9.3 9.3 9.3 9.3 9.3 9.3 vinyltrimethoxysilane 6.2 4.8 4.8 4.8 4.8 4.8 4.8 Aerosil OX 50 (filler, refractive index 1.455) 28 31.3 31.3 31.3 31.3 31.3 31.3 dibutyltindilaurate 0.9 0.75 0.75 0.75 0.75 0.75 0.75 dibutyltin diketonate 1,8-diazabicyclo [5.4.0] undec-7-ene Refractive index polymer comp. P 1,449 1,450 1,453 1,452 1,452 1,455 1,459 transparency + + ++ ++ ++ ++ ++ viscosity 41800 13800 15200 29600 26000 22000 17600 - continued - raw material 8th 9 10 See 1 See 2 See 3 See 4 Polymer 1 100 100 Polymer 2 100 100 100 Polymer 3 100 Polymer 4 100 methyl palmitate 17 4.5 42.6 Adipic acid, 2-ethylhexyl Diisoundecyphthalat 42.6 27.8 C _10-21 Alkylsulfo ⁿ acid phenyl aminopropyltrimethoxysilane 9.3 8.5 9.3 8.6 7.5 7.3 9.3 vinyltrimethoxysilane 4.8 12.7 13.9 8.6 11.4 10.9 4.8 Aerosil OX 50 (filler, refractive index 1.455) 31.3 30.9 33.3 24.6 27.3 26.1 31.3 dibutyltindilaurate 0.9 0.75 dibutyltin diketonate 0.75 1,8-diazabicyclo [5.4.0] undec-7-ene 1 1.1 1 0.9 Refractive index polymer comp. P 1,457 1,449 1,451 1,453 1,452 1,443 1,442 transparency ++ + ++ ++ ++ - - viscosity 9200 46200 12500 110200 66800 71000 12400 Table 2 material 1 2 3 4 5 6 7 See 4 beech 5.1 4.1 4.1 3.9 4.1 4.6 5.2 3.4 alumimium 2.9 3.9 3.9 3.4 4.6 4.6 5.0 3.7 polycarbonate 4.7 3.9 3.6 4.0 4.3 4.3 4.6 3.6

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0520426 B1 [0104]
• US 4472560 [0131]

Cited non-patent literature

• - CAS no. [109-63-7] [0066]
• - CAS No 022984-54-9 [0115]
• - 034206-40-1 [0115]
• - CAS No. 16230-35-6 [0115]

Claims (22)

A transparent, curable composition having a viscosity of less than 60,000 mPas (measured with a Brookfield Viscometer Type RVDVII +, spindle No. 7, 10 rpm at 23 ° C) comprising: a) a prepolymer component P comprising a1) an alkoxy- and / or acyloxysilane-terminated Polymer having at least one end group of the general formula (I) -A _n -R-SiXYZ (I) wherein A denotes a divalent linking group, R denotes a divalent hydrocarbon radical optionally containing one heteroatom with 1-12 C atoms, and X, Y, Z, independently of one another, denote C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy or C ₁ - C _{8 are} 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; a2) a bonding agent; a3) a catalyst; and a4) a plasticizer; and b) a filler F; characterized in that the prepolymer component P has a refractive index (measured with an Abbe refractometer at 20 ° C) which does not deviate more than 0.01 from the refractive index of the filler F. A curable composition according to claim 1, characterized in that the refractive index of the prepolymer component P by not more than 0.005 of the refractive index of the filler F deviates. A curable composition according to claim 1 or 2, characterized in that the refractive index of the plasticizer in the range of 1.39 to 1.55, in particular 1.43 to 1.50. Curable composition according to one of preceding claims, characterized in that the refractive index of the prepolymer component P in the range of 1.43 to 1.48, especially 1.45 to 1.46. Curable composition according to one of preceding claims, characterized in that the alkoxy- and / or acyloxysilane-terminated polymer at least has two end groups of the general formula (I). Curable composition according to one of preceding claims, characterized in that X is an alkyl group and Y and Z are an alkoxy group or X, Y and Z are an alkoxy group. Curable composition according to one of preceding claims, characterized in that X, Y, Z are each independently methyl, a Ethyl, a methoxy or an ethoxy group, in particular a Methyl or methoxy group. Curable composition according to one of preceding claims, characterized in that R is a hydrocarbon radical having 1 to 6 C atoms, in particular a Methylene, ethylene or propylene radical. Curable composition according to one of preceding claims, characterized in that A is an amide, carbamate, urea, imino, carboxylate, carbamoyl, Amidino, carbonate, sulfonate or sulfinate group or an oxygen or nitrogen atom. Curable composition according to one of preceding claims, characterized in that the alkoxy- and / or acyloxysilane-terminated polymer is a backbone which is selected from the group polyurethanes, Polyethers, polyesters, polyacrylates, poly (meth) acrylates, polyacrylamides, Poly (meth) acrylamides, polyvinyl esters, polyolefins, alkyd resins, phenolic resins, Vinyl polymers, styrene-butadiene copolymers, and copolymers of one or more of the aforementioned frameworks. Curable composition according to one of the preceding claims, characterized the alkoxy- and / or acyloxysilane-terminated polymer has a molecular weight M _n of 4,000 to 100,000, in particular 8,000 to 50,000, g / mol. Curable composition according to one of preceding claims, characterized in that she 100 parts by weight of the alkoxy- and / or acyloxysilane-terminated Poylmers, 0.5-25 parts by weight of a primer, 0.01-10 Parts by weight of a catalyst 5-125 parts by weight the plasticizer, 5-125 parts by weight of the filler, 0-25 Parts by weight of a desiccant or water scavenger, and optionally 0-10 parts by weight of further additives, such as pigments, stabilizers, UV absorbers, anti-aging agents, Antioxidants, rheological aids, thinner or Reactive diluents and / or solvents, as well Contains fungicides and flame retardants. Curable composition according to one of the preceding claims, characterized in that the prepolymer component P is a silane of the general formula (II) R'R''NR-SiXYZ (II) as adhesion promoter, wherein R 'and R "independently of one another are hydrogen or C ₁ -C ₈ -alkyl radicals, a divalent hydrocarbon radical optionally containing one heteroatom with 1-12 C-atoms, and X, Y, Z independently of one another C ₁ -C _{8 are} 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 one of preceding claims, characterized in that the viscosity is 5,000 to 55,000, especially 9,000 to 40,000, mPas (measured with a Brookfield viscometer type RVDVII +, Spindle No. 7, 10 rpm at 23 ° C). Curable composition according to one of preceding claims, characterized in that the plasticizer is selected from a fatty acid ester, a dicarboxylic acid ester, an ester OH-bearing or epoxidized fatty acids, a fat, a glycolic 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, as well as mixtures of two or more from that. Curable composition according to one of the preceding claims, characterized in that the filler is a highly disperse silica having a BET surface area of 10 to 90 m ² / g, in particular from 35 to 65 m ² / g. Curable composition according to one of the preceding claims, characterized in that the filler is a highly disperse silica having a measured by laser diffraction average particle size d ₅₀ of less than 25 microns, preferably from 5 to 20 microns. Curable composition according to one of preceding claims, characterized in that she is tin-free. Process for the preparation of a transparent, curable composition according to one of Claims 1 to 18, characterized in that a) a prepolymer component P comprising a1) an alkoxy and / or acyloxysilane-terminated polymer having at least one end group of the general formula (I) -A _n -R-SiXYZ (I) wherein A denotes a divalent linking group, R denotes a divalent hydrocarbon radical optionally containing one heteroatom with 1-12 C atoms, and X, Y, Z, independently of one another, denote 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; and a2) an adhesion promoter; a3) a catalyst; and a4) a plasticizer; and b) a filler F are mixed together. Method according to claim 19, characterized added plasticizer to the curable composition is until the prepolymer component P has a refractive index (measured with an Abbe refractometer at 20 ° C), which is not more than 0.01, in particular not more than 0.005, of the refractive index of the filler F deviates. Use of a composition according to one of Claims 1 to 18 or a composition produced according to a method according to one of claims 19 and 20 as adhesive, sealing or coating material. Use according to claim 21 for bonding plastics, Metals, glass, ceramics, wood, wood-based materials, paper, paper materials, Rubber and textiles.