DE102008003155A1 - Curable composition, useful e.g. as sealants, coatings and curable adhesives, comprises organopolysiloxanes, crosslinking agent, emulsifier, crosslinking catalyst, aqueous silicon-free polymer dispersion, filler and optionally water - Google Patents

Abstract

Curable composition comprises: (a) at least an organopolysiloxane, which contains at least a hydroxyl group and/or group which is hydrolyzed, in aqueous dispersion; (b) at least an organopolysiloxane with a dynamic viscosity of 0.05-7 (measured according to Brookfield DV-II+, spindle 3, 23[deg] C), which is free of hydroxyl groups and/or groups which are hydrolyzed, in aqueous dispersion; (c) at least a crosslinking agent; (d) at least a emulsifier; (e) at least a crosslinking catalyst; (f) at least an aqueous silicon-free polymer dispersion; (g) at least a filler; and (h) optionally water.

Description

The The present invention relates to curable compositions based on aqueous dispersions of hydroxy-functional Organopolysiloxanes and their use as adhesives and sealants.

Under Exclusion of water storable, upon access of water At room temperature to elastomers vulcanizing one-component sealants are known as so-called "silicone sealants" Products are in large quantities for example in the construction industry used. The basis of these blends are polymers by Silyl groups are terminated, the reactive substituents such as hydrolyzable Bear groups. The hydrolyzable groups can be used for Example alkoxy groups, acetoxy groups, amino groups or oxime groups be. These sealants are characterized by their appearance on a variety of substrates excellent adhesion exhibit. A disadvantage of these sealants, however, that the hydrolyzable groups during the crosslinking process be split off from the polymer chain in the first step and in escape the surrounding atmosphere. The application in closed Rooms are therefore without odor and / or occupational hygiene impairment only possible to a limited extent.

since For some time already aqueous dispersions are on the Base of viscous silicone oils known after evaporation the water from the dispersion by splitting off of water to a Can crosslink elastomers. Volatile, organic Compounds are used in these aqueous systems, in particular in the dispersions based on hydroxylated silicone oils, not released to any appreciable extent. Another advantage The aqueous preparations is their easier processability.

It is known, for example, that the inclusion of crosslinking agents (in particular colloidal silica, alkali silicate, polyalkoxysilane, polyalkenyloxysilane, polyacyloxysilane, polycetiminoxysilane, polyamino or polyamidosilane, siliconate, polysilicate, silsesquioxane resin, reactive hydroxylated, alkoxylated or acyloxylated silicone resin) in an aqueous emulsion of hydroxylated Silicone oil after incorporation of fillers and organometallic catalysts allowed to obtain a dispersion which can crosslink by elimination of water to form an elastomer, see for example US-A-4,221,688 ; US-A-4,244,849 ; US-A-3,355,406 ; US-A-3,294,725 ; U.S.-A-4,584,341 ; US-A-4,618,642 ; U.S.-A-4,608,412 ; US-A-4 554 187 ; EP-A-266 729 ; EP-A-332,544 ; EP-A-304 719 ; EP-A-365 439 ; FR-A-2 642 765 ; FR-A-2 637 606 ; FR-A-2 638 166 ).

In the scriptures DE-A-2047919 ; DE-A-2157580 ; DE-A-2129987 and EP-A-169,098 It is proposed to start from an already polymerized hydroxylated oil to give an aqueous emulsion of hydroxylated silicone oil and to add this to an aqueous emulsion by stabilizing the emulsions with an anionic and / or nonionic surfactant. The conventional methods (use of ball-mill type apparatus, homogenizer) are limited to the emulsification of polymers having a viscosity of less than about 5000 mPas; However, it is difficult to emulsify viscous oils, but to the detriment of the grain size and thus the stability of the emulsion thus obtained, the grain size remains very coarse, much more than 1 micron. For this reason, the reactive silicone oil emulsion used is generally obtained by emulsion polymerization of cyclic or linear low molecular weight oligomers which are easy to emulsify according to classical methods, ie, using an anionic surfactant which also preferably plays the role of the polymerization catalyst ( US-A-3,294,725 ; US-A-3,360,491 ).

According to the recommendations of the U.S.-A-4,608,412 dispersed polymers with very high molecular weights (MW> 200,000) are required to obtain sealants with good mechanical properties, in particular elongation at elevated fracture, before and after storage of the dispersion in a hermetically sealed cartridge; according to this process, the aqueous dispersions are obtained by emulsion polymerization in the presence of an ionic, often anionic, surfactant which damages the stability of the sealant and reduces its performance, such as lack of adhesion to a range of substrates found in the construction sector and inadequate mechanical properties ,

WO 94/09059 describes aqueous dispersions comprising at least one organopolysiloxane oil, which is crosslinkable by condensation to form an elastomer, optionally a crosslinker, a silane, a mineral filler and a catalytic amount of a curing compound. These dispersions are produced by kneading a silicone oil phase having a viscosity of at least 3 Pas, this silicone oil phase, the crosslinkable organopolysiloxane oil and optionally the crosslinking agent, the silane, the filler and the curing agent. In addition, the mixture contains an aqueous phase containing water and at least one emulsifier. The weight ratio of water to water plus emulsifier is chosen so that the viscosity of the aqueous phase is at least as high as the viscosity of the silicone oil phase. This mixture should be kneaded with sufficient shear until an oil-in-water emulsion with a particle size of 0.1 to 5 microns is formed. Optionally, this emulsion may subsequently be diluted with water to a solids content of 25 to 97%. These dispersions are said to be useful in making elastomeric paints, water repellents for facades, sealants and / or fire-retardant elastomeric products.

EP 0 410 899 discloses an aqueous silicone oil dispersion containing an oil-in-water emulsion of an α, ω-dihydroxypolysiloxane stabilized with at least one anionic or nonionic emulsifier, an aqueous dispersion of an organic (co) polymer having a particle size between 0.01 and 0 , 5 microns and a solids content between 20% and 70% (by weight), a crosslinker, at least one non-silicate filler and optionally a metal catalyst. This silicone dispersion should have a solids content of at least 40 wt .-%. The document suggests that these dispersions are useful in hair cosmetic compositions, particularly to increase the durability of a porous elastomer film formed on the hair.

Out WO 93/1 51 59 Pressure-sensitive adhesive compositions are known which contain an adhesive acrylate adhesive. As an additive, this adhesive should contain about 2 to 10% by weight (based on the dry substance) of a polydimethylsiloxane having a number-average molecular weight of between 1,300 and 15,000. This addition of polysiloxane is intended to improve the cutting properties of the pressure-sensitive adhesive and in particular to prevent the bleeding of the cut edges.

The font DE 29919310 U1 describes means for water repellent treatment of surfaces are suitable. These contain at least two silicone oils of different viscosity and an acrylic acid ester dispersion and an aliphatic / aromatic hydrocarbon mixture of C ₁₀ to C ₁₂ hydrocarbons. The means are intended to treat glass surfaces to provide these water repellent and to improve the transparency, so that the disc in question clear and almost transparent acts.

It So there is still a need for water-based silicone sealants, which have fully satisfactory mechanical properties. In particular, they are supposed to work on a variety of substrates, like them occur in the construction sector (especially on plastic surfaces), have good adhesion.

task The present invention therefore provides novel water-based silicone oil preparations to provide elastomers with high elasticity harden and have a good adhesion spectrum. Further is a user-friendly curing time in the application he wishes.

• a) mindestens ein Hydroxylgruppen oder hydrolisierbare Gruppen enthaltendes Organopolysiloxan,
• b) mindestens ein niederviskoses Organopolysiloxan, frei von Hydroxylgruppen,
• c) ein Vernetzungsmittel
• d) mindestens einen Emulgator,
• e) mindestens einen Vernetzungskatalysator,
• f) mindestens eine wässrige siliziumfreie Dispersion,
• g) mindestens einen Füllstoff,
• h) Wasser.

The subject matter of the present invention can be found in the patent claims, it consists in providing an aqueous dispersion of silicone oils

• a) at least one organopolysiloxane containing hydroxyl groups or hydrolyzable groups,
• b) at least one low-viscosity organopolysiloxane, free of hydroxyl groups,
• c) a crosslinking agent
• d) at least one emulsifier,
• e) at least one crosslinking catalyst,
• f) at least one aqueous silicon-free dispersion,
• g) at least one filler,
• h) water.

One Another object of the present invention is the use a preparation of dispersions of the above type as curable Adhesive or sealant or coating agent with improved Adhesion properties.

The Hydroxyl groups or hydrolyzable groups containing organopolysiloxane is preferably an α, ω-functional organopolysiloxane, which has at least two functional groups per molecule, which, optionally after hydrolysis, are condensable.

such Organopolysiloxanes can be represented by the general formula (1) being represented.

• – a = 0 oder 1,
• – b = 0 oder 1,
• – mit a + b = 0; 1 oder 2,
• – n besitzt einen ausreichenden Wert, um dem Polymeren der Formel (1) die gewünschte Viskosität zu verleihen, vorzugsweise ist n = 500 –10.000 bzw. 750 –10.000, besonders bevorzugt 1.100 – 6.000, insbesondere 1.500 – 2.000,
• – die Reste X sind identisch oder verschieden und bedeuten – eine OH-Gruppe mit a + b = 2, – einen Alkoxy- oder Alkenyloxyrest mit 1 bis 10 Kohlenstoffatomen, – einen Aryloxyrest mit 6 bis 13 Kohlenstoffatomen, – einen Acyloxyrest mit 1 bis 13 Kohlenstoffatomen, – eine Ketiminoxygruppe mit 1 bis 8 Kohlenstoffatomen oder – eine funktionelle Amino- oder Amidogruppe mit 1 bis 6 Kohlenstoffatomen, die an das Silicium durch eine Si-N-Bindung gebunden sind;
• – die Reste R¹ und R² sind gleich oder verschieden und organische aliphatische Alkyl-, Alkenylreste mit 1 bis 10 Kohlenstoffatomen, aromatische Phenylreste bedeuten, wobei diese Reste gegebenenfalls durch Halogenatome oder Cyanogruppen substituiert sind, wobei bevorzugt mindestens 80% der Reste Methylgruppen sind;
• – die Reste R³ und R⁴ sind gleich oder verschieden und bedeuten organische aliphatische Alkyl-, Aminoalkyl-, Polyaminoalkyl-, Epoxyalkyl-, Alkenylreste mit 1 bis 13 Kohlenstoffatomen, aromatische Arylreste mit 6 bis 13 Kohlenstoffatomen; wobei mindestens 2 und bevorzugt mindestens 3 gegebenenfalls nach Hydrolyse kondensierbare funktionelle Gruppen pro Molekül vorhanden sind und bevorzugt mindestens 80% der Reste R¹ bis R⁴ eine Methylgruppe bedeuten.

In formula (1)

• - a = 0 or 1,
• - b = 0 or 1,
• - with a + b = 0; 1 or 2,
• N is of sufficient value to impart the desired viscosity to the polymer of formula (1), preferably n is 500-10,000 or 750-10,000, more preferably 1,100-6,000, in particular 1,500-2,000,
• The radicals X are identical or different and denote - an OH group with a + b = 2, - an alkoxy or alkenyloxy radical having 1 to 10 carbon atoms, - an aryloxy radical having 6 to 13 carbon atoms, - an acyloxy radical having 1 to 13 Carbon atoms, - a ketoiminoxy group having 1 to 8 carbon atoms, or - an amino or amido functional group having 1 to 6 carbon atoms bonded to the silicon through a Si-N bond;
• - The radicals R ¹ and R ² are identical or different and are organic aliphatic alkyl, alkenyl radicals having 1 to 10 carbon atoms, aromatic phenyl radicals, these radicals being optionally substituted by halogen atoms or cyano groups, wherein preferably at least 80% of the radicals are methyl groups;
• The radicals R ³ and R ⁴ are identical or different and denote organic aliphatic alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl, alkenyl radicals having 1 to 13 carbon atoms, aromatic aryl radicals having 6 to 13 carbon atoms; wherein at least 2, and preferably at least 3, optionally condensable by hydrolysis functional groups per molecule are present and preferably at least 80% of the radicals R ¹ to R ^{4 is} a methyl group.

• – Alkoxy, wie beispielsweise Methoxy, Ethoxy, Octyloxy,
• – Alkenyloxyl, wie beispielsweise Vinyloxy, Hexenyloxy, Isopropenyloxy,
• – Aryloxy, wie beispielsweise Phenyloxy,
• – Acyloxy, wie beispielsweise Acetoxy,
• – Ketiminoxy, wie beispielsweise ON=C(CH3)C2H5; Aminoderivate, wie beispielsweise Ethylamino, Phenylamino,
• – Amidoderivate, wie beispielsweise Methylacetamido.

As an example of the radical X, the following groups can be mentioned:

• Alkoxy, such as methoxy, ethoxy, octyloxy,
• Alkenyloxyl, such as vinyloxy, hexenyloxy, isopropenyloxy,
• Aryloxy, such as phenyloxy,
• Acyloxy, such as acetoxy,
• Ketiminoxy such as ON = C (CH 3) C 2 H 5; Amino derivatives such as ethylamino, phenylamino,
• - Amido derivatives, such as Methylacetamido.

• – für R¹, R²: beispielsweise die Gruppen Methyl, Ethyl, Octyl, Trifluorpropyl, Vinyl, Phenyl;
• – für R³, R⁴: beispielsweise die Gruppen Methyl, Ethyl, Octyl, Vinyl, Allyl, Phenyl; -(CH₂)₃-NH₂; -(CH₂)₃-NH-(CH₂)₂-N H₂.

As organic aliphatic or aromatic radicals may be mentioned

• For R ¹ , R ² : for example the groups methyl, ethyl, octyl, trifluoropropyl, vinyl, phenyl;
• For R ³ , R ⁴ : for example the groups methyl, ethyl, octyl, vinyl, allyl, phenyl; - (CH ₂ ) ₃ -NH ₂ ; - (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ .

The organopolysiloxane (s) of formula (1) have at 25 ° C a dynamic viscosity of 35 to 1000 Pa · s, preferably from 50 to 1000 Pa · s, preferably from 75 to 500 Pa · s, especially 100 to 160 Pa · s (measured at a shear gradient of 1 s ^-1 ).

The low viscosity organopolysiloxane free of hydroxyl groups, can be represented by the following formula (2).

Here, the radicals R ¹ to R ^{4 have} the same meaning as stated above for the formula (1), R ⁵ may have the same meaning as R ¹ or R ² , particularly preferably low-viscosity organopolysiloxanes in which at least 80% of R ¹ to R ^{5 is} a methyl group. n is a number from 3 to 100, preferably 5 to 50, in particular 8 to 15.

The low-viscosity organopolysiloxane is preferably at 25 ° C. a dynamic viscosity of 0.2 to 7 Pa · s, preferably 0.4 to 3.5 Pa · s, in particular from 0.5 to 1 Pas. In this case, the dynamic viscosities mentioned here are customary measured with rotational viscometers, for example with a Brookfield RVP viscometer. The amount of low viscosity used in the preparation Organopolysiloxane can be varied within wide limits, preferably are for 100 parts hydroxlgruppenhaltiges or hydrolyzable Group-containing organopolysiloxane 1 to 30 parts of low viscosity Organopolysiloxane added.

In Silicone-sealants can be used as crosslinking agents known as concrete examples of crosslinking agents to be used may be mentioned: colloidal silica, sodium silicate, fumed or precipitated silica, alkali metal organosilicates, Microemulsions of a silsesquioxane resin, reactive silicone resins low molecular weight alkoxy and / or acyloxy groups, High molecular weight silicone resins (insoluble in toluene), hydroxylated silicone resins, alkoxysilanes, alkylaminosilanes, alkylamidosilanes. It is also possible to use mixtures of the abovementioned crosslinking agents be used. To 100 parts organopolysiloxane or mixture Organopolysiloxanes use from 0.1 to 100 parts of crosslinker.

The for the preparation of the dispersions of the invention can be used surfactant (emulsifier) in principle an anionic, cationic or nonionic emulsifier be. Typically, however, nonionic emulsifiers are used preferably they have an HLB value (Hydrophilic Lipophilic Balance) from 8 to 15. Preferred nonionic emulsifiers are ethoxylation products of long-chain fatty alcohols, alkoxylation products of alkylphenols or it may also be block copolymers of polypropylene oxide / polyethylene oxide Find use. Further examples of suitable emulsifiers are alkyl glycosides, alkyl polyglycosides, polyalkoxylated fatty amides, Sugar ethers or sugar esters. If necessary, too Mixtures of several of the aforementioned emulsifiers used become. The emulsifiers are available in quantities of 1 to 20 parts 100 parts organopolysiloxane or organopolysiloxane mixture used.

When Curing catalysts can be a variety of customary catalysts are used in silane chemistry, it is preferably carboxylic acid salts of lead, zinc, zirconium, Titanium, iron, barium, calcium, manganese and in particular tin. It can also chelate compounds such as dicarbonyl chelates the aforementioned metals are used. For the tin compounds In particular, the diorganotin dicarboxylates, such as As dibutyltin dilaurate (DBTL), dioctyltin dilaurate, dibutyltin diacetate or Dioctylzinndiacetat be used. Typical quantity ranges for the crosslinking catalysts to be used are 0.01 to 3 parts of the crosslinking catalyst per 100 parts organopolysiloxane or Organopolysiloxanes.

One essential part of the invention Compositions are aqueous silicon-free polymer dispersions. These aqueous dispersions may consist of polyacrylates, Polymethacrylates and acrylate / methacrylate copolymers, polystyrene, Styrene copolymers with acrylates or methacrylates, vinyl acetate polymers or copolymers of vinyl acetate with ethylene and / or acrylates or styrene, polyolefins and especially polyurethane dispersions to be selected. It is also possible mixtures use of silicon-free polymer dispersions.

The aqueous polyurethane dispersion is prepared by processes known per se. there For example, an NCO-terminated prepolymer is usually first prepared by reacting bifunctional alcohols (polyols) with diisocyanates. These can then optionally by chain extension, z. B. further reacted with diamines to high molecular weight polyurethanes. So that a self-emulsifying polyurethane dispersion is formed in water, hydrophilic groups z. As anionic carboxy or sulfonic acid groups or cationic groups incorporated into the molecule. For reasons of viscosity, these polyurethanes can initially be prepared in inert organic solvents. The solvent or solvent mixture in this case is removed from the emulsion by distillation after the dispersion step in the aqueous phase.

As isocyanates, it is possible in principle to use all industrially available aromatic, aliphatic or cycloaliphatic di- or polyisocyanates. However, the following aliphatic or cycloaliphatic diisocyanates are particularly preferred:
4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate ( H ₆ XDI), 1-methyl-2,4-diisocyanato-cyclohexane, m- or p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI), dimer fatty acid diisocyanate, tetramethoxybutane-1,4-diisocyanate, butane-1,4 diisocyanate, hexane-1,6-diisocyanate (HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, butane-1,4-diisocyanate and 1,12-dodecane diisocyanate (C ₁₂ DI). Possibly. It is also possible to use the corresponding trimeric biuretization or isocyanurization products of the abovementioned diisocyanates.

When Polyols include polyether polyols, polyalkylene diols, polyester polyols for use. As polyether polyols find the known per se Polypropylene glycols or polybutylene glycols use. examples are Di- and / or trifunctional polypropylene glycols with two or three Hydroxyl groups per molecule in the molecular weight range from 400 to 20,000, preferably in the range of 1,000 to 6,000 may also be random and / or block copolymers of ethylene oxide and propylene oxides are used. Another group of preferably polyethers to be used are the polytetramethylene glycols (polybutylene glycols, poly (oxytetramethylene) glycol, Poly-THF) having a molecular weight range of polytetramethylene glycols between 600 and 6000.

When Polyester polyols are those which are suitable for the condensation of Di- or tricarboxylic acids, such as. For example adipic acid, Sebacic acid, glutaric acid, azelaic acid Suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, Terephthalic acid, isophthalic acid, hexahydrophthalic acid, Dimer fatty acid or mixtures thereof with low molecular weight Diols or triplets such. Ethylene glycol, propylene glycol, diethylene glycol, Triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, dimer fatty alcohol, Glycerol, trimethylolpropane or mixtures thereof are produced can. Another group of polyols are the polyesters on the basis of ε-caprolactone, also "polycaprolactone" called.

It but also polyester polyols of oleochemical origin become. Such polyester polyols may, for example by complete ring opening of epoxidized Triglycerides of an at least partially olefinically unsaturated Fatty acid-containing fat blend with one or more Alcohols with 1 to 12 C-atoms and subsequent partial Transesterification of the triglyceride derivatives to alkyl ester polyols with 1 to 12 C atoms are prepared in the alkyl radical. Other suitable polyols are polycarbonate polyols and dimer diols (Cognis) and castor oil and its derivatives, such as. B. partially dehydrated castor oil.

When hydrophilic groups can be cationic groups in the form of Polyamines are incorporated into the polyurethane molecule, however, preferred are anionic sulfonic acid groups and in particular carboxyl groups. Suitable carboxylic acid for Incorporation into the polyurethane framework are dihydroxypropanoic acid, Dihydroxysoxic acid, dihydroxybenzoic acid or also α, α-Dimethyloalkansäuren such. B. 2,2-dimethylolacetic acid, 2,2-dimethylpropionic acid, 2,2-dimethlylolbutyric acid and 2,2-dimethylolpenthanoic acid. For emulsification or dispersion of the carboxylated polyurethane in the aqueous phase, the carboxyl groups with a Neutralizing neutralized, this are preferably tertiary amines such as trimethylamine, triethylamine, Tributylamine, diethylaniline, triphenylamine, dimethylethanolamine, Diethylethanolamine, methyldiethanolamine or triethanolamine. there The neutralization step can be carried out both in the organic phase as well as in the aqueous phase. It is also possible, commercially available polyurethane dispersions for the sealant according to the invention Preparations to use, examples of which are U-5200VP or U-350VP from Alberdingk-Boley.

The aqueous silicon-free polymer dispersions are used in amounts of from 0.01 to 50 parts, preferably from 0.5 to 10 parts, of the polymer dispersion based on 100 parts of organopolysiloxane oil or organopoly siloxane mixture used.

When Fillers can be silicon-containing (reinforcing) Fillers are used to the extent that, in the silicon-containing additives are not already used as crosslinking agents were used. Examples are colloidal silica, fumed silica, precipitated silica. Examples of semi-reinforcing fillers are diatomaceous earth, ground quartz. Examples of silicate-free Fillers are natural, ground or precipitated Calcium carbonate, hydrated alumina, magnesium hydroxide, Carbon black, titanium dioxide, aluminum oxide, mica, zinc oxide, talc, Iron oxide, barium sulfate, slaked lime or mixtures of these Fillers. The fillers, especially the chalks (Calcium carbonates), may optionally be surface-treated ("Coated"). The mean particle size These fillers should in the range between 0.001 to 300 microns lie. The fillers are available in quantities of 50 to 400 Part filler, based on 100 parts Organopolysiloxanöl or organopolysiloxane mixture.

Examples of organofunctional silanes are 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3- (2,3-epoxypropoxy) propyltrimethoxysilane, 3- (2,3-epoxypropoxy) propyltriethoxysilane, 3- (2,3-epoxypropoxy) propyldiethoxymethylsilane, 3 (2,3-epoxypropoxy) propylethoxydimethylsilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropylethoxydimethylsilane and mixtures of the aforementioned silanes. Furthermore, oligomers of the above silanes can be used, examples include Dynasylan ^® 1146, Dynasylan ^® 6490, Dynasylan ^® 6498, Dynasylan ^® 6598, Dynasylan ^® 9896, Dynasylan ^® HYDROSIL 1151, Dynasylan ^® HYDROSIL 2627 Dynasylan ^® HYDROSIL 2776 Dynasylan ^® HYDROSIL 2909 or Dynasylan ^® HYDROSIL® 2926 the firm. Evonik. The amount of adhesion-promoting or adhesion-promoting organofunctional silanes depends on the substrates to be bonded, they are preferably used in amounts of less than 5, more preferably less than 2 wt .-%, based on the total composition of the sealant dispersion.

When other customary auxiliaries and additives can the compositions according to the invention tackifying Resins, other adhesion-promoting additives, pigments, plasticizers and / or stabilizers catalysts or mixtures thereof in amounts from 0 to 50 parts per 100 parts Organopolysiloxanöl or Organopolysiloxane oil mixture included.

The Amount of added to the preparation according to the invention Water depends on the water content of the organopolysiloxane oil used. Dispersion and / or silicon-free polymer dispersion and after the required rheological properties of the composition, it typically contains 1 to 30 parts, preferably 2 to 20 parts of water based on 100 parts Organopolysiloxanöl or organopolysiloxane oil mixture.

The Compositions according to the invention can in a known manner in mixing units with high shear be prepared, these include, for. Kneaders, planetary mixers, Internal mixer, so-called "Banbury mixer", twin-screw extruder and similar mixing units known to those skilled in the art.

Across from the previously known sealants, adhesives or Beshichtungsmitteln based on aqueous organopolysiloxane dispersions draw the compositions of the invention by improved adhesion on a variety of substrates, especially in the sanitary and kitchen area vorzufindenden plastic surfaces.

In the following embodiments, the invention be explained in more detail, with the selection of the Examples not limiting the scope of the subject invention should represent.

Examples

example 1

A silicone emulsion, as in WO1994009059 described, is mixed with a commercial PU dispersion (U-350 VP, Alberdingk-Boley) in a ratio of 90:10 parts by weight. After one week curing time on poly (carbonate) surfaces, the peel force increases by 300% compared to the same silicone emulsion without dispersion addition.

Example 2

A silicone emulsion, as in WO1994009059 described, is mixed with a commercial PU dispersion (U-5200 VP, Alberdingk-Boley) in a ratio of 90:10 parts by weight. After one week curing time on poly (ester) surfaces, the peel force increases by 200%.

Example 3 Preparation of a PU dispersion

A Polyurethane prepolymer is prepared by the known processes from 19.4 g of poly (THF) (Mw 1000 g / mol), 3.2 g of dimethylolpropionic acid and 12.6 g of TMXDI and then dispersed in 64 g of water.

Example 4

A silicone emulsion, as in WO1994009059 described, is mixed with a dispersion of Example 3 in the ratio 95: 5 parts by weight. After one week curing time on poly (carbonate), poly (vinyl chloride) and poly (methyl methacrylate) surfaces, the peel force increases by 150%.

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

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• WO 1994009059 [0042, 0043, 0045]

Claims (12)

Aqueous dispersions of silicone oils, including: a) at least one hydroxyl group or hydrolyzable Group-containing organopolysiloxane, b) at least one low-viscosity Organopolysiloxane, free of hydroxyl groups or hydrolyzable Groups, c) a crosslinking agent, d) at least one emulsifier, e) at least one crosslinking catalyst, f) at least one aqueous silicon-free polymer dispersion, G) at least one filler, h) water. Dispersion according to claim 1, characterized in that that the dispersion additionally contains at least one organofunctional Silane contains. Dispersion according to claim 1 or 2, characterized that the crosslinking agent is selected from colloidal Silica, sodium silicate, pyrogenic or precipitated Silica, alkali metal organosilicates, a microemulsion a silsesquioxane resin, a reactive silicone resin with low Molecular weight with alkoxy and / or acyloxy groups, a silicone resin high molecular weight which is insoluble in toluene, a hydroxylated silicone resin, an alkoxysilane, an alkylaminosilane, an alkylamidosilane or mixtures thereof. Dispersion according to at least one of the claims 1 to 3, characterized in that the emulsifier is a non-ionic Emulsifier is. Dispersion according to at least one of the claims 1 to 4, characterized in that the emulsifier or the mixture of emulsifiers has an HLB value of at least 8. Dispersion according to at least one of the claims 1 to 5, characterized in that the silicon-free polymer dispersion is selected from aqueous dispersions of Poly (meth) acrylates, polystyrene, styrene copolymers, vinyl acetate polymers or copolymers, polyurethanes or mixtures thereof. Dispersion according to at least one of the claims 1 to 6, characterized in that the polyurethane dispersion anionic Has groups. Dispersion according to at least one of the claims 1 to 7, characterized in that the hydroxyl-containing Organopolysiloxane a dynamic viscosity at 25 ° C. from 35 to 1000, especially 100 to 160 Pa · s. Dispersion according to at least one of the claims 1 to 8, characterized in that the low-viscosity organopolysiloxane a dynamic viscosity at 25 ° C from 0.2 to 7 Pa · s, in particular 0.5 to 1 Pa · s has. Dispersion according to at least one of the claims 1 to 9, characterized in that the polyurethane polymer Polyether polyols, polyester polyols, amino-terminated polyoxyalkylenes, hydroxy-functional polyolefins and polyisocyanates and dihydroxycarboxylic acids is constructed. Dispersion according to at least one of the claims 1 to 10 containing 100 parts Organopolysiloxanöl or Organopolysiloxane oil mixture a) 0.1 to 100 parts at least one crosslinking agent, b) 1 to 20 parts of a nonionic emulsifier or a mixture of emulsifiers, c) 0.01 to 3 parts of a crosslinking catalyst, or a catalyst mixture, d) 0.01 to 50 parts, preferably 0.5 to 10 parts of at least one aqueous polyurethane dispersion, e) 50 to 400 parts at least one filler, f) 1 to 30 parts, preferably 2 to 20 parts water, g) 0 to 50 parts of further auxiliary and Additives. Use of a preparation of dispersions according to at least one of claims 1 to 11 as hardenable adhesive, sealant or coating agent with improved adhesion properties.