DE19914884A1 - Special polyurethane dispersion for coating glass fibres or other coating applications, made by reacting isocyanate prepolymer with chain extenders and monoamino-functional alkoxy-silane chain stopper - Google Patents

Abstract

Special polyurethane (PUR) dispersions with terminal alkoxysilane groups, containing dispersed and/or dissolved products obtained by reacting isocyanate-functional prepolymers with chain extenders and then with chain stoppers consisting of monoamino-functional alkoxysilanes (g). Independent claims are also included for (i) glass fibre coating materials containing these PUR dispersions as the essential film-forming component, especially with blocked polyisocyanate crosslinkers (which may also contain hydrophilic groups); (ii) a process for the production of these PUR dispersions by reacting polyol(s) (a) with isocyanate(s) (b), optionally in presence of hydrophilising components (c) and/or chain extenders (d) to form a prepolymer, reacting some of the remaining NCO groups (in organic solution or after dispersion) with another chain extender (e), optionally (c) and optionally a blocking agent (f), reacting the rest of the NCO groups with chain stopper (g) before, during or after dispersion and then removing any solvent (added before, during or after prepolymer production) by distillation; (iii) a process for the production of PUR dispersions by reacting tri- or higher-functional polyisocyanates with the required amount of monofunctional alkoxysilane to form a difunctional, alkoxysilane-modified isocyanate component (bg), reacting this with (a), optionally di-isocyanate (b), component (c) as above and optionally (d) to form an NCO-functional prepolymer, reacting some of the remaining NCO groups (in solution or dispersion) with (e), optionally (c) and (f), and then optionally removing solvent as above.

Description

The invention relates to polyurethane dispersions containing alkoxysilane end groups hold a process for the preparation of such dispersions and their use in or as finishing.

Polyurethane dispersions with alkoxysilane groups that can be crosslinked at room temperature, which harden to hard, water- or solvent-resistant and scratch-resistant paints and Z. B. for painting wood, (PVC) floors, metallic substrates as well as are well suited for road marking paints are e.g. B. from the WO 94/13723 known. Such dispersions are especially important for glass fiber sizes less suitable due to their molecular structure and high degree of cross-linking net, as well as those described in US Pat. No. 5,554,686, cures at room temperature baren, purely ionic, preferably with carboxylate groups, hydrophilized silanters minimized polyurethane dispersions. Such dispersions show in size formu Inadequate stability, and a carboxylate hydro Philating the susceptibility of corresponding glass fiber reinforced plastics to hydrolysis. This can lead to a rapid degradation of the mechanical properties of the plastics to lead.

EP-A 814 105 describes silane-functional polyurethane dispersions based on of special polyesters, isocyanate-functional adducts and silane-functional ones Polyisocyanates, as well as their use in two-component paints for the Painting of metallic substrates. Two-component paints require the Separate storage of two components that were only mixed shortly before application will. This is associated with increased effort and carries the risk of reduced Properties due to mixing errors. A suitability of such products for Glasfa no arbitration is given.

US Pat. No. 5,041,494 describes cationically hydrophilized polyurethane dispersions with pH values of 3 to 6 and higher contents of alkoxysilane groups (defined by a content of at least 1.3% by weight SiO ₃ structure elements) the paints to be crosslinked dry.

The US-A 3,941,733 describes curable, silanol group-containing polyurethane Dispersions that are purely ionically hydrophilized and none in their production Chain extension reagents are used. With such products must because of the chain extension caused by the isocyanate-water reaction with heavy reproducible product properties, and due to the ionic hydrophilization stability problems can be expected in common sizing formulations.

US Pat. No. 4,582,873 describes a process for the production of water-dispersible materials Polyurethanes with pendent, reactive siliconate anion structures, which by before preferably use of difunctional organosilanes in the production of it will hold.

WO 90/10026 describes alkoxysilane-terminated polyurethanes, herge made from hydrophilic polyethylene glycols, hydrophobic polyols, polyisocyanate and alkoxysilane, chain extension reactions not being carried out. The products are suitable for finishing textile fiber materials containing polyester net.

There is still a need for improved polyurethane dispersions for glass fiber sizing, which above all have good processing properties and good reinforcement have properties when used in glass fiber reinforced plastics have to.

Surprisingly, it has now been found that glass fiber sizes, the special Polyurethane dispersions with alkoxysilane end groups contain, improved appli cation properties, improved processability of glass coated with it fibers and very good mechanical properties of corresponding glass fiber reinforced Show plastics.

Surprisingly, it has been found that special polyurethane dispersions that a predominantly linear structure, a high molecular weight and from finally contain terminal alkoxysilane groups in a relatively low amount, the Enable the production of high quality glass fiber sizes.

The polyurethane dispersions according to the invention show in particular an excellent marked adhesion to glass, glass fibers or glass-like substrates. Surprise in this way, glass fibers sized with the dispersions according to the invention show when used in thermoset reinforcement, a particularly low and thus advantageous styrene solubility.

The mechanical properties of corresponding reinforced plastics are very good Well. The hydrolysis resistance is also good.

Due to the small amount of alkoxysilane end groups take place after the appli cation Crosslinking reactions - if at all - then only to a very limited extent Scope. The coatings are therefore neither cross-linked nor are they scratch-resistant or a pronounced solvent resistance.

The outstanding suitability of the poly according to the invention is all the more surprising urethane dispersions for sizing or coating of glass.

The dispersions according to the invention are for the sake of simplicity as polyurethane Denotes dispersions, but they also contain urea or polyurine fabric segments. The term dispersion also includes dispersions contain dissolved polymer components. The proportion of dissolved polymers can be, for. B. influenced by the molecular weight or the content of hydrophilizing components be flowing.

The invention therefore relates to special polyurethane dispersions for glass fiber sizes with alkoxysilane end groups, which by chain extension of a Isocyanate-functional prepolymer and subsequent chain termination reaction with a monaminofunctional alkoxysilane can be obtained.

The polyurethane dispersions according to the invention with alkoxysilane end groups are composed of reaction products present in dispersed or dissolved form

• a) at least one polyol component,
• b) at least one di- and / or polyisocyanate component,
• c) at least one hydrophilic, nonionic structural component, consisting from compounds with at least one reaction against isocyanate groups ven group and at least one hydrophilic polyether chain and given if at least one (potentially) ionic compound with at least one, optionally present at least partially neutralized, for Group capable of salt formation and at least one towards isocyanate group pen reactive group,
• d) optionally one or two of a) to c) different low molecular weight Build-up component of the molecular weight range 62 to 450 with min at least two isocyanate-reactive groups,
• e) at least one chain extension component of the molecular weight 32 to 350 with at least two isocyanate-reactive groups pen,
• f) optionally a monofunctional blocking agent and
• g) at least one monoamino-functional alkoxysilane as a chain terminator reagent,

component (s) c) being used in such an amount that a stable dis persion arises.

The polyurethane dispersions according to the invention with alkoxysilane end groups are preferably composed of reaction products present in dispersed or dissolved form

• a) 40 to 75 wt .-% of at least one polyol component of the hydroxyl number range 5 to 350,
• b) 10 to 45% by weight of at least one di-, tri- and / or polyisocyanate composite nent,
• c) 4 to 22% by weight of hydrophilic structural components, consisting of at least a hydrophilic, nonionic compound with at least one against group reactive via isocyanate groups and at least one hydrophilic group Polyether chain and optionally at least one (potentially) ionic Compound with an optionally at least partially neutralized before lying group capable of salt formation and at least one opposite Isocyanate group reactive group,
• d) 0 to 5% by weight of one or two structural components different from a) to c) nente of the molecular weight range 62 to 450 with at least two group reactive towards isocyanate groups,
• e) 0.1 to 7.5% by weight of at least one chain extension component of the Molecular weight 32 to 350 with at least two against isocyanate groups reactive groups,
• f) 0 to 7% by weight of a monofunctional blocking agent and
• g) 0.25 to 10% by weight of at least one monominofunctional alkoxysilane as a chain termination reagent,

component (s) c) being used in such an amount that a stable dis persion arises.

The polyurethane dispersions according to the invention with alkoxysilane end groups are particularly preferred reaction products present in dispersed or dissolved form

• a) 40 to 69 wt .-% of at least one polyol component of the hydroxyl number range 5 to 350,
• b) 12 to 35 wt .-% of at least one di-, tri- and / or polyisocyanate composite nent,
• c) 6 to 18% by weight of hydrophilic structural components, consisting of at least a hydrophilic, nonionic compound with at least one against group reactive via isocyanate groups and at least one hydrophilic group Polyether chain and optionally at least one (potentially) ionic Compound with an optionally at least partially neutralized before lying group capable of salt formation,
• d) 0 to 3% by weight of one or two structural components different from a) to c) nente of the molecular weight range 62 to 450 with at least two group reactive towards isocyanate groups,
• e) 0.2 to 6.0 wt .-% of at least one chain extension component of the Molecular weight 32 to 350 with at least two against isocyanate groups reactive groups,
• f) f 0 to 3.5% by weight of a monofunctional blocking agent and
• g) 0.5 to 5 wt .-% of at least one monominofunctional alkoxysilane as Chain termination reagent,

components c) being used in such an amount that a stable dispersion sion arises.

The polyurethane dispersions according to the invention with alkoxysilane end groups are very particularly preferred reaction products present in dispersed or dissolved form

• a) 40 to 69 wt .-% of at least one polyol component of the hydroxyl number range 5 to 350,
• b) 12 to 35% by weight of at least one aliphatic and / or cycloaliphatic Diisocyanate component with a molecular weight of 168 to 262,
• c) 6 to 18 wt .-% hydrophilic structural components, consisting of one hydrophilic, nonionic compounds with an opposite isocyanate groups reactive group and a hydrophilic polyether chain and one ionic compound with an at least partially neutralized the sulphonic acid group and two isocyanate-reactive groups Groups,
• d) 0 to 3% by weight% by weight of one or two structures different from a) to c) component of the molecular weight range 62 to 450 with at least two group reactive towards isocyanate groups,
• e) 0.2 to 6.0 wt .-% of at least one chain extension component of the Molecular weight 32 to 350 with two or three opposite isocyanate group pen reactive primary and / or secondary amino groups,
• f) 0 to 3.5% by weight of a monofunctional blocking agent and
• g) 0.75 to 3% by weight of a monoamino-functional alkoxysilane as chains termination reagent,

component (s) c) being used in such an amount that a stable dis persion arises, and taking all neutralizing agents before dispersing be admitted.

The invention also relates to a process for the production of an alkoxysilane end polyurethane dispersions containing groups, characterized in that from given at least one polyol a), at least one isocyanate component b) if with the use of hydrophilizing components c) or a compo nente d) first an isocyanate-functional prepolymer is prepared, then a Part of the remaining isocyanate groups either in organic solution or after dispersing with a chain extension component e), optionally one hydrophilizing component c) and optionally a blocking agent f) is reacted and then the remaining isocyanate groups either before, wäh rend or after dispersing with a monoamino-functional alkoxysilane g) be made to react and then before, during or after the Pre polymer production, optionally added solvents, optionally by distillation Will get removed.

In one variant of the process, trifunctional or higher-functional polyisos are first used cyanates reacted with such amounts of monofunctional alkoxysilanes that one difunctional alkoxysilane-modified isocyanate component bg) results with at least one polyol a) optionally a diisocyanate component b), min at least one hydrophilizing component c) and optionally a com Component d) converted to an isocyanate-functional prepolymer, then a part the remaining isocyanate groups either in organic solution or after Dispersing with a chain extension component e), optionally with one hydrophilizing component c) and optionally a blocking agent f) implemented and then before, during or after the prepolymer production optionally added solvent is optionally removed by distillation. The invention also relates to the use of special polyurethane dispersers sions with alkoxysilane end groups in or as sizes, especially for glass fiber sern.

The invention also relates to the use of special polyurethane dispersers sions with alkoxysilane end groups in or as a coating and / or lacquer.

The invention also relates to the use of special polyurethane dispersers sions with alkoxysilane end groups in combination with blocked polyisocyanate crosslinking in or as sizes, in particular sizes for glass fibers.

The invention also relates to the use of special polyurethane dispersers Sions with alkoxysilane end groups and blocked bound to the polymer Isocyanate groups in or as sizes, in particular sizes for glass fibers.

Polyol components suitable for producing the dispersions according to the invention a) are e.g. B. Polyester polyols (e.g. Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, Volume 19, pp. 62-65). Suitable raw materials for making this poly Ester polyols are difunctional alcohols such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-, 1,4-, 2,3-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylhexane diol, triethylene glycol, hydrogenated bisphenols, trimethylpentanediol, diethylene digly kol, dipropylene diglycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and difunctional carboxylic acids or their anhydrides such as adipic acid and phthalic acid acid (anhydride), isophthalic acid, maleic acid (anhydride), terephthalic acid, tetrahydro phthalic acid (anhydride), hexahydrophthalic acid (anhydride), succinic acid (anhydride), Fumaric acid, azelaic acid, dimer fatty acid. Also suitable polyester raw materials are monocarboxylic acids such as benzoic acid, 2-ethylhexanoic acid, oleic acid, soybean oil fat acid, stearic fatty acid, peanut oil fatty acid, linseed oil fatty acid, nonanoic acid, cyclo hexane monocarboxylic acid, isononanoic acid, sorbic acid, conjuene fatty acid, higher func tional carboxylic acids or alcohols such as trimellitic acid (anhydride), butanetetracar acid, trimer fatty acid, trimethylolpropane, glycerine, pentaerythritol, castor oil, Dipentaerythritol and other polyester raw materials not mentioned by name.

Also suitable polyol components a) are polycarbonate diols z. B. by Implementation of diphenyl or dimethyl carbonate with low molecular weight di- or Triplets or ε-caprolactone-modified di- or triols can be obtained.

Likewise suitable are polyester diols based on lactone, which are homo- or copolymers of lactones, preferably around terminal hydroxyl groups having addition products of lactones such. B. ε-caprolactone or gamma-butyrolactone acts on difunctional starter molecules. Suitable starters molecules can include the diols mentioned above, but also low molecular weight polyester or polyether diols. Instead of the polymers of lactones, the corresponding hydroxycarboxylic acids are used.

Polyether polyols are also suitable polyol components a). You are in particular by polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, Sty roloxid and / or epichlorohydrin with itself, for. B. in the presence of BF ₃ or basic catalysts or by addition of these compounds, if necessary, as a mixture or in succession, of starter components with reactive hydrogen atoms, such as alcohols, amines, amino alcohols or water.

The polyol components a) mentioned can also be used as mixtures, if appropriate also together with other polyols a) such. B. polyester amides, polyether esters, Polyacrylates, polyols based on epoxy resin, are used.

The hydroxyl number of the polyols a) is from 5 to 350, preferably from 8 to 200 mg KOH / g substance. The molecular weights of the polyols a) are between 300 and 25,000, preferably between 300 and 15,000, in a preferred embodiment at least partially polyols a) with a molecular weight of <9000 g / mol are used.

Preference is given as component a) to hydrolysis-stable polyols of the molecular weight weight 300 to 3500 based on carbonate diols, tetrahydrofuran diols and / or di- or trifunctional polyethers on propylene oxide or propylene oxide / Ethylene oxide base or mixtures of the hydrolysis-stable polyols mentioned sets, with the use of trifunctional polyether polyols this at most in Amounts up to 4% by weight based on the total solids content of the polymer be set.

These hydrolysis-stable polyols can also preferably be used together with ordered amounts of polyester polyols with comparatively good hydrolysis stability mobility, such as B. polyesters based on phthalic anhydride, isophalic acid, dimer fat acid, hexanediol and / or neopentyl glycol can be used.

Polyols based on polyester with molecules are also preferred as component a) largewichten from 400 to 950 are used, optionally also as a mixture of Polyester polyols of molecular weight 400 to 950 and others mentioned above Polyols.

In a particularly preferred embodiment, component a) is used in amounts used from 40 to 49 wt .-%.

The total proportion of trifunctional or - less preferably - higher functional components a) to g) is 0 to 6, preferably 0 to 4% by weight based on the total solids material content of the polymer.

Component b) consists of at least one organic di-, tri- or poly Isocyanate with a molecular weight of 140 to 1500, preferably 168 to 262. Suitable are z. B. hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diiso cyanatodicyclohexyl methane (H12MDI), 1,4-butane diisocyanate, hexahydrodiisocya natotoluene, hexahydrodiisocyanatoxylene, nonane triisocyanate. In principle suitable however, aromatic isocyanates such as 2,4- or 2,6-diisocyanates are not preferred totoluene (TDI), xylylene diisocyanate and 4,4'-diisocyanatodiphenylmethane. Likewise Polyisocyanates based on the known per se can also be used mentioned and also other isocyanates with uretdione, biuret, allophanate, isocya nurate, iminoxadiazinedione, or urethane structural units, but this is not preferred.

The exclusive use of aliphatic and / or is particularly preferred cycloaliphatic difunctional isocyanates with a molecular weight of 168 to 222, in particular of isophorone diisocyanate and / or hexamethylene diisocyanate and / or Diisocyanatodicyclohexylmethane (Desmodur® W, Bayer AG).

Component c) consists of at least one hydrophilic, nonionic coating construction component consisting of connections with at least one opposite Isocyanate-reactive group and at least one hydrophilic polyether chain and optionally at least one (potentially) ionic compound with min at least one, optionally present at least partially neutralized, for Group capable of salt formation and at least one towards isocyanate groups reactive group.

The ionic compounds c) are, for. B. at least one, preferably wise one or two hydroxyl and / or primary or secondary amino groups containing carboxylic acid, sulfonic acid and phosphoric acid or their salts. Suitable acids are e.g. B. hydroxypivalic acid, dimethylolacetic acid, 2,2'-dime ethylolpropionic acid, 2,2'-dimethylolbutyric acid, aminobenzoic acid, 2,2'-dimethyl olpentanoic acid, addition products of acrylic acid and diamines such as. B. ethylene diamine or isophoronediamine. The use of gebe is also suitable sulfonate diols optionally containing ether groups of those in US Pat. No. 4,108,814 described type. Also suitable are amino-functional sulphonates with one or two reactive, d. H. primary or secondary amino groups.

The free acid groups, in particular carboxyl and sulfonic acid groups, represent the "potentially ionic or anionic" groups mentioned above, while the salt-like ones obtained by neutralization with bases or acids Groups, especially carboxylate groups and sulphonate groups, around those above addressed "ionic or anionic" groups.

In a preferred embodiment, anionic components c) consist of the addition product of equivalent amounts of acrylic acid and isophoronediamine. This results in a favorable compatibility and a reduced tendency to crystallize Obtainment of the polymer and improved application properties.

In a particularly preferred embodiment, there are anionic components c) from compounds containing sulphonate groups with one or preferably two reactive hydroxyl or amino groups.

This improves the compatibility with other binder components and the hydrolysis resistance and the stability of the sizes positively influenced.

(Potentially) anionic component c) with two or three reactive primary and / or secondary amino groups can also be used as chain lengthening components nent e) can be used.

Nonionic hydrophilic compounds c) are mandatory and have pro Molecule has one or two isocyanate-reactive groups, in particular hydroxyl and / or primary or secondary amino groups and min at least one hydrophilic polyether chain. The polyether chains of these compounds consist of 30% to 100% of built-in ethylene oxide units, with one preferred embodiment 40 to 95% incorporated ethylene oxide units in addition to 5 up to 60% built-in propylene oxide units are present. Suitable such compo nents c) have molecular weights of 300 to 6000 and are z. B. monofunk tional polyethylene / propylene glycol monoalkyl ethers such as Breox® 350, 550, 750 from BP Chemicals, Polyether LB 25, LB 30, LB 34, LB 40 from Bayer AG, polyethylene / propylene glycols such as Carbowax® 300, 400, 1000, 2000, 6000 from Union Carbide, di- or monofunctional polyetheramines such as Jeffamine® ED600, ED900, ED4000, Texaco M715, M1000, M2070.

Preference is given to nonionic monofunctional components c) of the molecular weight 1000 to 2500 with a content of built-in propylene oxide from 10 to 57% and a content of built-in ethylene oxide of 90 to 43%.

A mixed hydrophilization of nonionic hydrophilic is preferred Components c) in amounts of 4 to 15% by weight and anionic components c) with carboxylate groups, preferably from the reaction product of isophorone diamine and acrylic acid are used in amounts of 0.5 to 6% by weight.

A mixed hydrophilization of nonionics is particularly preferred hydrophilic components c) in amounts of 4 to 15 wt .-% and anionic Components c) with sulphonate groups are used in amounts of 0.5 to 6% by weight.

Purely nonionic hydrophilization by means of com is also particularly preferred components c) in amounts of 15 to 21% by weight.

The component d) is one of a), b) and c) different never the molecular structural component of the molecular weight range 62 to 450 with at least two isocyanate-reactive groups. This reactive Groups are preferably hydroxyl groups.

Suitable components d) are, for. B. ethylene glycol, 1,2-, 1,3-propylene glycol, 1,4- Butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, trimethylolpro pan, glycerol, the reaction product of 2 moles of propylene carbonate and 1 mole Hydrazine and / or mixtures of the above, optionally also with others Components d). Components d) are used in amounts of from 0 to 5, preferably from 0 to 3% by weight of 2 are used.

Component e) is at least one of a) to d) different dene chain extension component of molecular weight 32 to 350 with min at least two isocyanate-reactive groups. Reactive groups are preferably primary or secondary amino groups. Suitable components ten e) are z. B. ethylenediamine, diethylenetriamine, isophoronediamine, hexamethylene diamine, 4,4-diaminodicyclohexylmethane, hydroxyethylethylenediamine, ethanolamine, Diethanolamine, isopropanolamine, diisopropanolamine, N-methylethanolamine, ami nomethylpropanol, hydrazine (hydrate), propylenediamine, dimethylethylenediamine, Adi pinic acid dihydrazide and / or mixtures of these, optionally also with further components e). The components e) are used in amounts of 0.1 5 to 5, preferably from 0.2 to 3.5 and very preferably from 0.2 to 2.5% by weight.

Preference is given to difunctional amines, optionally in combination with a triamine used.

In a preferred embodiment, the chain extender e) is 0.1 to 1.0% by weight of hydrazine or an equivalent amount of hydrazine hydrate, if appropriate used in combination with other components e) mentioned above.

Di- and / or trifunctional (potentially) anionic components c) with two or three reactive primary and / or secondary amino groups, such as. B. 2-amino ethylaminoethane sulphonate or the 1: 1 reaction product of acrylic acid and Isophoronediamine can also be used as chain extension reagent e). This can be done in combination with other above-mentioned compounds e), however, a component c) can also be used as the sole chain extension reagent e) act.

By suitable selection of component e), the increase in molecular weight can influenced by chain lengthening or chain branching and in a defined way and the way high molecular weights are built up.

Suitable monofunctional blocking agents f) can, for. B. be: butanone oxime, Cyclohexanone oxime, acetone oxime, malonic ester, triazole, ε-caprolactam, phenol, di methylpyrazole, monofunctional amines such as. B. Di-butylamine, diisopropylamine, monofunctional alcohols such as. B. butanol, cyclohexanol, isopropanol, tert-buta nol. Mixtures of different blocking agents can also be used the, in particular mixtures of blocking agents used at different Unblock temperatures and so a preferred embodiment, a staged wise response, enable.

Preferred blocking agents are butanone oxime, epsilon-caprolactone, dimethyl pyrazole and alcohols or mixtures of these blocking agents. The blockage Agents can be used in amounts from 0 to 7, preferably from 0 to 4% by weight be set.

In the preparation of the dispersions according to the invention, preference is given to every equivalent of any blocking agent used is one equivalent lent of a trifunctional chain extender e) used to ge desired to achieve high molecular weights.

Suitable monoamino-functional alkoxysilanes as chain termination component g) are z. B. 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino propyltributoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2- Aminoethyltributoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutyltrimethoxy silane, 3-aminopropylmethyldiethoxysilane, 4-amino-3,5-dimethylbutylmethyldieth oxysilane, reaction products of the alkoxysilanes mentioned with malonic acid dialkyl esters such as B. diethyl malonate, dimethyl malonate or malonic acid dibutyl esters, compounds of the type mentioned in which one or two of the alkoxy groups are replaced by alkyl groups and mixtures of the above and also other alkoxysilanes. Component e) is used in amounts of 0.25 to 10, preferably wise from 0.5 to 5, particularly preferably from 0.75 to 3 wt .-% used.

In a particularly preferred embodiment, the mathematically determined content of —Si- (O-) _{3 in} the solids of the polyurethane dispersions is less than 1.25% by weight.

In a preferred embodiment, chain extenders are e), Gege optionally blocking agents f) and monoamino-functional alkoxysilanes g) in Amounts of 35 to 85 equivalent percent of reactive amino and / or Hydroxyl groups based on the free isocyanate groups of the prepolymer from the Components a) to d) are used. I. E. that is the amount of isocyanate-reactive group pen in e), f), and g) 35 to 85% of the amount of reactive isocyanate groups of the Pre polymers from a) to d).

In a further preferred embodiment, contain the invention Dispersions of different blocked isocyanate groups, the isocyanate groups deblock at different temperatures and so once to a good Ver bundle of fiberglass to size and in the second step for a good bond of the sized glass fibers contribute to plastic.

The polyurethane dispersions according to the invention with alkoxysilane groups show A practical storage stability at room temperature up to 65 ° C. According to the appli cation, drying takes place at temperatures of 90 to 280 ° C, preferably at 110 to 200 ° C.

The dispersions according to the invention are prepared in such a way that from at least a polyol a), at least one isocyanate component b) optionally under Use of hydrophilic components c) or a component d) first an isocyanate-functional prepolymer is produced, then part of the remaining isocyanate groups either in organic solution or after Dispersing with a chain extension component e), optionally one hydrophilizing component c) and optionally a blocking agent f) is reacted and then the remaining isocyanate groups either before, wäh rend or after dispersing with a monoamino-functional alkoxysilane g) be made to react and then before, during or after the Pre polymer production, optionally added solvents, optionally by distillation Will get removed.

In a preferred variant of the method, at least one polyol is initially used a), at least one diisocyanate b) a monohydroxy-functional, non-ionic rule hydrophilization component c), optionally a mono- or dihy hydroxy-functional (potentially) anionic hydrophilization component c) and optionally di- and / or trihydroxy-functional components d) an isocya Naturally functional prepolymer produced, this then either before dispersing, then in the presence of a solvent, or after dispersing first with the Chain extender e) and optionally f) and then with the chain terminating agent g) is made to react, and then before, during or any solvents added after prepolymer production If necessary, is removed by distillation, the entire amount of neutralizing agent before is added to the dispersing.

In a further preferred variant of the method, at least one is initially selected a polyol a), at least one diisocyanate b), a monohydroxy functional, nonionic hydrophilization component c) and optionally di- and / or trihydroxy-functional components d) an isocyanate-functional prepolymer placed, this then either before dispersing, then in the presence of solvent medium, or after dispersing first with a mixture of a diamino functional (potentially) ionic hydrophilicizing agents c) and chain lengthening agents r means e) and optionally f) brought to reaction and then with the Chain terminator g) is implemented, and then before, during or solvents optionally added after the prepolymer production is removed by distillation, the total amount of neutralizing agent before Dispersing is added.

In a further variant of the method, tri- or higher-functional ones are initially used Polyisocyanates reacted with such amounts of monofunctional alkoxysilanes that a difunctional alkoxysilane-modified isocyanate component bg) results, the with at least one polyol a) optionally a diisocyanate component b), at least one hydrophilizing component c) and optionally one Component d) converted to an isocyanate-functional prepolymer, then a Part of the remaining isocyanate groups either in organic solution or after dispersing with a chain extension component e), optionally one (potentially) anionic hydrophilization component c) and optionally one Blocking agent f) implemented and then before, during or after Prepolymer production, if appropriate, added solvents, if appropriate, distil is removed relatively.

The implementation of the components can be carried out with the addition of catalysts such. B. Dibutyltin dilaurate, tin 2-octoate, dibutyltin oxide or diazabicyclononane be guided.

To convert the acid groups into salt groups, for. B. amines such as triethyl amine, N-methylmorpholine, diisopropylamine, hydroxyamines such as diethanolamine, Triethanolamine, diispropanolamine, aminomethylpropanol, potassium or sodium hydroxide, ammonia and di- or polyamines such as hexamethylenediamine, isophorone diamine, dimethylethylenediamine, 1,4-cyclohexanediamine, trimethylhexanediamine, Dimethylhexanediamine, Jeffamine® (Texaco) such as e.g. B. 3,3 '- [1,4-butanediyl bis (oxy)] bis-1-propanamine, 4,4'-methylene-bis- (2,6-diethylcyclohexanamine), 4,4'- Methylenebis (2-methylcyclohexanamine), 4,4'-methylenebis-cyclohexanamine are set.

The degrees of neutralization are generally between 40 and 120%, preferably wisely at 100 to 120%.

In a preferred embodiment, the complete amount of Neutralisa tion means even before the prepolymer or polymer is dispersed in / with Water added.

After dispersing in / through water, the mixture is stirred until all of it any isocyanate groups still present have reacted. Is also possible complete implementation of all isocyanate groups with the above com components before dispersing in / with water.

The solvents optionally used to prepare the dispersion can partially or preferably completely separated from the dispersion by distillation will. The dispersions particularly preferably contain less than 2% by weight volatile solvents and neutralizing agents. Preferred solvents are in particular Acetone or methyl ethyl ketone, but also N-methylpyrrolidone.

Optionally, the polymers can be used before, during or after dispersing also auxiliaries and additives, such as anti-settling agents, defoamers, thickeners, emulsions gators, catalysts, leveling aids, adhesion promoters, biocides, antistatic agents, Sunscreens, lubricants, thermal stabilizers, etc. but also special oligo mer or polymeric compounds with or without hydrophilic groups added will.

The dispersions according to the invention have average particle diameters (be true z. B. by laser correlation spectoscopy) from 20 to 900, preferably from 50 to 400 nm.

The solids contents of the dispersions are from 10 to 150 at viscosities Seconds flow time (DIN 4 cup, 23 ° C) at least 30%. The pH values are between preferably 5.0 and 11.0.

The dispersions according to the invention are particularly suitable for use in or as sizes, preferably glass fiber sizes. The dispersions can be used as sole binder or together with other polymers such as. B. Polyurethane dispersions, polyacrylate dispersions, polyester dispersions, polyether dispersions, Polyepoxide dispersions, polyvinyl ester or polyvinyl ether dispersions, Polysty rol or polyacrylonitrile dispersions, blocked polyisocyanates, blocked poly isocyanate dispersions, amino crosslinking resins such. B. melamine resins are used will.

In a preferred application form, the dispersions according to the invention are in combination with blocked ones optionally containing hydrophilic groups Polyisocyanates based on hexamethylene diisocyanate, isophorone diisocyanate and / or Desmodur W are used.

Preferred mixing ratio of inventive dispersion to polyiso cyanate crosslinker is 65 to wt .-% to 35 to 10 wt .-%, each based on Solids content.

Suitable blocking agents for these polyisocyanate crosslinkers are, for. B. Butanone oxime, ε-caprolactam or dimethylpyrrazole. Suitable hydrophilization Medium are above all the ionic and non-ionic substances mentioned for component c) compounds, especially those with one or two, for reaction with Isocyanate groups available, hydroxyl groups.

The dispersions according to the invention or the sizes produced therewith can contain the usual auxiliaries and additives, such as. B. Defoaming Agents, Ver thickening agents, leveling agents, dispersing agents, catalysts, skin agents inhibitors, anti-settling agents, emulsifiers, biocides, adhesion promoters, e.g. B. on Basis of the well-known low or high molecular weight silanes, lubricants, wetting agents, Antistatic agents.

The finishes can be applied using any method, for example with the help of suitable devices such. B. spray or roller applicators. she can be applied to the glass filaments drawn from spinnerets at high speed immediately after their solidification, d. H. can be applied before winding. It it is also possible to place the fibers in an immersion bath after the spinning process to settle. The sized glass fibers can either be wet or dry when For example, it can be processed into cut glass. The drying of the end or Intermediate takes place at elevated temperatures. Is under drying not just understanding the removal of other volatile constituents, but z. B. also the solidification of the size components. The proportion of sizing is, based on the sized glass fibers, 0.1 to 4%, preferably 0.2 to 2% by weight.

Both thermoplastic and thermoset polymers can be used as matrix polymers be used.

The dispersions according to the invention obtained are also suitable for all purposes areas of application in which solvent-based, solvent-free or other types of aqueous Paint and coating systems with a higher profile of properties Ver find application, e.g. B. Coating of mineral substrates, painting and Ver sealing of wood and wood-based materials, painting and coating of metallic ones Surfaces, painting and coating of plastics as well as the coating of textiles and leather. The dispersions of the invention can be used as Primer, adhesive coat, adhesive primer, filler, top coat, one-coat paint, top coat or finish in the form of clear lacquers or clear coatings or in pig mentated form is used.

Examples example 1

In a 6-liter reaction vessel equipped with a stirrer, cooling and heating device, 1237 g of a difunctional adipic acid-butanediol polyester with the molecular weight 900 g / mol, 278 g of polyether LB25 (Bayer AG, monofunctional polyether Ethylene oxide / propylene oxide base, molecular weight 2245 g / mol), 27.2 g butanediol 1.4 and 116.4 g of a sodium sulphonate diol of molecular weight 432 g / mol weighed, homogenized at 75 ° C and then with 849 g of isophorone diisocyanate 100 ° C until the theoretical isocyanate value has been reached. That Isocyanate-functional polyurethane prepolymer is made after cooling to 75 ° C dispersed by adding 3300 g of distilled water in 10 minutes, then is a 25% aqueous solution of 8.0 g in about 15 minutes to extend the chain Hydrazine, 12.9 g of diethylenetriamine and 43.8 g of ethylenediamine were added and after 10 minutes reaction time followed by a chain termination solution made of 60.8 g of 3- Aminopropyltriethoxysilane and 440 g of water were added in about 15 minutes and Stirred at 50 ° C. until no isocyanate groups by infrared spectroscopy are more detectable. A finely divided polyurethane dispersion is obtained with Alkoxysilane end groups, which have a solids content of approx. 41%, a viscosity in DIN 4 flow cup (23 ° C) of 14 seconds and a pH of 6.6.

Example 2

In a 6-liter reaction vessel equipped with a stirrer, cooling and heating device, 1105 g of a polycarbonate diol with a molecular weight of 2000 g / mol (Desmophen C200, Bayer AG), 227.5 g of a difunctional polypropylene glycol with the molecular weight 1000, and 365 g polyether LB25 (Bayer AG, monofunctional polyether based on ethylene oxide / propylene oxide, molecular weight 2245 g / mol) weighed in, Melted at 70 ° C and then with 209 g of isophorone diisocyanate and 152.9 g Hexamethylene diisocyanate reacted until the theoretical isocyanate value has been achieved. The isocyanate-functional polyurethane prepolymer is then diluted with 1800 g of acetone and a 25% chain extender solution in water of 61.8 g of aminoethylaminoethanesulphonic acid in the form of the sodium salt, 2.3 g Hydrazine and 20.2 g diethylenetriamine were added quickly. Then through Addition of 3300 g of distilled water, followed by the addition of a dispersed 50% acetone solution of 42 g of the chain termination reagent 3-aminopro pyltrimethoxysilane. After the addition has ended, the acetone is distilled off, and one obtains an approx. 39%, finely divided dispersion with a viscosity of 20 seconds (measured in a DIN 4 flow cup at 23 ° C).

Example 3

In a 2 l reaction vessel with a stirrer, cooling and heating device, 135 g a bifunctional polypropylene glycol with a molecular weight of 2000 g / mol, 135 g of a difunctional adipic acid-butanediol polyester with the molecular weight 900, 43.9 g polyether LB25 (Bayer AG, monofunctional polyether Ethylene oxide / propylene oxide base, molecular weight 2245 g / mol) and 19.5 g of a sodium Sulphonate diol weighed in with a molecular weight of 432 g / mol, at 70 ° C. homo genized and then reacted with 124 g of isophorone diisocyanate until the theo retic isocyanate value has been reached. The isocyanate-functional polyurethane Prepolymer is then diluted at with 100 g of acetone and by adding 630 g dispersed in distilled water. Then a chain extension mixture of 1.5 g diethylenetriamine, 1.4 g hydrazine, 20.6 g isophoronediamine and 90 g of water were added in 2 minutes. 10 minutes after adding the mixture who 7.2 g of 3-aminopropyltriethoxysilane dissolved in 20 g of water were added. After this Distilling off the acetone gives a polyurethane dispersion with a solid material content of 40% and a viscosity (flow time in the DIN 4 cup at 23 ° C) of 25 seconds.

Example 4

400 g. Of of a difunctional tetrahydrofuran polyether having the molecular weight 2000 g / mol, 28 g of polyether LB25 (Bayer AG, monofunctional polyether on Ethylene oxide / propylene oxide base, molecular weight 2245 g / mol) and 20.3 g butane diol weighed in, homogenized at 70 ° C., mixed with 169.8 g of isophorone diisocyanate and reacted at 100 ° C until the theoretical isocyanate value has been reached is. The isocyanate-functional polyurethane prepolymer is ver with 800 g of acetone thin and then a chain extension solution of 22.8 g of aminoethylaminoethane sulphonic acid in the form of the sodium salt, 3 g of ethylenediamine and 50 g of water added give. 11 g of 3-aminopropyltriethoxysilane are then added, through Addition of 900 g of distilled water and dispersed the acetone by distillation far away. A polyurethane dispersion is obtained with a solids content of 41% and a viscosity of 18 seconds (DIN 4 flow cup, 23 ° C).

Example 5

1377 g. Of of a difunctional adipic acid-hexanediol-neopentyl glycol polyester with the Molecular weight 1700 g / mol and 365 g polyether LB25 (Bayer AG, monofunk functional polyether based on ethylene oxide / propylene oxide, molecular weight 2245 g / mol) are weighed out and homogenized at 70 ° C. Then with 288 g of Hexa added methylene diisocyanate and reacted at 85 ° C until the theoretical Isocyanate value has been reached. The isocyanate-functional polyurethane prepoly mer is diluted with 1400 g of acetone and then a chain extension solution 77 g of aminoethylaminoethanesulphonic acid in the form of the sodium salt, 4.4 g of hydrazine and 150 g of water are added. Then 41 g of 3-aminopropyltri methoxysilane added, dispersed by adding 3700 g of distilled water and the acetone is removed by distillation. A very finely divided polyurethane disco is obtained persion with a solids content of 34% and a viscosity of 12 seconds (DIN 4 flow cup, 23 ° C).

Example 6

1040 g. Of of a difunctional polycarbonate diol with a molecular weight of 2000 g / mol (Desmophen® 2020, Bayer AG), 520 g of a difunctional phthalic anhydride Hexanediol polyester with a molecular weight of 2000 and 234 g of polyether LB25 (Bayer AG, monofunctional polyether based on ethylene oxide / propylene oxide, Mole Weight 2245 g / mol) and homogenized at 70 ° C. Then with 369 g of Desmodur® W are added and reacted at 100 ° C until the theoretical Isocyanate value has been reached. The isocyanate-functional polyurethane prepoly mer is diluted with 1900 g of acetone and then a chain extension solution 30 g of aminoethylaminoethanesulphonic acid in the form of the sodium salt, 35.6 g of Isopho rondiamine and 150 g of water were added. 20 minutes after the addition is complete 23 g of 3-aminopropyltrimethoxysilane, diluted with 23 g of acetone, added through Addition of 3200 g of distilled water and dispersed the acetone by distillation far away. A finely divided polyurethane dispersion with a solids content is obtained of 42% and a viscosity of 19 seconds (DIN 4 flow cup, 23 ° C).

Example 7

1000 g. Of of a difunctional polycarbonate diol with a molecular weight of 2000 g / mol (Desmophen 2020, Bayer AG), 700 g of a difunctional tetrahydrofuran poly ethers with a molecular weight of 2000, 300 g of a difunctional polypropylene glycol with a molecular weight of 2000 and 70 g of polyether LB25 (Bayer AG, monofunctional polyether based on ethylene oxide / propylene oxide, molecular weight weight 2245 g / mol) and homogenized at 70 ° C. Then with 281 g Hexamethylene diisocyanate and 70 g of isophorone diisocyanate are added and the mixture is heated at 100.degree implemented until the theoretical isocyanate value has been reached. That Isocyanate-functional polyurethane prepolymer is diluted with 1500 g of acetone and then a chain extender solution of 3.2 g hydrazine, 10.8 g ethylenediamine and 20 g of water are added. 10 minutes after the addition is complete, 56.2 g 1: 1- Reaction product of 3-aminopropyltrimethoxysilane and maleic acid dimer ethyl ester added, dispersed by adding 4900 g of distilled water and the acetone removed by distillation. A very finely divided polyurethane dispersion is obtained sion with a solids content of 33% and a viscosity of 40 seconds (DIN 4 flow cups, 23 ° C).

Example 8

In a 10-liter reaction vessel with a stirrer, cooling and heating device, 1200 g of a difunctional polycarbonate diol with a molecular weight of 2000 g / mol (Desmophen 2020, Bayer AG), 800 g of a difunctional polypropylene glycol with the molecular weight of 2000 and 70 g of polyether LB25 (Bayer AG, monofunctional ler polyether based on ethylene oxide / propylene oxide, molecular weight 2245 g / mol) weighed in and homogenized at 70 ° C. Then with 310 g of hexamethylene diiso added cyanate and reacted at 100 ° C until the theoretical isocyanate value has been achieved. The isocyanate-functional polyurethane prepolymer is with Diluted 2500 g of acetone and then a chain extension solution of 138 g of des 1: 1 reaction product of isophoronediamine and acrylic acid and 150 g of water admitted. When the addition is complete, 35 g of 3-aminopropyltriethoxysilane are added added vigorous stirring, dispersed by adding 3700 g of distilled water and the acetone is removed by distillation. A polyurethane dispersion is obtained with a solids content of 39% and a viscosity of 35 seconds (DIN 4 Aus cup, 23 ° C).

Comparative example 1

Example 1) is repeated, but the 3-aminopropyltriethoxysilane is gone calmly. A dispersion is obtained with a solids content of approx. 40%, a Viscosity in the DIN 4 flow cup (23 ° C) of 13 seconds and a pH value of 7.1.

Comparative example 2

Example 1) is repeated, but the order in which the chains are added is extension solution or the chain termination solution vice versa, d. H. the chain ab Fractional solution is added first. A dispersion with a solid is obtained content of approx. 41%, a viscosity in the DIN 4 flow cup (23 ° C) of 12 seconds den and a pH of 7.0.

Comparative example 3

Example 1) is repeated, but instead of the monoamino-functional 3- Aminopropyltriethoxysilane an equivalent amount of the difunctional amino ethylaminopropyltriethoxysilane together with the chain extension solution admitted. A dispersion is obtained with a solids content of approx. 41%, a Viscosity in the DIN 4 flow cup (23 ° C) of 16 seconds and a pH value from 7, 8.

Dispersions according to Example 1) and from Comparative Examples 1), 2) and 3) who the with a film puller on a) degreased with dichloromethane glass plates and on b) Glass plates cleaned in a dishwasher, each in layer thicknesses of 10 or 35 µm dry film and applied once for 24 hours at room temperature, and in a second series of tests for 5 minutes at 50 ° C and then for 5 minutes at 150 ° C dried.

The adhesion of the coatings was then checked by means of a cross-cut test tested according to DIN 53 151:

Table 1

Cross cut test according to DIN 53 151

The values determined range from 0 (very good adhesion) to 5 (very poor adhesion) tion).

It can be seen that comparison dispersion 1), which is the only dispersion no Contains alkoxysilane groups, has significantly poorer adhesion than the three other dispersions.

This is particularly evident on the glass plates cleaned in the dishwasher noticeable, which probably still has traces of detergent on the surface sen.

The dispersion according to Example 1) and the comparative dispersions 2) and 3) show overall good to very good adhesion values. However, it can be seen that the inven proper dispersion tends to have the best adhesion, especially with not optimal cleaning of the glass surface.

Using the dispersions 1) according to the invention and the comparative dis persionen 2) and 3), the usual aids, including a lubricant and 3-amino propyltriethoxysilane as an adhesion promoter (10% based on the amount used Dispersion), glass fibers were produced in the usual and known manner, sized, cut and dried. The glass fibers were used for reinforcement in Polyamide 6.6 compounded in.

The processing properties of the sizes based on the invention Dispersion 1) and the dispersion from Comparative Example 2) were very good. It kicked no problems with the formation of specks or precipitates during the Use on. The processing of the dispersion according to comparative example 3) did not proceed optimally, an increased tendency to form specks was observed tet, which significantly hinders safe, reproducible processing. On a further testing of the properties of the dispersion according to comparative example 3) was therefore waived.

Testing the mechanical values of the using the dispersion according to Example 1) and Comparative Example 2) sized glass fibers produced Test specimen gave the following result:

Table 2

Mechanical test

It can be seen that when using dispersion 1) in comparison to comparison dispersion 2) better mechanical values of the glass fiber reinforced plastic will hold.

Using 85% by weight of dispersion 2) and 15% by weight of one not ionically hydrophilized and blocked with butanone oxime hexamethylene diisocyanate Trimersiats were made of sized glass fibers and encased them in polyamide compounded. Test specimens produced therefrom were subjected to a hydrolysis test 120 ° C in a water / ethylene glycol mixture. The initial bend strength was approx. 280 MPa, after 2 weeks the flexural strength was on average still approx. 160 MPa, after 4 weeks still approx. 140 Mpa and after 6 weeks still approx 130 MPa. Overall, these values can be assessed as very good.

Using the dispersion from Example 1), from Example 7) and from Comparative Example 1), coated glass fibers were produced and used to reinforce unsaturated polyester resins. The styrene solubility of the size during processing should be as low as possible. The following values were found:

Example 1) 18% Example 7) 23% Comparative example 1) 40%

The Charpy Impact values of corresponding test specimens were determined as follows (the values given are not absolute values but percentage values, with the best product being set at 100%):

Example 1) 100% Example 7) 95% Comparative example 1) 85%

Overall, the polyurethane dispersions according to the invention allow the manufacture development of high quality glass fiber sizes for different applications areas and different requirement profiles.

Claims (23)

1. Special polyurethane dispersions with alkoxysilane end groups, characterized in that they represent the reaction product of an isocyanate-functional prepolymer, which is present in dispersed and / or dissolved form, first with chain-extending components and then with chain-terminating, monoamino-functional alkoxysilanes. 2. Special polyurethane dispersions with alkoxysilane end groups according to claim 1, characterized in that they represent reaction products present in dispersed or dissolved form

• a) at least one polyol component,
• b) at least one di- and / or polyisocyanate component,
• c) at least one hydrophilic, nonionic structural component, consisting of compounds with at least one group reactive toward isocyanate groups and at least one hydrophilic polyether chain and optionally at least one (potentially) ionic compound with at least one, optionally at least partially neutralized, capable of salt formation Group and at least one isocyanate-reactive group,
• d) optionally one or two low molecular weight synthesis components different from a) to c) and having a molecular weight range of 62 to 450 with at least two groups which are reactive toward isocyanate groups and
• e) at least one chain extension component different from a) to d) and having a molecular weight of 32 to 350 with at least two groups which are reactive toward isocyanate groups
• f) optionally a monofunctional blocking agent and
• g) at least one monoamino-functional alkoxysilane as a chain terminator,

component (s) c) being used in such an amount that a stable dispersion is formed. 3. Polyurethane dispersions according to Claims 1 and 2, characterized in that they represent conversion products present in dispersed or dissolved form

• a) 40 to 75 wt .-% of at least one polyol component of the hydroxyl number range 5 to 350,
• b) 10 to 45% by weight of at least one di-, tri- and / or polyisocyanate component,
• c) 4 to 22 wt .-% hydrophilic structural components, consisting of at least one hydrophilic, nonionic compound with at least one isocyanate-reactive group and at least one hydrophilic polyether chain and optionally at least one (potentially) ionic compound with at least one, if applicable partially neutralized group capable of forming salts and at least one group which is reactive toward isocyanate groups,
• d) 0 to 5% by weight of one or two structural components different from a) to c) and having a molecular weight range of 62 to 450 with at least two isocyanate-reactive groups,
• e) 0.1 to 5% by weight of at least one chain extension component different from a) to d) and having a molecular weight of 32 to 350 with at least two groups which are reactive toward isocyanate groups,
• f) 0 to 7% by weight of a monofunctional blocking agent and
• g) 0.25 to 10% by weight of at least one monominofunctional alkoxysilane as a chain termination reagent,

component (s) c) being used in such an amount that a stable dispersion is formed. 4. Polyurethane dispersions according to Claims 1 to 3, characterized in that they represent conversion products present in dispersed or dissolved form

• a) 40 to 69% by weight of at least one polyol component of the hydroxyl number range 5 to 350,
• b) 12 to 35 wt .-% of at least one di-, tri- and / or polyisocyanate component,
• c) 6 to 18 wt .-% hydrophilic structural components, consisting of at least one hydrophilic, nonionic compound with at least one isocyanate-reactive group and at least one hydrophilic polyether chain and optionally at least one (potentially) ionic compound with an optionally at least partially neutralizes any group that is capable of forming salts and at least one isocyanate-reactive group,
• d) 0 to 3 wt .-% wt .-% of one or two of a) to c) different structural components of the molecular weight range 62 to 450 with at least two isocyanate-reactive groups
• e) 0.2 to 3.5% by weight of at least one chain extension component different from a) to d) and having a molecular weight of 32 to 350 with at least two groups that are reactive toward isocyanate groups,
• f) 0 to 3.5% by weight of a monofunctional blocking agent and
• g) 0.5 to 5% by weight of at least one monominofunctional alkoxy silane as a chain termination reagent,

component (s) c) being used in such an amount that a stable dispersion is formed. 5. Polyurethane dispersions according to claims 1 to 4, characterized in that they represent implementation products present in dispersed or dissolved form from

• a) 40 to 69 wt .-% of at least one polyol component of the hydroxyl number range 5 to 350,
• b) 12 to 35% by weight of at least one aliphatic and / or cycloaliphatic diisocyanate component with a molecular weight of 168 to 262,
• c) 6 to 18% by weight of hydrophilic structural components, consisting of a hydrophilic, nonionic compound with a group that is reactive toward isocyanate groups and a hydrophilic polyether chain and an ionic compound with an at least partially neutralized sulphonic acid group and two groups that are reactive toward isocyanate groups,
• d) 0 to 3% by weight of one or two structural components different from a) to c) and having a molecular weight range of 62 to 450 with at least two isocyanate-reactive groups,
• e) 0.2 to 2.5% by weight of at least one chain extension component different from a) to d) and having a molecular weight of 32 to 350 with two or three groups which are reactive toward isocyanate groups,
• f) 0 to 3.5% by weight of a monofunctional blocking agent and
• g) 0.75 to 3% by weight of monoamino-functional alkoxysilane as a chain terminating agent,

component (s) c) being used in such an amount that a stable dispersion is formed, and all neutralizing agents are added before dispersing. 6. Polyurethane dispersions according to Claims 1 to 5, characterized draws that component a) consists of polycarbonate diols, polytetra hydrofurandiols and / or di- or trifunctional polypropylene glycols of molecular weight 300 to 3500, with a maximum of 4% trifunctional Contain polyether polyols based on the total solids content of the polymer are. 7. Polyurethane dispersions according to Claims 1 to S. thereby marked draws that component a) polyester diols with molecular weight 400 to 950 contains. 8. Polyurethane dispersions according to Claims 1 to 5, characterized indicates that component a) is contained in amounts of 40 to 49% by weight. 9. Polyurethane dispersions according to Claims 1 to 5, characterized draws that as component b) isophorone diisocyanate and / or hexame ethylene diisocyanate and / or diisocyanatodicyclohexyl methane is included. 10. Polyurethane dispersions according to Claims 1 to 5, characterized draws that the anionic hydrophilization component c) exclusively Compounds containing sulphonate groups with two hydroxyl and / or Amino groups are included. 11. Polyurethane dispersions according to Claims 1 to 5, characterized shows that the anionic hydrophilization component c) is carboxylate group-containing reaction products of isophoronediamine and acrylic acid are included. 12. Polyurethane dispersions according to Claims 1 to 5, characterized distinguishes that a mixed hydrophilization of nonionically hydrophilic Components c) in amounts of 4 to 15 wt .-% and anionic hydrophi len components c) is contained in amounts of 0.5 to 6 wt .-%. 13. Polyurethane dispersions according to Claims 1 to 5, characterized shows that the nonionic hydrophilic component c) is a monohydroxy functional polyether of molecular weight 1000 to 2500 with a Built-in propylene oxide content of 10 to 57% and a content of incorporated ethylene oxide of 90 to 43 wt .-% is included. 14. Polyurethane dispersions according to Claims 1 to 5, characterized indicates that as a chain extension component e) 0.1 to 1.0 wt .-% Hydrazine or an equivalent amount of hydrazine hydrate is included 15. Polyurethane dispersions according to claims 1 to 5, characterized in that the mathematically determined content of the solids of the polyurethane dispersions of -Si- (O) ₃ structural units is less than 1.25% by weight. 16. Polyurethane dispersions according to claims 1 to 5, characterized records that the amount of isocyanate-reactive amino and / or hydroxyl groups of chain extenders e), blocking agents f) and mono amino-functional alkoxysilane g) 35 to 85 equivalent percent based on free isocyanate groups of the prepolymer from a) to d). 17. Polyurethane dispersions according to Claims 1 to 5, characterized indicates that blocking agent f) in amounts of 1) to 3.5 wt .-% ent are holding. 18. Glass fiber sizing containing polyurethane dispersions according to the claims chen 1 to 5 as an essential film-forming component. 19. Glass fiber sizing containing polyurethane dispersions according to the claims chen 1 to 5 as the essential film-forming component and blocked polyiso cyanate crosslinkers, which may contain hydrophilic groups. 20. Process for the preparation of special polyurethane dispersions with alkoxy Silane end groups according to Claims 1 to 5, characterized in that of at least one polyol a), at least one isocyanate component b) optionally with the use of hydrophilizing components c) or a component d) initially an isocyanate-functional prepolymer is made then some of the remaining isocyanate groups either in organic solution or after dispersing with a chain extension ration component e), optionally a hydrophilizing component c) and optionally a blocking agent f) is reacted and then the remaining isocyanate groups either before, during or after dispersing with an amino-functional alkoxysilane g) for reaction and then before, during or after the prepoly mer production, if necessary, added solvents, if necessary, distillate tiv is removed. 21. Process for the preparation of special polyurethane dispersions with alkoxy silane end groups according to claims 1 to 5, characterized in that initially trifunctional or higher-functional polyisocyanates in such amounts monofunctional alkoxysilanes are implemented, which is a difunctional alkoxysilane-modified isocyanate component bg) results, with min at least a polyol a) optionally a diisocyanate component b), min at least one hydrophilizing component c) and optionally one Component d) converted to an isocyanate-functional prepolymer, then some of the remaining isocyanate groups are either organic Solution or after dispersing with a chain extension compo nente e), optionally with a hydrophilizing component c) and optionally a blocking agent f) implemented and then the optionally added before, during or after the prepolymer preparation Solvent is optionally removed by distillation. 22. Use of special polyurethane dispersions with an alkoxysilane end group pen according to claims 1 to 17 in or as sizes, in particular for Fiberglass. 23. Use of special polyurethane dispersions with an alkoxysilane end group pen according to claims 1 to 17 in or as a coating and / or lacquer.