FI58625C - GLASFIBRER FOER FOERSTAERKNING AV TERMOPLASTER - Google Patents

Description

[735 ^ 71 ΓΒ1 αη ANNOUNCEMENT rftAOc LBJ (11) utlAggningsskrift 006 ^ 5 C, 45) Patent issued 10 03 1931 Patent aeddelat ^ ^ (51) Kv.lk.3 / lnt.CI 3 C 03 C 25/02 ENGLISH - J * INLAND (21) Patent application - Patentantöknlnf 751582 (22) HakemlspUvi - Ansttknlngsdag 29.05.73 (23) Alkupilvft — Glltighetadag 29.05.75 (41) Interpreters for public use - Blivlt offentllf 02.12.75

Patent and Registration Office (44) Date of Nihtkvikilpanon and IcuuLJulkalsu. -

Patents and registration documents An * 6kan utiagd och utlJkrlften publlcerad 28.ll. 80 (32) (33) (31) fyjrdettjr privilege — Begird prlorltet 01.06.7 ^ 01.06.7 ^> 01.06.7 ^ Federal Republic of Germany- Förbundsrepubliken Tyskland (DE) P 2U26657-7 »P 2U26656.6, P 2it2665U.il > · (71) Bayer Aktiengesellschaft, Leverkusen, Federal Republic of Germany Förbunds- republiken Tyskland (DE) (72) Klaus Friederich, Leverkusen, Gerhard Heinze, Schildgen, Dietrich Michael, Krefeld-Bockum, Manfred Schön, Cologne, Peter Markusch, Cologne, Ulrich Haber-land, Krefeld, Dieter Dieterich, Leverkusen, Josef Merten, Korchenbroich, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE), Helmut Reiff,

Nev Martinsville, W.V.A., USA (US) (7U) Oy Kolster Ab (5U) Glass fibers for the reinforcement of thermoplastics - Glasfibrer för-stärkning av thermoplaster

The present invention relates to glass fibers for reinforcing thermoplastic plastics such as, for example, polyamide, polycarbonate or polyester.

It is known to use glass fibers to reinforce thermoplastic plastics, mainly in the form of cut strands consisting of bundles of endless fibers bonded together. In order to have a good reinforcing effect on the polymeric material, it is necessary that the glass fiber filaments do not lose their strength before being formed into the polymer and that the coating bonding the glass wires form a tight bond between cause undesired discoloration and partial degradation of the polymers.

The coating mass is usually applied to the glass fibers by coating the glass fibers drawn at high speed from the spinning nozzles immediately after stiffening 2,58625 ~~, i.e. before winding, with suitable equipment (forge system or spray), i.e. impregnated with an aqueous mixture and usually containing among other additives and called "glue" and finally dried at a temperature above 100 ° C. Here, "drying" means not only the removal of water and other volatile parts (solvent), but also the hardening of the parts of the adhesive, especially the film formers. Only after complete drying has the adhesive changed to a solid coating mass. This coating composition must allow trouble-free further processing of the fiberglass fibers (clothing industry) by re-spinning and / or cutting. If the glass fiber strands are formed into chopped strands in a known manner, it is very significant that this product has a high vibratory weight in order to save expensive transport space. Equally important, the stem glass silk can be emptied from - possibly very large - tanks quickly and without stopping and properly passed to the extruder by mixing with the polymer to be reinforced by means of corresponding dosing devices (vibrating troughs). In order to obtain the required properties for glass fiber filaments, for example staple glass silk, such as good strength, lint-free and flowability of private fibers, it is necessary to provide them with a coating mass, i.e. to coat them. In addition to the functions mentioned so far, the important function of the adhesive or the coating mass formed therefrom is to preserve for as long as possible the mechanical properties of the fiberglass-reinforced polymer obtained by reinforcing coated glass fibers during and after humidity or storage in cold, hot or boiling water.

The various requirements which have had to be imposed on glass fibers, in particular when used as stem glass silk for the reinforcement of polymers, have not yet been satisfactorily met.

SE application publications 1,922,441 and 2,300,560 recommend nonionic, curable, partially or completely blocked polyurethanes as film formers for adhesives to glass fibers used to reinforce polyamides. In addition, commercially available silane binders such as γ-aminopropyltriethoxysilane, γ-glyeidoxypropyltrimethoxysilane, p- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane or N- (β-aminoethyl) -Y-aminopropyltrimethyltrimethane are used as binders. The reinforcing effects obtained with such adhesives are unsatisfactory, especially with regard to the mechanical properties of glass fiber reinforced polyamides such as flexural strength, impact toughness and impact toughness of the notched article.

It is further known that uncoated ("water-coated") glass fibers only insufficiently improve the mechanical properties of thermoplastic polyesters, such as impact resistance. Therefore, but also to ensure proper handling and shaping, e.g., re-spinning and cutting in known ways, it is common to treat with adhesive the glass fibers used to reinforce thermoplastic and curable polymers, including thermoplastic polyesters, and thus to create a durable coating thereon. This coating must protect the glass fibers from mechanical damage and guarantee the strength of the individual yarns forming the glass fiber strands during the coating and processing steps between their manufacture according to a known nozzle method and their shaping into polymers to be reinforced and, above all, a long bond between the glass fiber and the polymer. the effect of water. By true bonding is meant a good bond between the two components of the glass fiber-polymer composite material, which is an important prerequisite for the optimal reinforcing effect of the glass fibers.

Thus, it is technically important to develop adhesives specific to glass fibers, in particular the known A, C and E glass fibers, as close as possible to the theoretically achievable reinforcing effects of these fibers on the polymers.

By adhesives for glass fibers is meant aqueous mixtures in which the essential parts are a film former and a binder.

The film former is generally an emulsifiable or dispersible organic polymer. The binder is usually a silane binder or a chromium complex compound such as "Volan A" (manufactured by Du Pont, USA). In addition, adhesives often contain a lubricant, antistatic agent, emulsifiers, and other additives.

Unsaturated polyester resins, the so-called UP resins, high-perfection bonded glass fibers for reinforcement are less suitable for thermoplastic polyesters. Also, additives specially recommended for glass-fiber-reinforced thermoplastic polyesters (epoxy-slian) to improve the mechanical properties of these materials (cf. DB application 2,206,604) are only partially satisfactory, since they do not achieve important mechanical properties, such as impact on the notched object. .

It is therefore an object of the present invention to provide glass fibers having 58625

It is especially suitable for the preparation of thermoplastic plastics. In particular, the flexural strength and impact resistance of the glass fiber and thermoplastic polymer composite material must be improved.

The thermoplastic reinforcing glass fibers according to the invention are characterized in that they are made of a coating with an aqueous polyurethane ionomer dispersion as the film former and epoxyalkylalkoxysilane as the binder or one of the following combinations a, b or c. ) epoxyalkylalkoxysilane and a low molecular weight aliphatic, primary or secondary monoamine, c) aminoalkylalkoxysilane and a low molecular weight monoepoxide, and optionally other additives such as a lubricant, wetting agent and antistatic agent.

Polyurethanes useful in the present invention are anionic or cationic. Such polyurethane ionomers are used in particular because the use of emulsifiers is eliminated in connection with these spontaneously water-dispersible substances. It has the advantage of saving costs and, in particular, of avoiding the disturbing side effects due to the hydrophilic nature of the emulsifiers, which can occur in glass-fiber-reinforced thermoplastics as certain tendencies with respect to the effects of water. The absence of emulsifiers also results in substantially better film formation, as well as a greatly increased exchange effect with the substrate, and thus improved bonding properties.

Ionic polyurethanes are generally described as "polyurethane ionomers" (cf. D, Dieterich et al., Angevandte Chemie, 82, (1970), pp. 53-63). According to it, the polyurethane ionomers used according to the invention are polyurethanes with ionic centers at greater distances, i.e. they are heteropolymers with a distinct segment structure. Due to the internal exchange effects of the substance (coulomb forces and hydrogen bridges), they have similar properties as elastomers. In polar organic solvents, these polyurethane ionomers spontaneously form stable aqueous dispersions when water is added, in which the ionomers are in the dispersed phase, so that the emulsifiers normally used are omitted. After removal of the organic solvent, the polyurethane ionomers are the emulsifier and the emulsifier. An essential advantage of the useful adhesives according to the invention is that they therefore do not contain emulsifiers or organic solvents which can interfere with the desired effects of the adhesives or the coating masses formed on the surface of the glass fibers according to the invention in the plastic material.

The water insolubility of the coatings separated from the aqueous dispersion of polyurethane ionomers and the formation of independent coatings are explained by the formation of hydrophobic bonds. The technically advantageous high change resistance of aqueous polyurethane ionomer dispersions is also explained by this.

One of the most present properties of polyurethane ionomers is their excellent film-forming ability even at low temperatures, which practically corresponds to the ability of solvent systems. Films formed from these polymers have high elasticity, tear and abrasion resistance, i.e. properties that are among the most important requirements for film formers of fiberglass adhesives. Another advantage of especially anionic polyurethane ionomers is their electrolyte stability and their good compatibility with other polymer dispersions and excipients. This is very important in the manufacture, handling and processing of fiberglass adhesives, as many such adhesives have two or three, sometimes even substantially more parts, so that good adaptability of individual components, especially the quantitatively dominant film former, is a technological and economic prerequisite for their addition. This is also clear from the fact that DE-A-1 922 1 * 1 * 1 requires special additives to overcome the tendency of non-ionic polymers to separate from the dispersion and settle on the adhesive coating devices, as a result of which the glass fibers drawn from the spinning nozzles often break and thus cause production interruptions.

Polyurethane ionomer dispersions can be prepared by various methods known to those skilled in the art, e.g., the acetone method or the melt dispersion method (cf. here D, Dieterich and H. Reiff, Angev. Macromol. Chemie 26, 85, 101 (1972)).

Polyurethane ionomer dispersions are preferred, such as those described in more detail in Angewandte Chemie, 82, 53 (1970). Furthermore, the ionomer dispersions obtained by the melt dispersion method (e.g. DT-OS 1 770 068 and DT-OS 1 913 271) are very suitable,

The best properties are obtained with dispersions whose dispersed particles have an average diameter of less than 1 μm and in particular 0.05-0.0 μm. Further preferred are dispersions of polyurethane ionomers having an ionic group content of 5 to 30 milliequivalents per 100 g of dry matter. Furthermore, cationic or anionic polyurethane dispersions with a dispersed phase having at least 6,58625 partially microgel lozymes are highly preferred. The microgel nature, on the other hand, should not be over-represented, otherwise the film-forming ability may be impaired. Particularly suitable dispersions, when diluted with about 4-10 times by weight of tetrahydrofuran, form a weakly opalescent solution. This weak and completely uniform turbidity is clearly visible as a layer about 2 cm thick, especially when lit from above. The sanity may also be stronger, however, the character of the milky turbid dispersion must not be retained when diluting with tetrahydrofuran. On the other hand, a clear "shimmering" solution should not be formed. Dispersion rolls according to the present criterion have a very strong swelling when diluted with tetrahydrofuran 11a, so that the slightly turbid "solutions" obtained when flowing do not form a smooth but optically "rough" surface.

Microgel character criterion; also applies to dispersions which have overreacted and no longer contain reactive groups.

However, dispersions having reactive groups or reactive crosslinkers, e.g. those described in DE-A-1,770,069 and 1,913 * 271, preferably also have a certain microgel nature when used as glass fiber pastes; however, they may also be completely unbound at the time of use. This is evident from the formation of a clear solution upon dilution of tetrahydrofuran. In any case, when using such unbound dispersions, it must be ensured that further reactions are obtained through further reactions of the glass fibers; bonded coating layer. This means that after drying and condensation at 140 ° C, the test dose of the added adhesive must form a film insoluble in aqueous tetrahydrofuran. Polyurethane dispersions which meet the above requirements can be formed from a wide range of monomer units in a wide variety of ratios. The versatility of the possibilities given for the formation of polyurethane ionomers is known to the person skilled in the art. Thus, in addition to urethane groups, suitable products according to the invention may also contain urea, amide, ester, ether, thioether, acetal, biuretate, ureido, allophanate, carbodiimide units. Very particularly preferred are polyester-polyurethanes, polyester-amide-polyurethanes and polyester-amide-polyurethane ureas, polyester-urethane biuretics.

Preferred components of the polyurethane dispersions according to the invention are: 1. polyester diols, molecular weight between 500 and 3000, prepared from adipic acid, phthalic acid, isophthalic acid, tetrahydrofral acid, hexahydrophthalic acid and ethylene glycol, neophenol, neanediol, butanediol. A particularly good glass bond is obtained with products containing phthalic acid; 2, diisocyanates, especially aliphatic or cycloaliphatic, e.g. hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diisocyanate dicyclohexylmethane; 3. chain extenders such as ordinary glycols, diamines, and tert-aminoglycol for cationic and sulfonate glycols or sulfonate diamines for anionic dispersions,

When anionic polyurethane dispersions, especially those with sulfonate groups, are unusually stable and resistant to a wide variety of additives, cationic dispersions give glass a special adhesive bond.

The attachment of several polyurethane ionomers to the glass fibers is so preferred, 0 * .... . . . .....

that, under more favorable conditions, the use of a conventional expensive silane binder can otherwise be omitted. This applies in particular to polyurethane ionomers based on a phthalate ester base.

Further interesting are those polyurethane ionomer dispersions containing at least 0.1% formaldehyde or an equivalent amount of methylol compounds which guarantee the crosslinked nature of the condensed adhesives, the dispersions prepared by the isocyanate polyaddition method generally represent (optionally bound) formaldehyde. 1-0.8%, calculated as dry matter, of dispersions formed from oligomeric precursors by formaldehyde polycondensation have a substantially higher amount of (bound) formaldehyde and are preferably about 2-10%,

Highly water-resistant polyurethane ionomers are those which are further chemically bonded with polyisocyanates or other reactive components such as formaldehyde or its derivatives.

Polymers of this type are therefore very suitable for the production of the glass fibers according to the invention,

Due to the microgel or gel nature of polyurethane ionomer adhesives, an optimal property is achieved: on the one hand the adhesive can be supplied very well to the glass fiber base and at lower temperatures the preferred dense, homogeneous film formation is achieved, on the other hand the adhesive This also involves the possible attachment of the paste via both the methylol groups to both the glass fibers and the plastic substrate. This favorable combination of the desired properties a 58625 θ of fiberglass adhesives was not previously achieved with prior art products.

In order to achieve optimal properties, it is still necessary that the dispersible polyurethane ionomers themselves dry on high molecular weight plastics with good properties. Preferred are polyurethanes which, when their dispersion is poured on a flat surface and dried, form a film having the following values:

Tensile strength: greater than 50 kp / cm, preferably more than 100 kp / cm

Elongation at break: 100-000 #

Shore-A hardness: 50-90 A.

Swelling in water at 20 C: sea: less than 50 #

Very particularly preferred are dispersions of anionic polyurethanes, especially those with sulfonate groups and carboxylate groups.

The concentration of the polyurethane dispersion in a glue useful according to the invention is from 1 to 15% by weight, calculated as polyurethane dry matter. Concentrations of less than 1% by weight provide only an insufficient protective film for the fibers, concentrations higher than 15% by weight give purple thick coatings which lead to deterioration of the bonding material made with these fibers, in addition to cost factors prohibiting the use of even higher amounts of film-forming agents. Preferably, the concentration of the polyurethane dispersion in the adhesive is selected between 3 and 7 #. Experience has shown that the adhesion of such an adhesive to the fibers in the spinning process results in a coating of the dried fibers after evaporation of the water with about 0.4 to 1.5% by weight of the adhesive components, of which the film former is usually the largest in quantity. Such adhesive contents can be considered optimal from both a technical point of view and also from an economic point of view for the reinforcement of thermoplastic polyesters.

Although the molar ratio of the components of the binder of the combination according to the invention may be, as mentioned, between 5 * 1-1 * 5, it is expedient for economic reasons to add more expensive components, i.e. silane for combination types a) and b), silicon for epoxyalkyltralkoxysilane in combination type c), sparingly and correspondingly increase the proportion of the cheaper components in each case within the limits of the above-mentioned molar ratio range.

The concentration of the binder in the adhesive according to the invention is 0.05 to 1.5% by weight, but preferably 0.15 to 0.75% by weight. Concentrations above 1.5 wt.% Are uneconomical due to high silane costs. At concentrations below 0.05 wt.%, The effectiveness of the binder is not sufficient.

9,58625

Concentrations between 0.05 and 0.15 are chosen when the application of the adhesive to the glass fibers does not take place during the spinning process, i.e. in fractions of a second, but for example during the immersion of the glass fibers in an adhesive bath, which for practical reasons requires longer periods of adhesive acceptance. than brushing the paste in the spinning process.

Epoxyalkylalkoxysilanes useful in the present invention include epoxyalkyltrialkoxysilanes, epoxyalkylalkyl dialkoxysilanes, and epoxyalkylaryl dialkoxysilanes. Preferably, γ-glycidoxy-propyltrimethoxysilane and 3- (3,4-epoxyocyclohexyl) -ethyltrimethoxysilane are used.

Among the useful aminoalkylalkoxysilanes of the invention, γ-aminopropyltrialkoxysilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and (β-aminoethyl) -Y-aminopropyltrimethoxysilane are preferred.

The low molecular weight aliphatic monoamines of the invention include primary amines having 1 to 6 carbon atoms as well as secondary amines having 1 to 5 carbon atoms having an organic residue such as diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, ethylbutylamine, methylbutylamine, methylbutylamine , ethylamylamine, diamylamine.

Useful low molecular weight monoepoxides of the invention include alkylene oxides such as ethylene, propylene, butylene oxide, non-halohydrins such as epichlorohydrin and epibromohydrin, and aromatic monoepoxides such as styrene oxide.

Although the glass fibers registered according to the invention with aqueous polyurethane ionomer dispersions together with an epoxyalkyltrialkoxysilane form a thermoplastic bonding body with excellent properties, it is preferred that the binder combination according to the aforementioned groups a), b) or c)

Particularly preferred type a) composite adhesives consist of γ-glycidoxypropyltrimethoxysilane and n-propylamine or β- (3,4-epoxycyclohexyl) -ethyltrimethoxy8ilane.

A particularly preferred recombinant binder of type b) consists of γ-aminopropyltriethoxyethane and epichlorohydride.

Highly preferred combination binders of type c) consist of γ-aminopropyltriethoxysilane and Y-glycidoxypropyltrimethoxysilane or γ-aminopropyltriethoxysilane and β- (3,4-epoxycyclohexyl) -ethyltrimethoxyethylan.

58625 10

It is expedient to use a lubricant in the paste which can be used according to the invention. This lubricant can be selected from the following groups of substances: polyalkylene glycols, higher fatty acid amides containing 12-18 carbon atoms, polyolefin dispersions. The lubricant is suitably used in concentrations of 0.05 to 1% by weight. Higher values in this concentration range are particularly suitable when a polyolefin dispersion is selected as the lubricant. The lower values of said range are preferably used when polyalkylene glycol or a higher fatty acid amide is used as the lubricant. The use of a polyolefin dispersion is therefore noteworthy because it has an anionic or nonionic nature when anionic polyurethane is used as the film former, cationic or nonionic nature when a cationic polyurethane is used in order to avoid mutual coagulation of the adhesive dispersions. In addition to this limitation, the selection of a suitable lubricant from the above groups of substances is not critical. The lubricant is used appropriately to facilitate the subsequent use of glass fibers in the garment industry. However, it has no significant effect on the effect of improving the mechanical properties of the adhesive binder according to the invention, i.e. the fiberglass-polymer composite material.

The known types of glass used in the manufacture of glass silk, such as E, A, C and S glass, as well as known glass staple fiber products are suitable for the production of pasted glass fibers according to the invention. High-modulus and high-strength glasses developed for special purposes are also useful in the production of the glued glass fibers according to the invention. Among the mentioned types of glass for the manufacture of glass silk (so-called endless fibers), E-glass fibers play the greatest role in the reinforcement of plastics. For, unlike A and C fibers, E glass is almost alkali-free, which results in its good electrical insulating properties and its greater resistance to water or alkalis. Also in terms of tensile strength and modulus of elasticity, E-glass fibers are better than A-glass fibers.

E, A, S and C glasses have the following chemical composition in weight percentages (guideline values: Vende / Moebes / Marten "Glasfaserberstärkte Plaste", VEB Beutscher Verlag för GrunditoffIndustrie Leipzig, 1969.2 edition, e.74): 11 58625 s S »:! s! !

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The pasted glass fibers of the invention can be used to reinforce thermoplastic plastics having regularly polar groups in the chain structure. By "polar groups" is meant those which, under known conditions for shaping pasted glass fibers, are in a thermoplastic in a state such that they form physical and / or chemical bonds to pasted glass fibers according to the invention such that a clear reinforcing effect of the glass fibers can be demonstrated. bending strength, impact toughness, notched object impact toughness, etc. In this sense, there are polar groups: primary, secondary, and tertiary amino groups, amide and imide groups, carbonyl, carboxyl, ester, ether, ion groups, acetal, oxirane, oxirane, oxirane, oxirane , nitrile and sulfone groups. Particularly suitable for reinforcement with pasted glass fibers according to the invention are polyamides, polycarbonates, thermoplastic polyesters such as polyethylene and polybutylene terephthalates, styrene-acrylic triilyl copolymers, acrylonitrile-butadiene-styrenes * terrylenes

The following examples illustrate the method of the invention in more detail.

Example 1 a) Adhesive composition Weight%

Polyurethane anionomer dispersion ηα. 1 ($ 40 dry matter) 12.5 γ-aminopropyltriethoxyethylane 0.53 epichlorohydrin 0.17 polyethylene dispersion (40 dry matter) 1 * 25 deionization treated water 85.73 b) Polyurethane anionomer dispersion no. Preparation 1 209 g (0.125 moles) of hexanediol neopentyl glycol dust dioate (average molecular weight 1670) are dewatered at 120 ° C under water pump vacuum for 30 min. stirring over time. Allow to cool to 70 ° C and add 38 g (0.226 mol) of 1,6-diisocyanatohexane. After the exothermic reaction has subsided, the reaction mixture is stirred for 2 hours at 120 ° C. After cooling to 70 ° C, 700 ml of acetone are added and the bath temperature is set at 60 ° C, keeping the reaction mixture at 53 ° C.

Prepare an extension solution consisting of 13 to 75 g of a solution of the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid (43 wt.% Dry matter) (0.0313 moles), 1.90 g (0.0317 moles). moles) of ethylenediamine and 58 g of water, and this extension solution is added to the 55 ° C reaction mixture, stirred for 5 min, and then 270 ml of distilled water are added and finally acetone is distilled off with a water jet pump.

The resulting finely divided anionic polyurethane dispersion has a dry matter content by weight, contains 0.96% by weight of dry matter, and has a particle size of 15Ο to 2Ο mp. The dispersed phase has a microgel nature (slightly turbid solution when diluted with tetrahydrofuran), c) Preparation of the adhesive

Place about half of the required water in the mixing bowl. The polyurethane dispersion is added with stirring. Finally, the addition of polyethylene dispersion, silane and epichlorohydrin takes place with still stirring. After the addition of the final water, the pH of the adhesive is adjusted to 5.9-6.0 with acetic acid.

(d) Manufacture of glass fiber polycarbonate compound material and testing of its dyeing and mechanical properties:

The E-glass fibers impregnated with the adhesive according to the invention in a known manner are metered into a length of 6 mm in the form of chopped strands, each consisting of 1 + 00 single wire with a diameter of 12 μm, in a twin-screw extruder and mixed with molten polycarbonate "Makrolon 3 200" Bayer AG, Leverkusen) and extruded. Makrolon granules containing 20% by weight are used to make test specimens with a screw extruder. The following mechanical properties are measured on these test pieces in accordance with the standard publications mentioned below:

Bending strength Din 53 ^ + 52 1Ö27 kp / cm ^ 2

Impact strength Din 53 ^ 53 61.8 cmkp / cm

O

Impact resistance of the notched part Din 53U53 15.0 cmkp / cm ^

Fiberglass-reinforced polycarbonate is virtually colorless. The absence of interfering discoloration of the reinforced polycarbonate and the hitherto unattainable level of the given mechanical properties clearly show the superiority of the pasted glass fibers according to the invention.

Example 2

The technical advantages of the invention become apparent in a comparative experiment with glass fiber reinforced polycarbonate (Makrolon 3200) reinforced as described above with 20 weight percent commercial E-glass fibers in the form of 6 mm long stem glasses, the manufacturer describing these glass fibers as optimal for polycarbonate reinforcement. The test pieces of this material had the following mechanical properties: (,, 58625

Every 2

Flexural strength Din 53 ^ 53 1591 kp / cm 2

Impact strength Din 53 ^ 53 * + 9.7 cmkp / cm 2

Impact resistance of the notched part Din 53 ^ 53 9.8 cmkp / cm This fiberglass-reinforced polycarbonate is clearly yellow-colored. The staining shows that the commercial glass fibers are inferior to those pasted according to the invention, since in both cases E-glass was used as the reinforcing material and "Makrolon 3200" as the base material, and the processing and experimental conditions were kept exactly the same,

The following examples illustrate other adhesives used in accordance with the invention. The preparation of these adhesives follows the procedure described in Example 1. Also, the production of glass fiber-reinforced polycarbonates from "Makrolon 3200" and E-glass fiber strands impregnated with glass fibers pasted according to the invention (fiber length 6 mm, U00 single fiber with a diameter of 12 μm) and their testing take place as described in Example 1. The glass content of the reinforced polycarbonates is sometimes 20% by weight. The following examples give the adhesive composition of the reinforced polycarbonates, the mechanical values obtained for the test pieces and the color.

Example 3 a) Adhesive composition: Weight #

Polyurethane anion atom dispersion No. 2 (30 wt.% Dry matter) 16.7 K-glycidoxypropyltrimethoxysilane 0.25 polyethylene dispersion (U0 wt.% Dry matter) 1.25 deionized water 81.8 b) Polyurethane anionomer Preparation of Dispersion No. 2 Dose: 1) 5080 g of hexanediol-neopentyl glycol polyadipate having an average molecular weight of 1980 2) 980 g of 1,1,1-trimethylolpropane-tetrahydrophthalic anhydride adduct in a molar ratio of 1: 1.2; 80 wt.% Solution in methyl isobutyl ketone 3) 350 g of urea k) 200 g of 2-dimethylaminoethanol 5) 1000 g of 1,6-diisocyanothexane 6) 170 g of methyl isobutyl ketone (MIBK) 7) 170 g of ethylene oxide and propylene oxide and glycerol polyether 8) 70 g of ethoxylated nonylphenol 9) 500 g of 30 # formaldehyde in water 11 * 500 ml of water.

15 58625

Performance:

To the anhydrous ester (1) is added a chain extender (2), urea (5), and MIBK (6). At 35 ° C, diisocyanate (3) is added and stirred for 1.5 hours at 60-68 ° C. Finally, heat to 135 ° C and stir for 1 hour at this temperature. Polyether (7) and ethoxylated nonylphenol (8) are added to the melt. Disperse at a stirring speed of 100 rpm. 2.5 l of water are added with the amine (4) in 2 minutes, then the temperature is lowered from 95 ° C to 85 ° C. Stir for another hour at 80 ° C and one hour under cooling with running water. A 32 # PU dispersion with a pH of 7 and an FBV ^ <26 "is obtained. The dispersion was diluted to 30 and was indefinitely stable at room temperature. After drying and heating at 140 ° C, a sample of the dispersion gives $ 80: a film insoluble in tetrahydrofuran.

(c) Mechanical properties of the test piece:

Bending strength DIN 53452 1704 kp / cm2

Impact resistance DIN 53453 57 »4 cmkp / cm2 2

Impact resistance of the notched part DIN 53453 11.0 cmkp / cm d) Color Practically unchanged.

Example 4 a) Does the purchase glue:

Polyurethane dispersion no. 1 ($ 40 ca.) 12.5 weight- $ γ-aminopropyltriethoxysilane 0.25 "γ-glycidoxypropyltrimethoxysilane 0.25"

Polyethylene dispersion ($ 40 incl.) 1 »25"

Deionized water 85 * 75 "b) Mechanical properties of the test piece:

Bending strength Din 53452 1677 kp / cm2 o

Iskusitkeye Din 53453 55 * ° cmkp / cm p

Impact resistance of the notched part DIN 53453 15 * 8 cmkp / cm c) Color Practically unchanged.

Example 5 a) Adhesive composition:

Polyurethane dispersion no * 1 (40 56 ka) 12.5 wt.% Y-glycidocipropyltrimethoxysilane 0.4 "n-propylamine 0.1"

Polyethylene dispersion (40 # ka.) 1.25 "

Deionized treated water 85.75 "16 58625 b) Mechanical properties of the test piece: 2

Bending strength Din 531 + 52 1659 kp / cm 2

Impact strength Din 531 + 53 59.1+ cmkp / em 2

Impact resistance of the notched part Din 53 1 + 53 16.1 cmkp / cm c) Color Practically unchanged Example 6 a) Adhesive composition:

Polyurethane Dispersion No. 1 (1 + 0 # ka.) 12.5 Weight # [N-aminopropyltriethoxysilane 0.25 "β- (3,1 + -epoxycyclohexyl) -ethyltrimethoxysilane 0.25"

Polyethylene dispersion (1 + 0 # ka.) 1.25 "

Deionized water 05.75 "(b) Mechanical properties of the test piece:

Bending strength Din 53 1 + 52 1739 kp / cm 2

Impact strength Din 53 ^ + 53 57.0 cmkp / cm 2

Impact resistance of the notched part Din 531 + 53 16.1 cmkp / cm c) Color Practically unchanged.

Example 7 a) Composition of the adhesive according to the invention:

Polyurethane anionomer dispersion No. 3 (1 + O # ka,) 12.5 wt.% N-aminopropyltriethoxysilane 0.5 "

Polyethylene dispersion 1.25 "

Deionized Water 85.75 "b) Preparation of Polyurethane Anionomer Dispersion No. 3 209 g (0.125 moles) of hexanediol neopentyl glycol polyadipate (average molecular weight 1670) are dewatered at 120 ° C with a water jet pump under stirring for 30 minutes with stirring. To 38 DEG C. and 38 g (0.226 mol) of 1,6-diisocyanatohexane are added, and after the exotherm has subsided, the reaction mixture is stirred for 2 hours at 120 DEG C. To C, keeping the reaction mixture at 55 ° C.

Prepare an extension solution of 13.75 g of an aqueous solution of the sodium salt of N- (2-aminoethyl) -2-arairioethanesulfonic acid (1 + 3 wt.% Dry matter) (0.0313 moles), 1.90 g (0.0317 moles). moles) of ethylenediamine and 58 g of water, and T 58625 this extension solution is added to 55UC of the reaction mixture. Stir for 5 min, then add 270 ml of distilled water and finally distill off the acetone with a water jet pump.

The resulting finely divided anionic polyurethane dispersion has a dry matter content of 100% by weight, contains 0.96% by weight of dry matter and has a particle size of 150-200 nm. The dispersed phase has a microgel nature.

c) Manufacture of adhesives

Place about half of the required water in the mixing bowl. The polyurethane anionomer dispersion is added with stirring. Finally, the addition of the polyethylene dispersion and the silane is followed by the stirring, the pH is adjusted to 5.9-6.0 with acetic acid after the addition of the final water.

d) Experimentation of the reinforcing effects of glass fibers prepared according to the invention in polyamide:

S

E-glass fibers prepared according to the invention with the above-mentioned adhesive in the form of 6-μm cut strands, always consisting of LOO single yarns of diameter 12, are formed in a biaxial extruder into polyamide 6 ("Durethane BK31F", manufactured by Bayer AG, Leverkusen), in glass fiber reinforced polyamide is 35%. This material is used to make test specimens on an injection molding machine, the mechanical properties of which are tested in accordance with the following standards:

Flexural strength Din 53 ^ 52 2767 kp / cm ^

Impact strength Din 53 ^ + 53 68.7 cmkp / cm ^ 2

Impact strength of the notched body Din 53 ^ 53 13, ^ cmkp / cm

Example 8 a) Composition of the adhesive used according to the invention:

Polyurethane Anionomer Dispersion No. 3 (HO% ca.) 12.5 wt-γ-glycidoxypropyltrimethoxysilane 0.25 "

Deionization treated water 8?, 25 "

The preparation of the adhesive as well as the experiments on the reinforcing effects of the glass fibers according to the invention in polyamide take place as described in Example 7. The following mechanical properties are measured:

Flexural strength Din 53 ^ 52 27 ^ 8 kp / cm 2

Impact strength Din 53 ^ 53 67.8 cmkp / cm 2

Impact strength of the notched body Din 53 ^ 53 13.5 cmkp / cm, β 58625

Example 9 a) Composition of the adhesive used according to the invention:

Polyurethane anionomer dispersion No. 3 (1 + 0 # ka.) 12.5 wt.% -Aminopropyltriethoxysilane 0.33 "

Epichlorohydrin 0.17 "

Polyethylene dispersion (1 + 0 # ka,) 1, 25 "

Deionized treated water 85.75 "

The preparation of the adhesive as well as the experiments of the glass fibers according to the invention on the reinforcing effects in polyamide take place as given in Example 7. The following mechanical property values are obtained:

Bending strength Din 53 ^ * 52 3031 kp / cm ^ o

Impact strength Din 53 ^ 53 72.1 cmkp / cm 2

Impact resistance of the notched part Din 531 + 53 17 »8 cmkp / cm

Example 10

Non-inventive adhesive from DE 2 300 368, example 1+:

Urethane latex (non-ionic) X-1033 (1 + 0 # ca.) 12.5 wt. #

Manufacturer: Wyandotte Chemical Corp ,,

Wyandotte, Mich. U.S.

2-aminopropyltriethoxysilane 0.25 "

Polyolefin emulsion (1 + 0 # ka.) 1.0 "This adhesive is prepared as described in DE 2 300 368, Example 1 and used to reinforce glass fibers as described in Example 7. Modification to polyamine 6 (" Durethane BK 31 F ") and the experimentation of the mechanical properties is likewise carried out exactly as mentioned in Example 7:

The following mechanical property values were obtained:

O

Flexural strength Din 53 ^ 52 2697 kp / cm 2

Impact strength Din 53 ^ + 53 66.0 cmkp / cm 2

Impact resistance of the notched part Din 531 + 53 12.8 cmkp / cm

The results of Examples 7 to 10 show the superiority of the adhesives used according to the invention compared to an adhesive containing non-ionic polyurethane instead of the polyurethane anionomer used according to the invention.

The following Examples 11-11 + describe other adhesives used in the invention. These adhesives are prepared by the method described in Example 7. Also, the preparation of the glass fiber reinforced polyamides and the testing of the mechanical properties take place in the ways described in Example 7, so that in addition to the Liis grain compositions, only the mechanical properties are shown. The glass content of glass fiber reinforced polyamides is 35% by weight.

Example 11 a) Adhesive composition:

Polyurethane Anionomer Dispersion No. 3 12.5 wt-N-aminopropyltriethoxysilane 0.25 "γ-glycidoxypropyltrimethoxysilane 0.25"

Polyethylene dispersion (1 + 0 # ka.) 1 * 25 "

Deionized water 85.75 "(h) Mechanical properties of test pieces:

Bending strength Din 531 + 52 2976 kp / cm 2

Impact strength Din 531 + 53 66.3 cmkp / cm 2

Impact strength of the notched body Din 53 ^ + 53 1 ^, 6 cmkp / cm

Example 12 a) Adhesive composition

Polyurethane anionomer dispersion No. 3 12.5 wt.% K-aminopropyltriethoxysilane 0.25 "β- (3,1 + -epoxycyclohexyl) -ethyltrimethoxysilane 0.25

Polyethylene dispersion 1> 25 "

Deionized water 85.75 "(b) Mechanical properties of the test piece:

Bending strength Din 531 + 52 2967 kp / cm 2

Impact resistance Din 531 + 53 7 ° »9 cmkp / cm 2

Impact resistance of the notched part Din 531 + 53 16.5 cmkp / cm

Example T3 a) Adhesive composition:

Polyurethane Anionomer Dispersion No. 3 12.5 wt.% N'-glycidoxypropyltrimethoxysilane 0.1+ "n-propylamine 0.1"

Polyethylene dispersion (1 + 0 # ca.) 1.25 M

Deionized water 85.75 "(b) Mechanical properties of the test piece:

Bending strength Din 531 + 52 2792 kp / cm 2

Impact strength Din 531 + 53 69.6 cmkp / cm 2

Impact resistance of the notched part Din 531 + 53 13.9 cm / cm 2o 5 8 6 2 5

Example lU

a) Adhesive composition:

Polyurethane Anionomer Dispersion No. k (UO% ca.) 12.5 wt% aminopropyltriethoxysilane 0.25 "

Epichlorohydrin 0.25 "

Stearic acid amide 0.05 "

Deionization-treated water 86.95 "b) Preparation of polyurethane anionomer dispersion No. k:

Composition: 5080 g hexanediol neopentyl glycol polyadipate, avg. molecular weight 1980 980 g of 1,1,1-trimethylpropane-tetrahydrophthalic anhydride adduct in a molar ratio of 1: 1.2; 80 wt.% Solution in methyl isobutyl ketone 350 g urea 200 g 2-dimethylaminoethanol 1000 g 1,6-diisocyanothexane 1000 ml methyl isobutyl ketone (MIBK) 170 g ethylene oxide and propylene oxide and glycerol polyether 70 g ethoxylate nonylphenol 500 ml of 30 # formaldehyde in water 11 + 500 ml of water.

Procedure: A chain extender, urea and MIBK are added to the anhydrous ester. At 35 °, diisocyanate is added and stirred for 1.5 hours at 60 ° C (Triax 68 °). Finally, heat to 135 ° C and stir for one hour at this temperature. Polyether and ethoxylated nonylphenol are added to the melt. Disperse at a stirring speed of 100 rpm. Add 2.5 L of water with amine over 2 minutes.

7 l of water and finally 5 l of water with formaldehyde are added in 7 minutes, then the temperature drops from 95 ° C to 85 ° C. Stir for an additional hour at 80 ° C and one hour under running water cooling. A 32 # PU dispersion with a pH of 7 and a FBV ^ = 26 "is obtained. The dispersion is diluted to 30 #, it is indefinitely stable at room temperature. A sample taken from the dispersion, after drying and heating at 11 + 0 ° C, gives 80 a film insoluble in silicon tetrahydrofuran.

(c) Mechanical properties of the test piece:

Bending strength Din 531 + 52 2856 kp / cm 2

Impact strength Din 531 + 53 70.3 cmkp / cm

O

Impact strength of the notched part Din 531 + 53 1; +, 2 cmkp / cm '21 58625

Example 15

For the specimens from polyamide 6 ("Durethane BK 31 F"), which was reinforced with 35 # commercially available, in the form of E-ias cut strands (length 6 mm) described as excellent for reinforcing polyamides, the following mechanical measurement results were obtained: p

Bending strength Din 531 + 52 251 + 1 + kp / cm 2

Impact strength Din 531 + 53 61, 6 cmkp / cm 2

Impact strength of the notched part Din 53 * + 53 11.0 cmkp / cm

Comparing the mechanical properties of the polyamide 6 reinforced with the glass fibers of the invention shown in Examples 7 to 9 and 11 to 1U to the mechanical values of Example 15 measured from the same polyamide 6 but reinforced with commercial E-glass fibers in the same weight ratio (35 weight #), the superiority of the adhesives according to the invention becomes clear.

Example 16 a) Composition of the adhesive used according to the invention:

Polyurethane anionomer dispersion (1 + 0 # ca.) 12.5 wt.% (3,1 + -epoxycyclohexyl) -ethyltrimethoxysilane 0.25 "

Polyethylene dispersion (1 + 0 # ka.) 1.25 "

Deionized Treated Water 86.0 "b) Preparation of Plylyurethane Anionomer Dispersion: 209 g (0.125 moles) of hexanediol neopentyl glycol polyadipate (average molecular weight 1670) are dewatered at 120 ° C with a water jet pump under stirring for 30 minutes. To 38 DEG C. and 38 g (0.226 mol) of 1,6-diisocyanatohexane are added, the reaction mixture is quenched for 2 hours at 120 DEG C. after the exotherm has subsided, cooled to 70 DEG C. and 700 ml of acetone are added and the bath temperature is adjusted to 60 DEG C. to which time the reaction mixture is maintained at 55 ° C.

Prepare an extension solution of 13.75 g of a solution of the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid (1 + 3 wt.%) (0.0313 mol), 1.90 g (0.0317 mol) ) ethylenediamine and 58 g of water, and this extension solution is added to the reaction mixture at 55 ° C. Stir for 5 min. then 270 ml of distilled water are added and finally the acetone is distilled off with a water jet pump.

The fine anionic polyurethane dispersion obtained has a dry matter content of 1 + 0% by weight, contains 0.96% by weight of dry matter and has a particle size of 150-200 nm.

22 5 8 6 2 5 c) Manufacture and use of adhesives.

Place about half of the required water in the mixing bowl. The polyurethane anionomer dispersion and the polyethylene dispersion are added successively with constant stirring. The pH of the mixture is then adjusted to 5.0. Finally, (3,1 + -epoxycyclohexyl) -ethyltrimethoxysilane hydrolyzate prepared according to the silane manufacturer's instructions (Union Carbide Corporation, New York) is added. About 15 min. after mixing, the adhesive is ready for use. It is applied to a conventional fiberglass gluing apparatus and applied to glass fibers drawn from conventional spinning nozzles in a manner known therein, e.g.

(d) Coating of glass fiber filaments, their modification into polybutylene terephthalate, manufacture of test pieces, mechanical properties of test pieces:

After drying, the glass fiber coils (spinning cake) are disassembled and cut to a length of about 6 mm with a suitable cutting device. The cut strands ("chopped glass silk" or "chopped strands") are mixed with molten polybutylene terephthalate in a biaxial extruder at 260 ° C. The glass fiber-polymer mixture is then extruded in a known manner and granulated. From the granulate (glass content 29.1+%), specimens are prepared with a screw injection molding machine, from which the mechanical properties are measured in accordance with the standards: 2

Impact strength Din 53 * + 53 1 + 7.0 cmkp / cm 2

Impact strength of the notched piece Din 531 + 53 10.8 cmkp / cm o

Bending strength Din 531 + 52 1856 kp / cm 2

Tensile strength Din 531 + 55 1520 kp / cm

Veto-E-module Din 531 + 57 103/1 + 00 kp / cm ^

Example 17 a) The composition of the adhesive used according to the invention:

Polyurethane cationomer dispersion (1 + 3% ca.) 11.6 wt-γ-glycidoxypropyltrimethoxysilane 0.25 "

Stearic acid amide 0.05 "

Deionized water 88.1 "b) Preparation of polyurethane cationomer dispersion: 19,200 g (11.361 moles) of adipic acid-phthalic acid-ethylene glycol polyester are dewatered for 2 hours with stirring at 120 ° C with a water jet pump. Cooled at 70 ° C. 2,880 g (17.11 + 3 moles) of 1,6-diisocyanato-23 5 86 25 hexane are added and, after quenching the heat of reaction, the mixture is stirred for a further 2 hours at 120 [deg.] C. The temperature is then adjusted so that the reaction mixture is maintained at 55 ° C, 1 + 65 g (3.908 moles) of N-methyldiethanolamine are dissolved in 1.5 l of acetone and added to the reaction mixture, and finally diluted with a further 1.5 l of acetone. 9: 1 acetone is added over the next 3 hours to reduce the viscosity, then a solution of polyurethane in acetone is added, U53 g (3.595 moles) of dimethyl sulfate in 1.5 l of acetone, stirred for 30 minutes and then an extension solution containing 165 g ( 2.75 * + moles) ethylenediamine 7.5 g (0.073 moles) of diethylenetriamine and 1.600 g of water.

'30 min. the IR spectrum taken later no longer shows NCO lines.

To the reaction mixture are added 1 + 50 ml of 20 # phosphoric acid and 30 l of distilled water heated to 50 ° C, and finally the acetone is distilled off with a water-pump vacuum. To the resulting fine dispersion is added 300 cm of an aqueous formaldehyde solution of Ho #, stirred for one hour at 50 [deg.] C. and the dispersion is finally allowed to cool with stirring.

A finely divided cationic polyurethane dispersion with a dry matter content of 1 + 3% and a pH of 3, containing 0.23% by weight of quaternary nitrogen calculated as dry matter and having a particle size of 75-100 mm is obtained. The dispersion phase is microgel-like.

The use and manufacture of the adhesive, the coating of the glass fibers, their modification with polybutylene terephthalate, the preparation and testing of the test pieces take place as in Example 16.

c) Mechanical properties of the test piece, glass content 28.3% by weight #

Impact strength Din 53 ^ 53 U6.8 cmkp / cm ^ 2

Impact strength of the notched body Din 53 ^ + 53 11.1 cmkp / cm 2

Bending strength Din 531 + 52 1858 kp / cm 2

Tensile strength Din 53 ^ + 55 1511 kp / cm 2

Veto-E-module Din 53 ^ + 57 10 ^, 200 kp / cm "Example 18

In the same manner as in Example 16, with a non-inventive adhesive consisting of a commercial mixture for fiberglass adhesives: polyvinyl acetate dispersion (5 # ka.) 10 wt.% N-methacryloxypropyltrimethoxysilane 0.25 "stearic acid amide 0.05" deionized ", 58625 2h was impregnated with glass fibers and also in the same manner as described in Example 16 was used to reinforce the same polybutylene terephthalate as also used in Examples 16 and 17. The following mechanical properties were measured on test specimens of the reinforced material (glass content 30.2 wt.%): 2

Impact strength Din 53 ^ 55 ^ 1.1 * cmkp / cm 2

Impact strength of the notched part Din 53 ^ 53 8.9 cmkp / cm

Flexural strength Din 53 ^ 52 kp / cm2

Tensile strength Din 53 ^ + 55 1087 kp / cm2

Veto-E modulus Din 53 ^ 57 85.1 + 00 kp / cm2

Example 19

In the same manner as in Example 16, the glass fibers were impregnated with a non-inventive adhesive consisting of a commercial mixture: a styrene-acrylonitrile copolymer dispersion (1+ # ka.) 12.5 wt. 0% ca.) 0.25 "and in a similar manner to Example 16 was used to strengthen the same polybutylene terephthalate. The test pieces of the material thus reinforced (glass content 29.6 wt.%) Gave the following mechanical properties: p

Impact strength Din 531 + 55 30.3 cmkp / cm o

Impact strength of the notched part Din 531 + 53 8.6 cmkp / cnr

Bending strength Din 531 + 52 11 + 78 kp / cm2

Tensile strength Din 531 + 55 960 kp / cm2

Veto-E-module Din 531 + 57 91,500 kp / cm2

Comparing the mechanical values of Examples 16 and 17 obtained using the glass fibers of the invention with the mechanical values of Examples 18 and 19 obtained with the non-bonded glass fibers of the invention, the superiority of the glass fibers of the invention in the production of glass fiber reinforced polybutylene terephthalate is clear.

Example 19 shows that it is not sufficient to use epoxysilane as a binder and any film former in the adhesive, as described in DE-A-2 206 80L, in order to obtain an optimal reinforcing effect of the pasted glass fibers in the thermoplastic polyester. Rather, it is crucial to use the optimum combination of binder and film former in the adhesive as used in accordance with the invention, since a fiberglass adhesive generally contains ten to 1 + 0 times the amount of film former relative to the binder. As shown in Example 19, an unsuitable film former significantly damages the beneficial effect of the binder, so that the reinforcing effect of the glass fibers is clearly deteriorated.

Claims (13)

25 58625 Glass fibers for reinforcing thermoplastics, characterized in that they are made by coating an adhesive with an aqueous polyurethane ionomer dispersion as a film former and epoxyalkylalkoxysilane as a binder or one of the following combinations of a, b or e) alkylalkane and alkoxyalkylalkoxyalkyl epoxyalkylalkoxysilane and low molecular weight aliphatic, primary or secondary monoamine, c) aminoalkylalkoxysilane and low molecular weight monoepoxide, and optionally other additives such as e.g. lubricant, wetting agent and antistatic agent, Glass fibers according to Claim 1, characterized in that the aqueous polyurethane dispersion is a polyurethane anionomer dispersion. Glass fibers according to Claim 1 or 2, characterized in that the aqueous polyurethane dispersion is a polyurethane cationomer dispersion. Glass fibers according to one of Claims 1 to 3, characterized in that the concentration of the aqueous polyurethane dispersion in the adhesive is 1 to 15% by weight, preferably 3 to 7% by weight, calculated as polyurethane. Glass fibers according to one of Claims 1 to U, characterized in that the concentration of the binder in the adhesive is from 0.05 to 1.5% by weight, preferably from 0.15 to 0.75% by weight. Glass fibers according to one of Claims 1 to 5, characterized in that the epoxyalkylalkoxysilane used as binder is N-glycidoxypropyltrimethoxysilane. Glass fibers according to one of Claims 1 to 5, characterized in that the epoxyalkylalkoxysilane used as binder is (S- {3,1-epoxy-cyclohexyl) -ethyltrimethoxysilane. Glass fibers according to one of Claims 1 to 7, characterized in that polyurethane dispersions with an average particle size of less than 1 μm, preferably 0.05 μm to 0.5 μm, are used. Glass fibers according to one of Claims 1 to 8, characterized in that the dispersed polyurethane ionomers have an ionic group content of 5 to 3 milliequivalents per 100 g of dry matter. 26 58625 Glass fibers according to one of Claims 1 to 9, characterized in that polyurethane ionomer dispersions are used which, when dried, form a film with a tensile strength of more than 50 kp / cm, preferably more than 100 kp / cm1, with a elongation at break is 100-600%, has a Shore-A hardness of 50-90 and a swelling in water of less than 30%. Glass fibers according to Claim 1, characterized in that the film former is an aqueous polyurethane anionomer dispersion, the binder is a combination of N-aminopropyltriethoxysilane and epichlorohydrin and the lubricant is an anionic polyethylene dispersion. Glass fibers according to Claim 1, characterized in that the film former is an aqueous polyurethane anionomer dispersion, the binder is a combination of X-aminopropyltriethoxysilane and (5- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the lubricant is an anionic polyethylene ethylene. Glass fibers according to Claim 1, characterized in that the film former is an aqueous polyurethane anionomer dispersion, the binder is a combination of K-glycidoxypropyltrimethoxysilane and n-propylamine and the lubricant is an anionic polyethylene dispersion. 1 ^. Glass fibers according to Claim 1, characterized in that the film former is an aqueous polyurethane cationomer dispersion, the binder is β-glycidoxypropyltrimethoxysilane and the fatty acid amide having 12 to 18 carbon atoms as lubricant. 58625 27