EP3638717A1 - Surface-modified glass fibers for reinforcing concrete, and method for producing same - Google Patents

Abstract

The invention pertains to the field of chemistry and construction and relates to surface-modified glass fibers for reinforcing concrete, such as those which can be used in textile-reinforced concrete (textile concrete) for example. The aim of the invention is to provide surface-modified glass fibers for reinforcing concrete, said glass fibers being at least substantially protected from an exposure to alkali due to calcium hydroxide which is released during the cement reaction process and/or dissolution and leaching processes generated thereby. This is achieved by surface-modified glass fibers for reinforcing concrete, said glass fibers being at least partly coated at least with hydrolysis-stable and alkali-resistant cationic polyelectrolytes and/or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and/or a hydrolysis-stable and alkali-resistant polyelectrolyte complex and coupled to the glass fiber surface via a (polyelectrolyte) complex formation process by means of an ionic bond, thereby forming the hydrolysis-stable and alkali-resistant polyelectrolyte complex A, wherein at least one additional (co)polymer at least partly coats the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A via ionic and/or covalent bonds.

Description

 Surface modified glass fibers for concrete reinforcement and process for their preparation

The invention relates to the fields of chemistry and construction and relates surface-modified glass fibers for concrete reinforcement, as they can be used for example in textile-reinforced concretes (textile concrete).

Due to the mechanical properties and the price-performance ratio, glass fibers are widely used as reinforcing materials in duromer, thermoplastic and elastomeric materials / plastics - but also in construction as concrete reinforcing material.

 Glass fibers as commercial reinforcing materials are usually made from the melt and processed into numerous products.

For the different applications, glass fibers are usually processed into roving, nonwovens, mats or fabrics. For profile production, however, aligned fibers are used. Due to the low resistance to tensile forces to accommodate tensile and / or compressive forces in concrete in addition to steel as reinforcement material increasingly textile structures, such as AR glass fibers or carbon fibers (carbon), inserted as textile fiber reinforcements. Concrete with technical textiles of such fibers as reinforcements is generally referred to as textile concrete.

Structures and finished parts made of textile concrete are described for example in EP 2 530 217 A1 and DE 10 2015 100 438 A1.

The advantage of textile fiber reinforcement is u.a. The fact that they can be arranged in the near-surface edge zone of the component, as they do not rust, in contrast to reinforcements made of structural steel and therefore require little or no concrete cover.

For the different applications in textile concretes in each case specially manufactured types of glass fiber are produced and usually processed into roving.

Reinforcing fibers generally affect the properties of a composite material. Glass fibers as reinforcing fibers in different qualities are commercially available as [Wikipedia.org/wiki.Glassfiber, as of: 02.01.2017]:

 - E-glass (E = Electric): standard glass fiber with about 90% market share, not resistant in basic and acidic environment,

 - S-glass, R-glass: glass fiber with increased strength,

 - M-glass: glass fiber with increased rigidity (modulus of elasticity),

 - C-glass: glass fiber with increased chemical resistance,

 - ECR glass: glass fiber with particularly high corrosion resistance,

- D-glass: glass fiber with low dielectric loss factor,

 - AR (Alkaline Resistant) glass: glass fiber specially developed for use in concrete, enriched with zirconium (IV) oxide, substantially resistant to a basic environment,

- Q-glass (Q = quartz): quartz glass fiber (S1O2) for use at high temperatures of up to 1450 ° C - hollow glass fibers: glass fibers (usually E glass) with a hollow cross-section

Note: R-, S- and M-glass are alkali-free and increased moisture-resistant.

For use in textile-reinforced concretes, AR glass fibers have been specifically developed and used, which have a better alkaline stability compared to E glass fibers, but as current publications show, they are also damaged by alkaline attack [Orlovski dissertations on the durability of AR- Glass Reinforcement in Textile Concrete ", Diss. RWTH Aachen, 2004 and Scheffler" For the Evaluation of AR Glass Fibers in an Alkaline Environment ", Diss. TU Dresden, 2009].

The production of glass fibers is carried out according to the prior art using sizing. When using such notch-sensitive, sized glass fibers a good, especially textile finishing is achieved without the glass fibers break. The development of coatings took place primarily in the 1960s to 1980s. Almost without exception, the sizes consist of mixtures in which starch and / or polymers, such as, for example, polyurethane derivatives and / or epoxy resins and / or silanes and / or waxes etc., are used and processed as a dispersion. In polymer-based size formulations, other adjuvants, such as antistatics, lubricants and adhesion promoters, such as silanes, are often used. For technological simplification, the size formulations are prepared as a multicomponent or multicomponent mixture in the form of an aqueous dispersion in the one-pot processing system and processed in this way. The glass fibers are wetted in the manufacturing process via a dipping roll with sizing and the individual filaments usually bundled into rovings. The application of sizing also achieves a certain cohesion of the glass fiber filaments in the roving. The respective sizing composition is adjusted so that an optimal bonding of the structural elements is achieved, in which the roving is incorporated. Today's sizing formulations are mostly "black-box" systems, ie there is little or no publicly available information on the ingredients and their formulation. Slanted glass fibers usually have excellent slipperiness or lubricity with a minimum of wear or broken ends.

According to DE 23 15 242 A1, organosilazo-modified polyazamides, the preparation and use of which are known, have a secondary and / or tertiary amino group and a carboxamide group in their skeleton and are bonded to a silicon atom via a polyvalent organic group. The polyazamides, which are polar and hygroscopic, are prepared via a Michael addition reaction or haloalkylation.

 The investigation of the adhesion of these silicon-containing polyazamides was carried out in DE 23 15 242 A1 Example 54. The glass plates surface-treated with these organosilicon-modified polyazamide showed excellent adhesion between the glass surface and the cured epoxy resin.

 According to DE 23 15 242 A1 Example 54, after the application and curing of epoxy resin, the glass plates were treated in water, and it was found that the epoxy resin showed no adhesion to the polyethylene imine and unmodified polyazamide surface treated glass plates. Consequently, the use of unmodified polyelectrolytes, such as polyethyleneimine and polyazamide, would not be suitable for glass fiber modification, i. glass surfaces and glass fibers derived therefrom, which are treated with silane-free cationic polyelectrolytes, such as polyethyleneimine and polyazamide, and subsequently reacted with epoxy resin, do not form a (hydrolysis) stable composite in water.

Thus, this Example 54 states that the glass surfaces, and derived therefrom, glass fibers treated with polyethylene 1200 molecular weight and unmodified polyazamide and subsequently reacted with epoxy resin, do not form a (hydrolysis) stable composite in water and consequently as surface modifying agents Glass fibers are unsuitable.

As is known, sizing to glass fibers during the processing of the sized glass fibers by the formation of protective layers should prevent filament damage, such as glass fiber breakage and abrasion. Furthermore, the sizing establishes contact between the individual glass filaments and ensures the merging of the filaments into a workable thread. Therefore, the sizing must be distributed on the glass fiber surface and should retain an "adhesive" effect after drying.

 During the production of the glass fibers in the spinning process, the size is applied to the individual glass filaments by means of a sizing roll, wherein the solids of the sizing must not have a tendency to agglomerate.

Although the increased ZrO2 content in the AR fiber already provides some protection against the corrosive attack in the alkaline environment of concrete, the glass fiber size should act as an additional diffusion barrier, which is why it should be stable even at higher pH values.

Thomason and Dwight [Thomason, J.L .; Dwight, D.W .; Composites Part A: Applied Science and Manufacturing 30 (1999), 1401-1413] and Gao et al. [Gao, S.L .; Mäder, E .; Abdkader, A .; Offermann, P .; Journal of Non-Crystalline Solids 325 (2003), 230-241] have described that there is only irregular distribution of sizing on the glass fiber surface. A continuous protection of the glass fiber surface by the sizing is therefore not available.

The SEM images of Figs. 1 and 2 exemplify that sizing does not form a closed film on the glass fiber, but the size of the dispersion during glass fiber production is only locally, i. is present at points distributed on the glass fiber surface adsorbed. The predominant fiberglass surface is therefore unmodified as free / "bare" glass fiber, representing the problem of alkali resistance in the application of E-glass fibers as the standard fiber with the largest market share and also AR glass fibers in textile concrete.

This is the real problem for the use of glass fibers for textile reinforced concretes. The surface coverage of the sizing treatment is only incomplete, as a result of which the alkaline attack and the damage to the glass fibers in the textile concrete actually take place, as evidenced by the dissertations by Orlowski and Scheffler for AR glass fibers. Consequently, a subsequent coating of sized glass fibers with polymers, such as eg with epoxy resin, only leads to selective intensive interactions at the local sizing sites and not to a cohesive planar bond due to ionic interaction with the sizing between the glass fiber surface and the coating agent. The other, previously "bare" regions of the glass fiber are only in loose contact with the coating material, so that in the basic medium, such as concrete, these sites are infiltrated, which then leads over a longer period to damage the glass fiber as a reinforcing material overall For textile concrete specially developed, alkali-resistant AR glass fibers are attacked in an alkaline medium, as the PhD thesis of Orlowski and Scheffler prove.

AR glass fibers, which are developed and used in particular for reinforcing plaster, screed, concrete or mortar, lose their long-term release in cementitious binders with high pH values when stored in water, according to Orlowsky [Diss. RWTH Aachen, 2004] due to the following damage mechanisms ... in cementitious binder "on strength:

 - "Corrosion of AR glass through dissolution and leaching processes ...

- Mechanical damage caused by ingrowing hydration products, which both cause loss of ductility of the composite material and can exert transverse pressure on the filaments under load ...

 - Static fatigue: The growth of defects in the AR glass surface causes premature failure of the glass and the causes of defect growth are not clear. "

The object of the present invention is to provide surface-modified glass fibers for concrete reinforcement, which are at least substantially protected against an alkaline attack by the lime hydrates released in the cement reaction and / or dissolution and leaching processes generated thereby, and the disclosure of a simple and inexpensive process for Preparation of such surface-modified glass fibers.

The object is achieved with the invention specified in the claims, wherein combinations of the individual dependent claims in the sense are included as long as they are not mutually exclusive.

The surface-modified concrete strengthening glass fibers according to the invention are at least partially covered with a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or with a hydrolysis-stable and alkali-resistant polyelectrolyte complex and via (polyelectrolyte) complex formation by ionic bonding to the glass fiber surface with formation of the hydrolysis-stable and alkali-resistant polyelectrolyte complex A, wherein at least one further (co) polymer at least partially covers the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A via ionic and / or covalent bonds.

Advantageously, a hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present, which

 by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or

 by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or

 by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges which have been prepared before application to the glass fiber surface,

originated.

Likewise advantageously, the hydrolysis-stable and alkali-resistant polyelectrolyte complex A which has formed on the glass fiber surface essentially completely or completely covers the glass fiber surface and / or the further (co) polymer essentially completely or completely covers the polyelectrolyte complex A. Further advantageously, as a hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture

 Polyethyleneimine (linear and / or branched) and / or copolymers and / or

Polyallylamine and / or copolymers and / or

 - Polydiallyldimethylammoniumchlorid (PolyDADMAC) and / or copolymers and / or

 - Polyvinylamine and / or copolymers and / or

 - Polyvinylpyridine and / or copolymers and / or

 - Polyamideamine and / or copolymers and / or

 Cationically modified poly (meth) acrylate (s) and / or copolymers and / or

 Cationically modified poly (meth) acrylamide (s) with amino groups and / or copolymers and / or

 Cationically modified maleimide copolymer (s) prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or

 Cationically modified itaconic imide (co) polymer (s) prepared from itaconic acid (anhydride) (co) polymer (s) and N, N-dialkylaminoalkyleneamine (s)

available.

And also advantageously, as functionalities on the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture

 Unmodified primary and / or secondary and / or tertiary amino groups which have no substituents with a further reactive and / or activatable functional group and / or olefinically unsaturated double bond at the amine nitrogen atom, and / or quaternary ammonium groups which have no nitrogen atom Have substituents with a further reactive and / or activatable functional group and / or olefinically unsaturated double bond, and / or

- Amino groups and / or quaternary ammonium groups on the nitrogen atom, at least partially by alkylation reactions chemically with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond are modified,

and or

 Amino groups and / or quaternary ammonium groups and amide groups which are chemically modified by acylation reactions of amino groups for the amide with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond,

available.

It is also advantageous if at least one anionic polyelectrolyte or an anionic polyelectrolyte mixture without and / or with at least one further, different from the anionic group reactive as functionalities on the attached to the glass fiber surface hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte / or activatable functional group and / or having at least one olefinically unsaturated double bond.

It is furthermore advantageous if the anionic polyelectrolyte or anionic polyelectrolyte mixture

 (a) (meth) acrylic acid copolymers which are present without and / or with at least one further reactive and / or activatable functional group which has been introduced via the copolymerization, and / or which are at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of the (meth) acrylic acid group, are present, and which are preferably water-soluble, and / or

(b) modified maleic acid (anhydride) copolymers which are preferably present in the acid and / or monoester and / or monoamide and / or water-soluble imide form and / or which are present without and / or with residual anhydride groups and / or, which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or which have at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which has a polymer-analogous Implementation / modification of maleic acid (anhydride) groups are coupled, are present, and which are preferably water-soluble, and / or

 (c) modified itaconic acid (anhydride) (co) polymers which are preferably in the acid and / or monoester and / or monoamide and / or water soluble imide form and / or those which have no and / or residual Anhydride groups are present and / or which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of itaconic acid (anhydride) groups, are present, and which are preferably water-soluble, and / or

 (d) modified fumaric acid copolymers which are preferably present in the acid and / or monoester and / or monoamide form and / or those which have no and / or at least one further reactive and / or activatable functional group which exceeds the Copolymerization is present, and / or, which are present with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of fumaric acid groups, and which are preferably water-soluble, and or

 (e) anionically modified (meth) acrylamide (co) polymers which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization and / or which have at least one another reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of the (meth) -acrylamide group, are present, and which are preferably water-soluble, and / or

(f) sulfonic acid (co) polymers, such as styrenesulfonic acid (co) polymers and / or vinylsulfonic acid (co) polymers in acid and / or salt form, which can be reacted with at least one further reactive and / or activatable polymer functional group which has been introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, via a polymer-analogous reaction / modification of sulfonic acid groups such as Sulfonsäureamidgruppen coupled, are present, and which are preferably water-soluble, and / or

 (g) (co) polymers having phosphonic acid and / or phosphonate groups which are present, for example, bound as aminomethylphosphonic acid and / or aminomethylphosphonate and / or amidomethylphosphonic acid and / or amidomethylphosphonate and / or which are at least one further reactive and / or or activatable functional group which has been introduced via the copolymerization, and / or which are present with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which via a polymer-analogous reaction / modification (Co) Polymer are present, and which are preferably water-soluble,

available.

It is likewise advantageous if the hydrolysis-stable and alkali-resistant cationic polyelectrolytes or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture have a molecular weight of less than 50,000 daltons, preferably in the range of between 400 and 10,000 daltons.

It is also advantageous if at least one, at least difunctional and / or difunctionalized, oligomeric and / or macromolecular (co) polymer having functional groups and / or olefinic unsaturated double bonds is present as further (co) polymer.

It is also advantageous if thermoplastics and / or duromers and / or elastomers are present as further (co) polymer.

It is also advantageous if as thermosetting (co) polymers polyester resins (UP resins), vinyl ester resins and epoxy resins, and as thermoplastic (co) polymers polyurethane, polyamide and polyolefins, such as polyethylene or polypropylene, and PVC be present, the polyolefins are grafted with (meth) acrylic acid derivatives and / or maleic anhydride present. In the case of the reinforcing materials for textile concrete according to the invention with surface-modified glass fibers, a hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present on plain and silane-free glass fiber surfaces having at least partially covering functional groups and / or olefinically unsaturated double bonds and after reaction with functional groups and / or olefinically unsaturated double bonds chemically covalent bonds coupled with other (co) polymers present.

Advantageously, at least one, at least difunctional and / or difunctionalized, oligomeric and / or macromolecular (co) polymer having functional groups and / or olefinic unsaturated double bonds is present as further (co) polymers.

Likewise advantageously, thermoplastics and / or duromers and / or elastomers are present as (co) polymer.

Further advantageously, as functionalities of the adsorbed, coupled via ionic bonds hydrolysis-stable cationic polyelectrolyte are amino groups, preferably primary and / or secondary amino groups, and / or quaternary ammonium groups.

In the process according to the invention for the production of surface-modified glass fibers, during or after the production of glass fibers on the glass fiber surfaces from an aqueous solution with a concentration of at most 5 wt .-%, a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, at least partially covered, wherein hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess be applied to cationic charges, and subsequently at least one additional (co) polymer on the on the glass top surface emerged hydrolysis-stable and alkali-resistant polyelectrolyte complex A is applied at least partially covering.

Advantageously, polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation or are used as hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures are polyelectrolyte mixtures which are not subsequently alkylated after preparation and / or are used as the hydrolysis-stable and alkali-resistant cationic polyelectrolytes acylated and / or sulfamidated are used.

Also advantageously, as a hydrolysis-stable and alkali-resistant unmodified cationic polyelectrolyte

 Polyethyleneimine (linear and / or branched) and / or copolymers and / or

Polyallylamine and / or copolymers and / or

 - Polydiallyldimethylammoniumchlorid (PolyDADMAC) and / or copolymers and / or

 - Polyvinylamine and / or copolymers and / or

 - Polyvinylpyridine and / or copolymers and / or

 - Polyamideamine and / or copolymers and / or

 Cationically modified poly (meth) acrylate (s) and / or copolymers and / or

 Cationically modified poly (meth) acrylamide (s) with amino groups and / or copolymers and / or

 Cationically modified maleimide copolymer (s) prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or

 Cationically modified itaconic imide (co) polymer (s) prepared from itaconic acid (anhydride) (co) polymer (s) and N, N-dialkylaminoalkyleneamine (s)

used as pure substance (s) or in a mixture, preferably dissolved in water.

Furthermore advantageously, hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic ones are used Polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in a concentration of not more than 5 wt .-% in water or in water with the addition of acid, such as carboxylic acid, for example formic acid and / or acetic acid and / or mineral acid, without further Simple or sizing ingredients and / or silanes used.

And also advantageously, hydrolysis-stable and alkali-resistant cationic polyelectrolytes which are not post-alkylated and / or acylated and / or sulfamidated after preparation and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures which are not subsequently alkylated and / or acylated after preparation and / or acylated are sulfamidated, used in a concentration <2 wt .-% and particularly preferably <0.8 wt .-%.

It is also advantageous if hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons, preferably in the range between 400 and 10,000 daltons, are used.

It is also advantageous if a modified hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture which (s) after the preparation in a subsequent reaction partially alkylated and / or acylated and / or reacted with carbonic acid derivatives and / or sulfamidated and thus provided with a substituent with reactive and / or activatable groups for a coupling reaction, subsequently with the reactive and / or activatable groups of the covalently coupled substituent without crosslinking of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture via at least one functional group and / or via at least one olefinically unsaturated double bond is reactively reacted with other materials to form a composite material. It is likewise advantageous if the partial alkylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is accompanied by introduction of substituents with reactive groups by haloalkyl derivatives and / or (epi-) halohydrin and / or epoxy compounds and / or or compounds which undergo a Michael analogue addition, such as advantageously acrylates and / or acrylonitrile with amines.

And it is also advantageous if the partial acylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture with introduction of substituents with reactive groups by carboxylic acids and / or carboxylic acid halides and / or carboxylic anhydrides and / or carboxylic acid esters and / or diketenes, or a quasi-acylation by isocyanates and / or urethanes and / or carbodiimides and / or uretdiones and / or allophanates and / or biurets and / or carbonates is realized.

It is also advantageous if the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in water, preferably in the form of ammonium compounds, are used Case of primary and / or secondary and / or tertiary amino groups to the aqueous solution of carboxylic acid (s) and / or mineral acid (s) are added to convert the amino groups in the ammonium form.

It is furthermore advantageous if modified glass fiber surfaces which are at least partially and preferably completely covered with at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges, directly after their preparation and coating / surface modification and / or reactively reacted later with other materials to form chemically covalent bonds. It is also advantageous if the modified glass fiber surfaces are wound up and / or temporarily stored as a roving and subsequently reacted reactively with other materials to form chemically covalent bonds.

And it is also advantageous if the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges reactive groups in the form of functional groups and / or olefinically unsaturated double bonds which are reactively reacted with functionalities of the other materials to form chemically covalent bonds.

Finally, it is advantageous if commercially prepared and sized glass fiber surfaces or plain and silane-free glass fiber surfaces have an aqueous solution with a maximum concentration of 5% by weight of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or is at least partially coated from a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, using cationic polyelectrolytes or cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons.

The solution according to the invention makes it possible for the first time to specify surface-modified glass fibers for concrete reinforcement which are at least substantially protected against alkaline attack by the lime hydrates released in the cement reaction and / or dissolution and leaching processes generated thereby, as well as a simple and cost-effective method of production specify such surface-modified glass fibers. With the solution according to the invention, it is in particular possible to specify simple surface-modified and therefore surface-protected glass fibers having as complete coverage as possible and in the first modifying step via ionic modification agents coupled via ionic and / or covalent bonds in subsequent modifications. Such surface-modified glass fibers for concrete reinforcement not only have improved properties as a whole, but are particularly suitable for further processing into textile concrete, since they have a high resistance to alkali in textile concrete. With the method according to the invention such surface-modified glass fibers can be produced as a strand or tape material.

This is achieved by surface-modified glass fibers for concrete reinforcement, which are at least partially covered with at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or with a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charge. ) Complex formation are coupled by ionic bonding to the glass fiber surface to form the polyelectrolyte complex A, and wherein at least one further (co) polymer at least partially covers the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A alkali-resistant via ionic and / or covalent bonds.

According to the invention, a hydrolysis-stable and alkali-resistant cationic polyelectrolyte is to be understood as meaning all the polyelectrolytes which are resistant to hydrolysis and / or alkali and have cationic charges and are colloquially also referred to as polycations.

According to the invention, a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is to be understood as meaning all mixtures of at least two or more polyelectrolytes which are hydrolysis-stable and / or alkali-resistant and have cationic charges and are also colloquially referred to as polycation mixtures. Such hydrolysis-stable and / or alkali-resistant cationic polyelectrolytes or hydrolysis-stable and / or alkali-resistant cationic polyelectrolyte mixtures can advantageously be used as

 Polyethyleneimine (linear and / or branched) and / or copolymers and / or

Polyallylamine and / or copolymers and / or

 - Polydiallyldimethylammoniumchlorid (PolyDADMAC) and / or copolymers and / or

 - Polyvinylamine and / or copolymers and / or

 - Polyvinylpyridine and / or copolymers and / or

 - Polyamideamine and / or copolymers and / or

 Cationically modified poly (meth) acrylate (s) and / or copolymers and / or

 Cationically modified poly (meth) acrylamide (s) with amino groups and / or copolymers and / or

 Cationically modified maleimide copolymer (s) prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or

 Cationically modified itaconic imide (co) polymer (s) prepared from itaconic acid (anhydride) (co) polymer (s) and N, N-dialkylaminoalkyleneamine (s)

to be available.

As functionalities of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture can be advantageously

 Unmodified primary and / or secondary and / or tertiary amino groups which have no substituents with a further reactive and / or activatable functional group and / or olefinically unsaturated double bond at the amine nitrogen atom, and / or quaternary ammonium groups which have no nitrogen atom Have substituents with a further reactive and / or activatable functional group and / or olefinically unsaturated double bond, and / or

- Amino groups and / or quaternary ammonium groups on the nitrogen atom, at least partially by alkylation reactions chemically with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond are modified, and / or

 - Amino groups and / or quaternary ammonium groups and amide groups by

Acylation reactions of amino groups to the amide are chemically modified with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond,

to be available.

Such functionalities on the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture affixed to the glass fiber surface may also be an anionic polyelectrolyte or an anionic polyelectrolyte mixture without and / or with at least one further reactive and / or activatable functional group other than the anionic group and / or with at least one olefinically unsaturated double bond.

In the event that an anionic polyelectrolyte or an anionic polyelectrolyte mixture is present as a carrier of one or more functionality (s), this can

 (a) (meth) acrylic acid copolymers which are present without and / or with at least one further reactive and / or activatable functional group which has been introduced via the copolymerization, and / or which are at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of the (meth) acrylic acid group, are present, and which are preferably water-soluble, and / or

(b) modified maleic acid (anhydride) copolymers which are preferably present in the acid and / or monoester and / or monoamide and / or in preferably water-soluble imide form and / or which are present without and / or with residual anhydride groups and / or which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or which have at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which has a polymer-analogous Implementation / modification of maleic acid (anhydride) groups are coupled, are present, and which are preferably water-soluble, and / or

 (c) modified itaconic acid (anhydride) (co) polymers which are preferably present in the acid and / or monoester and / or monoamide and / or in preferably water-soluble imide form and / or which contain no and / or are present with remaining anhydride groups and / or, which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of itaconic acid (anhydride) groups, are present, and which are preferably water-soluble, and / or

 (d) modified fumaric acid copolymers which are preferably present in the acid and / or monoester and / or monoamide form and / or those which have no and / or at least one further reactive and / or activatable functional group which exceeds the Copolymerization is present, and / or, which are present with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of fumaric acid groups, and which are preferably water-soluble, and or

 (e) anionically modified (meth) acrylamide (co) polymers which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization and / or which have at least one another reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of the (meth) -acrylamide group, are present, and which are preferably water-soluble, and / or

(f) sulfonic acid (co) polymers, such as styrenesulfonic acid (co) polymers and / or vinylsulfonic acid (co) polymers in acid and / or salt form, which can be reacted with at least one further reactive and / or activatable polymer functional group which has been introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, via a polymer-analogous reaction / modification of sulfonic acid groups such as Sulfonsäureamidgruppen coupled, are present, and which are preferably water-soluble, and / or

 (g) (co) polymers having phosphonic acid and / or phosphonate groups which are present, for example, bound as aminomethylphosphonic acid and / or aminomethylphosphonate and / or amidomethylphosphonic acid and / or amidomethylphosphonate and / or which are at least one further reactive and / or or activatable functional group which has been introduced via the copolymerization, and / or which are present with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which via a polymer-analogous reaction / modification (Co) Polymer are present, and which are preferably water-soluble,

be.

The hydrolysis-stable and alkali-resistant cationic polyelectrolytes present in the surface-modified glass fibers according to the invention or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture advantageously have a molecular weight below 50,000 daltons, preferably in the range between 400 and 10,000 daltons.

At least partially covering hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures are preferably present on the glass fiber surface.

These then form with the anionic glass fiber surface a hydrolysis-stable and alkali-resistant polyelectrolyte complex A which has been formed by (polyelectrolyte) complex formation and is coupled to the glass fiber surface by ionic bonding.

However, it is also possible for the glass fiber surface to be at least partially covered by an excess of cationic charges with a hydrolysis-stable and alkali-resistant polyelectrolyte complex formed before application to the glass fiber surface. Such a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges are according to the invention all polyelectrolyte complex compounds which have been prepared from at least one cationic polyelectrolyte and at least one anionic polyelectrolyte and which have an excess of cationic charges, and colloquially as "asymmetric Polyelektrolytkomplexe These hydrolysis-stable and alkali-resistant polyelectrolyte complexes are stable to hydrolysis under the respective processing conditions and, due to their composition and macromolecule structure (s), are soluble or dissolved in water and do not form gelatinous structures.

This hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges formed before application to the glass fiber surface forms with the anionic glass fiber surface a hydrolysis-stable and alkali-resistant polyelectrolyte complex A which is formed by (polyelectrolyte) complex formation and coupled to the glass fiber surface by ionic bonding.

According to the invention, a hydrolysis-stable and alkali-resistant polyelectrolyte complex A according to the invention should therefore be understood as meaning a polyelectrolyte complex which:

 by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or

by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or

 by complexing the glass fiber surface with hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges which have been produced before application to the glass fiber surface,

originated.

All of these polyelectrolyte complexes according to the invention are composed of the anionically charged glass fiber surface and the hydrolysis-stable material applied thereto and alkali-resistant cationic polyelectrolyte and / or polyelectrolyte mixture and / or polyelectrolyte complex with an excess of cationic charges during or after the preparation of the glass fibers by complex formation and are hereinafter also referred to as polyelectrolyte complex A. The polyelectrolyte complex A according to the invention thus always formed with the glass fiber surface.

The hydrolysis-stable and alkali-resistant polyelectrolyte complex A should substantially or completely cover the glass fiber surface as much as possible.

Furthermore, according to the invention at least one further (co) polymer is present on the glass fiber which at least partially covers the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A via ionic and / or covalent bonds.

As a further (co) polymer, at least one, at least difunctional and / or difunctionalized, low molecular weight and / or oligomeric and / or (co) polymer having the same or different functional groups and / or olefinic unsaturated double bonds may be present, such as advantageously thermoplastics and / or duromers and / or elastomers.

 In this case, the at least one further (co) polymer, which is formed during or after the addition and / or attached as (co) polymer, should cover the polyelectrolyte complex A substantially completely or as completely as possible.

According to the invention, at least partial coverage means a degree of coverage of at least more than 50% of the glass fiber surface and / or the glass fiber bundle surface by the polyelectrolyte complex A and also by the further (co) polymers, wherein according to the invention at least 80% and preferably 100% % coverage is to be achieved and achieved.

Likewise, the present invention, the hydrolysis-stable and alkali-resistant cationic and / or anionic polyelectrolytes or Polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic or anionic charges, both before application to the glass fiber surface, and thereafter, in particular under the respective necessary processing conditions, be stable.

In the context of the solution according to the invention, the definitions given below are understood to mean the corresponding complexes.

Polyelectrolyte complex A has been formed by a complex formation between the glass fiber surface and at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charge, and then at least partially, substantially completely or completely the glass fiber surface.

The hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charge is a starting material for the process according to the invention and is prepared before use in the process according to the invention.

Other polyelectrolyte complexes may be complexed

 between the polyelectrolyte complex A and an anionic polyelectrolyte and / or an anionic polyelectrolyte mixture and / or a polyelectrolyte complex with an excess of anionic charges and cover the polyelectrolyte complex A at least partially, substantially completely or completely, and / or

between the at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and an anionic polyelectrolyte and / or an anionic polyelectrolyte mixture to form a water-soluble polyelectrolyte complex with an excess of cationic charges as a (possible) starting material for the process according to the invention; /or between the at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and an anionic polyelectrolyte and / or an anionic polyelectrolyte mixture to form a water-soluble polyelectrolyte complex with an excess of anionic charges as a (possible) starting material for the process according to the invention.

The glass fiber surfaces at least partially covered according to the invention with the polyelectrolyte complex A are at least partially covered with at least one further (co) polymer and coupled via ionic and / or covalent bonds. The preferably complete covering with at least one further (co) polymer can be carried out on the individual glass fiber and preferably on glass fibers in a glass fiber bundle / glass fiber roving via the addition of a hydrolysis-stable and alkali-resistant (co) polymer or a hydrolysis-stable and alkali-resistant (co-) Polymer mixture having functional groups which are capable of a coupling reaction by covalent bonds with the surface of the polyelectrolyte complex A, by a cohesive, at least partially, advantageously complete Unnnantelantelung / covering the surface of the polyelectrolyte complex A or the glass fiber bundle / Glasfaserrovings done.

Advantageously, the cladding / covering of the glass fibers or of the glass fiber roving can take place by means of at least one further layer, as a result of which an alkali-resistant reinforcing material is present / arises.

It is essential to the invention that by the present solution, the surface of non-alkali-resistant glass fibers by an at least partially, advantageously as complete or complete coverage by a polyelectrolyte I and at least one other (co) polymer, the ionic and / or covalent bonds and cohesively is coupled to the glass fiber surface, at least substantially fully protected against alkaline attack by the concrete matrix environment and thus processing-stable and easy to handle reinforcing materials for textile concretes are present and can be produced. Although glass fiber ends created by fracture or cutting / cuts and / or surfaces locally damaged by handling may locally undergo an alkaline attack, this attack is limited to these locations only and does not migrate farther along the fiber surface since the covering is coupled cohesively on the glass fiber surface via ionic and / or covalent bonds, so that no continuous damage in the so modified glass fiber bundle / Glasfaserroving can be done.

Such a material bond between glass fiber surface and a cladding / covering according to the invention is not known in the prior art and does not exist in the known commercially available sized glass fibers, even if they were subsequently further surface-coated in a commercial manner.

As is well known in the art, the size after covering from the dispersion during glass fiber production is only local, i. selectively dispersed on the glass fiber surface, since coverage to the glass fiber is thus practically only localized via the sizing sites, i. punctually / locally and not over the entire surface and can not take place cohesively. In addition, the commercial sizing components that have been applied from a water dispersion are at least partially swellable, thereby lowering the mechanical strength between the glass fiber surface and the sizing material. Under the action of moisture and alkali as well as by diffusion of moisture and alkaline agent (s) into the interface between glass fiber surface and swollen sizing or other coating material, a reaction with the glass fiber surface occurs and over time leads to damage to the glass fiber and consequently weakening of the glass fiber Overall reinforcing effect.

The alkali resistance of the otherwise non-alkali-resistant glass fiber is due to the inventive dense cohesive, as completely as possible blanketing / covering the glass fiber surface without loose and / or swellable structures and / or capillaries and / or cavities for the diffusion of Moisture and / or dissolved alkaline agents in the boundary layer to the glass fiber surface achieved.

It has proven advantageous if the inventive tight cohesive, as completely as possible covering / covering of the glass fiber surface on the outer surface, which interacts with the concrete material, functional and / or polar groups such as carboxylic acid and / or Carbonsäureamid- / / or sulfonic acid and / or sulfonamide and / or phosphoric acid and / or phosphonic acid and / or urea and / or urethane and / or hydroxyl and / or amino groups and / or derivatives thereof via functional chains coupled via spacer chains and / or has polar groups of this fiber composite material as a reinforced concrete reinforcing material, which reinforce the interactions in textile reinforced.

Advantageously, the inventive tight cohesive, completely covering as possible cover / cover on the anionic glass fiber surface act as a kind of buffer, so that a possible alkaline attack is also buffered and thus chemically attenuated.

As further (co) polymers thermosetting and / or thermoplastic (co) polymers can be used. As thermosetting (co) polymers, for example, polyester resins (UP resins), vinyl ester resins and epoxy resins can be present and used. As thermoplastic (co) polymers, for example, polyurethane, polyolefins, e.g. Polyethylene or polypropylene, and PVC are used, the polyolefins with comonomers, such. (Meth) acrylic acid derivatives and / or maleic anhydride) modified as a copolymer and / or graft copolymer can be used.

The (co) polymer may also be an anionic / polyelectrolyte (mixture) or polyelectrolyte complex with an excess of anionic charges, but preferably also one or more, the modified glass fiber and / or the glass fiber strand enveloping polymers. The surface-modified glass fibers according to the invention can be reactively reacted and / or coated and / or coated with oligomers and / or polymers having reactive functional groups by further chemical modification reaction with one or more low molecular weight reagents on the surface by addition and / or substitution reactions Coupled with the surface-modified glass fibers according to the invention by a (melt) reaction on the surface are coated, preferably as glass fiber roving, and further modified during processing into a textile reinforced concrete reinforcing material.

The (further) processing of the surface-modified glass fibers according to the invention is preferably carried out as glass fiber roving in the known pultrusion or by sheathing with a thermoplastic to form a reinforced concrete reinforcing material, wherein the coupling is preferred by reactive conversion to cohesive bonds.

The surface modification and encapsulation of the glass fiber roving / glass fiber bundle by application of thermoplastic or thermosetting polymer preferably takes place directly on the surface-modified glass fibers according to the invention.

The surface modification and encapsulation of the glass fibers and the Glasfaserrovings / glass fiber bundle with a thermosetting polymer can be carried out by resin impregnation in the pultrusion, preferably using epoxy resin, vinyl ester resin, polyester resin (UP resin) or polyurethane resin and partially cured depending on the type of resin and method for producing the textile reinforced concrete reinforcing materials or cured. At least one further (protective) layer of thermosetting and / or preferably thermoplastic polymer, such as, for example, polyurethane (TPU) or maleic anhydride grafted polyolefin and preferably maleic anhydride grafted polypropylene for protection against alkaline attack of the glass fibers of Glasfaserrovings / Fiberglass bundles are applied, this layer is preferably chemically coupled and cohesively present with the duromer layer. A further surface modification and encapsulation of the glass fiber rovings / glass fiber bundles with preferably a thermoplastic polymer can be effected by sheathing the glass fibers modified as glass fiber roving / fiber bundles, for which preferably polyurethane (TPU) or polyolefin, such as polyethylene or polypropylene, for example as thermoplastic polymer, and preferably maleic anhydride-grafted polyolefin and more preferably maleic anhydride-grafted polypropylene or polyamide, such as PA6, PA66 or PA12, for protection against alkaline attack of the glass fiber is applied to the glass fiber bundle, said thermoplastic polymer layer preferably chemically coupled and cohesively bonded in contact with the surface-modified glass fibers according to the invention or the glass fiber roving / glass-fiber bundle with the surface-modified glass fibers according to the invention, and this material is present a reinforcing strand or a tape is further processed.

The qualitatively new and thus the patent-law / inventive difference to the reinforcing materials produced commercially, for example by the pultrusion method, is that for the fiber surface modification no size (dispersion (s)) is used, but according to the invention surface-modified glass fibers with a polyelectrolyte complex A and a covering with at least one further (co) polymer present.

The commercially produced glass fiber materials thus comprise sized glass fibers in which the glass fibers form a surface coating and a composite on the surface only at the local sizing regions and consequently can not consist of a continuous cohesive bond between the glass fiber surface and the sizing.

Since no cohesive bond of a protective layer to the glass fiber is thus present, the commercially sized glass fibers with the swellable sizing regions can thus not provide sufficient protection of the glass fiber against the alkaline / corrosive attack in the concrete. Prior art sizing or sizing niches consist of a variety of substances, some of which contain special silanes as adhesion promoter substances. Although these silanes, by reacting with the glass fiber surface, support a chemical bond between glass fiber and sizing agent, since it is formed only locally and not cohesively on the glass fiber surface, the silanes can not provide sufficient protection for the sized glass fibers.

The silanes usually used as alkoxysilane in sizing dispersions are known to be used in an aqueous sizing dispersion, which are not sufficiently stable over the period of use and change depending on the ambient conditions (such as temperature, pH, concentration, etc.). The changes are made by reactions with each other, for example, to form Si-O-Si bonds, that is, the silanes condense with each other and possibly also with sizing (constituents) and thus chemically change as sizing (ingredient). After application of such over time changing sizing or sizing mixtures to the glass fiber surface, which do not form a closed, cohesive surface film, the glass fibers are wound into a roving. By winding the glass fibers in the Rovingstrang lightly "stick together", which is also often desired for further handling.Afterwards, the Rovingstrang is usually still dried in direct Glasfaserl / Sehl ichtel - Schlichte2 / Glasfaser2 contact affects the local "bonding" between glass fibers and sizing components so that it comes from the glass fiber surfaces when unwinding the glass fibers from glass fiber roving and further processing for "demolition of sizing components" with each other, resulting in more defects on the glass fiber surfaces.

In SEM images (as also shown in FIGS. 1 and 2), primarily unmodified / "bare" glass fiber surfaces with isolated sizing sites or sites with "sizing blots" become visible.

In contrast, the present invention surface-modified glass fibers via the polyelectrolyte A and the other (co) polymers formed by ionic and / or covalent bonds with the polyelectrolyte complex A are coupled directly to the glass fiber surface a cohesive, flat, stable composite without capillary gaps and / or cavities for (in) diffusion of (glass) corrosive substances / media in the boundary layer / in the boundary layer area, so that no weakening of the glass fiber reinforcing effect in the composite by a corrosive / alkaline attack of liberated lime hydrate in the cement reaction and thus no damage to the glass fiber surface can be done, ie an alkaline attack is therefore not in the textile concrete.

According to the invention, the surface-modified glass fibers are produced in that a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture during or after the production of glass fibers on the glass fiber surfaces from an aqueous solution with a concentration of at most 5 wt. or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, at least partially covering, wherein hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess be used on cationic charges, and subsequently at least one further (co) polymer on the de At least partially covering the resulting hydrolysis-stable and alkali-resistant polyelectrolyte complex A is applied.

Polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation are advantageously used as hydrolysis-stable and alkali-resistant cationic polyelectrolytes, or polyelectrolyte mixtures which are not subsequently alkylated and / or acylated after preparation as hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures / or sulfamidated. As hydrolysis-stable and alkali-resistant, unmodified cationic polyelectrolyte or as hydrolysis-stable and alkali-resistant, unmodified cationic polyelectrolyte mixture can advantageously

 Polyethyleneimine (linear and / or branched) and / or copolymers and / or

Polyallylamine and / or copolymers and / or

 - Polydiallyldimethylammoniumchlorid (PolyDADMAC) and / or copolymers and / or

 - Polyvinylamine and / or copolymers and / or

 - Polyvinylpyridine and / or copolymers and / or

 - Polyamideamine and / or copolymers and / or

 Cationically modified poly (meth) acrylate (s) and / or copolymers and / or

 Cationically modified poly (meth) acrylamide (s) with amino groups and / or copolymers and / or

 Cationically modified maleimide copolymer (s) prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or

 Cationically modified itaconic imide (co) polymer (s) prepared from itaconic acid (anhydride) (co) polymer (s) and N, N-dialkylaminoalkyleneamine (s)

as a pure substance (s) or in a mixture, preferably dissolved in water, are used.

The list lists available / commercial and synthetically readily producible cationic polyelectrolytes, but is not exhaustive of the possible and useful cationic polyelectrolytes or cationic polyelectrolyte mixtures.

Preference is given to using unmodified cationic polyelectrolytes or unmodified cationic polyelectrolyte mixtures: polyethyleneimine and / or polyallylamine and / or polyamidoamine and / or cationic maleimide copolymers. However, modified cationic polyelectrolytes or cationic polyelectrolyte mixtures can also be used. The use of strong cationic polyelectrolytes with permanent charges, such as the PolyDADMAC with quaternary ammonium groups, can be independent of the pH.

When using weak cationic polyelectrolytes which carry only primary and / or secondary and / or tertiary amino groups, ie which do not have independent permanent charge independent of the pH, is carried out with addition of acid, preferably in the weakly acidic range of 4 to 6. By conformation of the dissolved polycations by repulsion of the same charged groups, that is, the generated ammonium groups, unfolding of the cationic Polyelektrolytmakromoleküls occurs, whereby a more effective attachment to the glass fiber surface is realized as a weak anionic polyelectrolyte. The use of the polyelectrolyte effect is important for the most optimal and permanent deposition of polycations, for example on glass fiber surfaces as polyanionic solid surfaces. Elongated polycations adsorb as thin films to oppositely charged solid surfaces.

The hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in a concentration of not more than 5% by weight are advantageously dissolved in water or in water with the addition of acid. such as carboxylic acid, for example formic acid and / or acetic acid and / or mineral acid, used without further sizing or sizing ingredients and / or silanes.

Advantageously, hydrolysis-stable and alkali-resistant cationic polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation , used in a concentration <2 wt .-% and particularly preferably <0.8 wt .-%. In the preparation according to the invention of the surface-modified glass fibers according to the invention, hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolytes or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixtures are present in a concentration of at most 5% by weight, advantageously in a concentration of <2% by weight and particularly preferred used in a concentration <0.8 wt .-%, wherein the concentration, depending on the nature of the hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixture, the charge density in the macromolecule, the type of cationic group (primary, secondary, tertiary amino group or quaternary ammonium group), the degree of branching and the molecular weight are each set, that is optimized, which is for the skilled person m It is possible with a few attempts. Furthermore, the adjustment of the concentration of hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixture also depends on whether the surface modification according to the invention is carried out directly in the glass fiber production process and / or subsequently, ie downstream. The adjustment of the concentration is adapted to the respective method, whereby an overcharge in the sense of polyelectrolyte chemistry is to be avoided by excessively high concentrations. Overloading then occurs or occurs due to excessively high concentrations if the packing or coverage density on the glass fiber surface is too high and the cationic polyelectrolyte molecules can not optimally arrange themselves on the glass fiber surface. In an aqueous medium, depending on the time, the pH, the type of added salt or salt mixture and the salt concentration and the temperature, a rearrangement in the direction of optimum coverage density takes place with (very) slow release of the too much deposited cationic polyelectrolyte macromolecules.

The covering of the glass fiber surface with hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixture takes place in water or in water with a solvent additive and / or acid addition, for example one or more carboxylic acids, such as formic acid and / or acetic acid, and / or mineral acids. It is particularly advantageous that for the production and further processing of the modified glass fiber surfaces according to the invention on the use of sizing or sizing components, such as silanes, can be completely dispensed with, but also with sizing modified glass fiber surfaces can be subsequently modified according to the invention.

According to the invention, a modified glass fiber surface was found which, in contrast to the statement in DE 2 315 242, Example 54, shows very good adhesion to the subsequently applied further materials and thus a very well adhering composite material can be produced and specified.

As a modified hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture can also be used which (s) after the preparation in a subsequent reaction partially alkylated and / or acylated and / or reacted with carbonic acid derivatives and / or sulfamidized and is equipped with a substituent with reactive and / or activatable groups for a coupling reaction, which subsequently with the reactive and / or activatable groups of the covalently coupled substituent without crosslinking of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture via at least one functional Group and / or via at least one olefinically unsaturated double bond is reactively reacted with other materials to form a composite material.

Unmodified cationic polyelectrolytes in the context of the present invention are understood and used to mean polycations or polycation mixtures which are not chemically modified, ie alkylated (for example by halogenoalkyl), after the preparation in a subsequent reaction with low molecular weight and / or oligomeric and / or polymeric agents. Derivatives and / or (epi-) halohydrin and / or epoxy compounds or derivatives) and / or acylated (for example, by agents (ien) with one or more carboxylic acid and / or Carboxylic acid halide and / or carboxylic acid anhydride and / or carboxylic acid ester groups and / or diketene and / or diketene-acetone adduct) and / or reacted with carbonic acid derivatives, that is quasi-acylated (for example, by agents (ies) with one or a plurality of isocyanate and / or urethane and / or carbodiimide and / or uretdione and / or allophanate and / or biuret and / or carbonate groups) and / or sulfamidized. In water, the cationic polyelectrolyte or the cationic polyelectrolyte mixture is preferably used dissolved as ammonium compound, that is, if the amino groups of the cationic polyelectrolyte or cationic Polyelektrolytgemisches present as primary and / or secondary and / or tertiary amino groups, these are at least partially by addition of acid in the Transferred ammonium form.

Advantageously, partial alkylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is effected by introducing substituents having reactive groups through haloalkyl derivatives and / or (epi-) halohydrin and / or epoxy compounds and / or compounds to undergo a Michael analogue addition, such as advantageously acrylates and / or acrylonitrile with amines.

The partial acylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture can also be advantageously carried out by introducing substituents with reactive groups by carboxylic acids and / or carboxylic acid halides and / or carboxylic anhydrides and / or carboxylic acid esters and / or diketenes, or a quasi-acylation be realized by isocyanates and / or urethanes and / or carbodiimides and / or uretdiones and / or allophanates and / or biurets and / or carbonates.

It is advantageous if the hydrolysis-stable and alkali-resistant cationic polyelectrolytes used and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight of less than 50,000 daltons, preferably in the range between 400 and 10,000 daltons, are used. The cationic polyelectrolytes synthesized synthetically via polymerization and / or polycondensation have molecular weights <50,000 D (daltons) and even more advantageously molecular weights <10,000 D, and the optimum range of molecular weight for each specific cationic polyelectrolyte must be determined in experiments. Too high molecular weights have proved to be unfavorable, since with these cationic polyelectrolyes, the optimal attachment and coverage of the glass fiber surface is not always easy. When branched polyethyleneimine, for example, the molecular weight range of 400 to 10,000 D has proved favorable.

According to the invention, the surface-modified glass fibers are advantageously also prepared by using the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in water, preferably as ammonium compound be in the case of primary and / or secondary and / or tertiary amino groups to the aqueous solution of carboxylic acid (s) and / or mineral acid (s) are added to convert the amino groups in the ammonium form.

Advantageously, modified glass fiber surfaces according to the invention as polyelectrolyte complex A, which are at least partially and preferably completely covered with at least a hydrolysis-stable and alkali-resistant cationic polyelectrolyte or a hydrolysis-stable and alkali-resistant polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, directly after their Production and coating / surface modification and / or reactively reacted later with other materials to form chemically ionic and / or covalent bonds.

This can be done, for example, if the invention with the polyelectrolyte complex A modified glass fiber surfaces a hydrolysis stable and alkali-resistant anionic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant anionic Polyelektrolytgennisch and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of anionic charges is coupled.

This can be done, for example, if the thus modified glass fiber surfaces are wound up as a roving and / or temporarily stored, and subsequently reacted reactively with other materials to form chemically covalent bonds.

It is particularly advantageous if the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges on the glass fiber surface as polyelectrolyte A complex or after further modification with further polyelectrolyte (mixture ) and / or polyelectrolyte complexes reactive and / or activatable groups in the form of functional groups and / or olefinically unsaturated double bonds, which are reacted with functionalities of the other materials to form chemically covalent bonds reactive.

The modification according to the invention of the glass fiber surface can advantageously also be realized on commercially produced and sized glass fiber surfaces or plain and silane-free glass fiber surfaces by adding an aqueous solution with a maximum concentration of 5% by weight of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or at least partially covering a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, using cationic polyelectrolytes or cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons.

In this case, for example, the treatment of preferably still moist with or without a water-soluble lubricating agent, such as a surfactant or Surfactant mixture and / or glycerol and / or polyethylene glycol and / or polypropylene glycol for improving the sliding properties, prepared, wound glass fibers, which are preferably taken for surface modification by being pulled through a bath or stored in a bath, for example in a bath with a solution of hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte or from a hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixture and / or from a dissolved, hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, previously prepared from a cationic polyelectrolyte (mixture) and an anionic polyelectrolyte (mixture) be post-treated, wherein when using water-soluble lubricants these then go into solution and the cationic polyelectrolyte or the cationic polyelectrolyte mixture and / or the g Moisture polyelectrolyte complex with an excess of cationic charges on the glass fiber surface attach or these lubricants are replaced by the cationic agents.

In the context of the present invention, cationic agents are understood to mean the cationic polyelectrolytes used and present on the glass surface and / or the cationic polyelectrolyte mixture and / or the polyelectrolyte complex with an excess of cationic charges.

Contrary to the statement in DE 2 315 242, Example 54, for the cationic polyelectrolytes polyallylamine, polyethyleneimine (branched), polyamidoamine, cationic copolymerimide (prepared from alternating propene / maleic anhydride copolymer reacted with N, N-dimethylamino-n-propylamine and imidized ) and a 1: 1 mixture of polyethylenimine (branched) and polyallylamine and polyDADMAC depending on the type of polycation (mixture) s, the charge density, the degree of branching and the molecular weight surprisingly complete and very stable coverage of the glass fiber surfaces via pH-dependent Zeta potential measurements detected. As a further detection method, the known addition reaction of the amino-group-sensitive fluorescent marker fluorescamine was used in the case of cationic agents with amino groups for the detection. Also a intensive washing with dilute acids or alkalis or refluxing or extraction for several hours in water with dilute acetic acid did not change the analytical statements that the surface modification is in an optimal coverage.

The hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolytes or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixtures form with the glass fiber surface a hydrolytically stable and alkali-resistant polyelectrolyte complex A which is stable in pH-dependent zeta potential measurements by the stable position of the isoelectric point ( where the zeta potential = 0) is detectable. The position of the isoelectric point and the course of the zeta potential curves are almost congruent before and after washing or extraction, which proves the stability of this surface modification on the glass fibers.

Compared to untreated glass fibers and commercial size-treated glass fibers, both the position of the isoelectric point and the course of the zeta potential curves in the surface-modified glass fibers of the present invention change.

Depending on the used hydrolysis-stable and alkali-resistant cationic agents and especially depending on the degree of branching at pH <7 a largely mono (macro) molecular coverage of the glass fiber surface is achieved with cationic agents in the form of a thin film.

A complete separation / elimination of the inventively applied hydrolysis-stable cationic agents of the glass fiber surface has not been achieved or detected.

Too high a concentration of cationic agents or a pH> 7 for weak cationic agents should be avoided, since then the attachment of the cationic agents to the glass surface is not optimal, ie the coverage is not optimal, and with the glass surface a so-called Forms "asymmetric polyelectrolyte complex". By "asymmetric polyelectrolyte complex" is meant when there is a higher concentration of cationic charge agents as compared to anionic charge agents in the polyelectrolyte complex, thus forming "asymmetric polyelectrolyte complexes" that can change and stabilize by rearrangement. In the presently discussed case, an excessively high concentration of agents with cationic charges would be present in comparison to the anionic glass fiber surface and thus form an asymmetric polyelectrolyte complex as polyelectrolyte complex A.

At too high a concentration of cationic agents, for example, by (subsequent) storage in water or boiling or extraction with water, the equilibrium reaction between the glass surface and cationic agents towards stable surface coverage are shifted, which as a subsequent, practical remedy for a faulty concentration cationic agents and consequently defective surface modification can be used or used.

By rearrangement reactions of the cationic agents on the glass fiber surface as a function of time, temperature, pH and salt concentration then a stabilization of cationic agents to be modified fiber surface is achieved in the direction of optimal and stable coverage. In a few experiments, the person skilled in the art can determine the technological window, ie the sufficiently optimal concentration, for the respective cationic agents in order to avoid too high a concentration and a subsequent treatment.

The glass fiber surfaces modified according to the invention can be further modified directly in the glass fiber production process or below. The thus modified glass fibers can be further processed directly after the glass fiber manufacturing process or subsequently to a reinforcing material for textile concrete. Glass fibers can be modified according to the invention directly after the glass fiber production or wound up and stored for example only as glass fiber roving, and then according to the invention modified to a reinforcing material for textile be further processed.

After the preparation of the glass fibers and the inventive surface modification to the polyelectrolyte A, the existing surface modification can be further modified by adding hydrolysis-stable and alkali-resistant anionic polyelectrolytes or hydrolysis-stable and alkali-resistant anionic polyelectrolyte mixtures to another polyelectrolyte complex. This is necessary in particular when cationic polyelectrolytes having quaternary ammonium groups are used in order to form reactive and / or activatable groups in the form of functional groups via the formation of a further stable polyelectrolyte complex, wherein the attached hydrolysis-stable and alkali-resistant anionic polyelectrolytes or hydrolysis-stable and alkali-resistant anionic polyelectrolyte mixtures / or olefinically unsaturated double bonds for coupling reactions, and to be able to produce cohesive composites during cladding / covering with further (co) polymers in a further subsequent process for modifying and coating the glass fibers or Glasfaserrovings example in the pultrusion process by pulping.

As anionic polyelectrolytes or anionic polyelectrolyte mixtures preferably dissolved in water, for example:

 (Meth) acrylic acid copolymers which are present without and / or with at least one further functional group other than carboxylic acid which has been introduced via the copolymerization and / or which are at least one further functional group other than carboxylic acid and / or or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of the (meth) acrylic acid group, are present, and which are preferably water-soluble, and / or

- Modified maleic acid (anhydride) copolymers, preferably partially or completely in the acid and / or monoester and / or Mono- amide and / or water-soluble imide form and / or present without and / or with residual anhydride groups and / or present without and / or with at least one further functional group introduced via the copolymerization, and / or or, which are present with at least one further functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of preferably maleic acid (anhydride) groups, and / or are preferably water-soluble, and / or

 modified itaconic acid (anhydride) (co) polymers, which are preferably present in the acid and / or monoester and / or monoamide and / or water-soluble imide form and / or which are present without and / or with residual anhydride groups and / or which are present without and / or with at least one further functional group introduced via the copolymerization, and / or which have at least one further functional group and / or at least one olefinically unsaturated double bond which has a polymer-analogous reaction / Modification of preferably itaconic acid (anhydride) groups are coupled, and which are preferably water-soluble, and / or

 modified fumaric acid copolymers which are preferably present in the acid and / or monoester and / or monoamide form and / or which are present without and / or with at least one further functional group introduced via the copolymerization and / or or, which are present with at least one further functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of preferably fumaric acid groups, and which are preferably water-soluble, and / or

anionically modified (meth) acrylamide (co) polymers which are present without and / or with at least one further functional group which has been introduced via the copolymerization, and / or which have at least one further functional group and / or with at least one olefinically unsaturated double bond which has a polymer-analogous Implementation / modification of the preferred (meth) Arcylamidgruppe coupled, are present, and which are preferably water-soluble, and / or

 Sulfonic acid (co) polymers, such as styrenesulfonic acid (co) polymers and / or vinyl sulfonic acid (co) polymers in acid and / or salt form, which react with at least one further reactive functional group for coupling reactions, the have been introduced via the copolymerization, and / or which are coupled with at least one further reactive functional group for coupling reactions and / or at least one olefinically unsaturated double bond for radical coupling reactions which are coupled via a polymer-analogous conversion / modification to sulfonic acid groups, for example via sulfonic acid amide groups, are present, and which are preferably water-soluble, and / or

 (Co) polymers having phosphonic acid and / or phosphonate groups which are present, for example, bound as aminomethylphosphonic acid and / or aminomethylphosphonate and / or amidomethylphosphonic acid and / or amidomethylphosphonate and / or which have at least one further reactive functional group for coupling reactions which exceed the Copolymerization is present, and / or, which are present with at least one further reactive functional group for coupling reactions and / or with at least one olefinically unsaturated double bond for radical coupling reactions, which are coupled via a polymer analogous reaction / modification to the (co) polymer, and which are preferably water-soluble.

The selection of the agents and the implementation of further processing to the composite materials of the invention, with the hydrolysis-stable and alkali-resistant cationic polyelectrolytes or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or with the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges modified glass fiber surfaces, as polyelectrolyte complex A are chemically coupled via ionic bonds to the glass fiber surface, and / or, with hydrolysis-stable and alkali-resistant anionic polyelectrolytes or hydrolysis-stable and alkali-resistant anionic polyelectrolyte mixtures and / or with the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of anionic charges as further polyelectrolyte complex modified glass fiber surfaces carried out according to the familiar for the skilled chemical knowledge and is explained in more detail in the examples of a few concrete embodiments.

The use of cationic polyelectrolytes or cationic polyelectrolyte mixtures modified prior art prior to application in the glass fiber manufacturing process and having no silane groups and modified with specific functional groups for reaction and / or compatibilization with a matrix material or at least one component of the matrix material / equipped and / or equipped with functions such as for improving slip properties by amidation with fatty acids, has proved to be less effective in terms of attachment and optimal occupation density on the glass fiber surface and the reinforcing effect, since the direct attachment and interaction with the Glass fiber surface, usually superimposed by steric effects, is impaired.

The subsequent chemical modification of the, with the hydrolysis-stable and alkali-resistant cationic polyelectrolytes or hydrolysis-stable and alkali-resistant cationic Polyelektrolytgemischen and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges modified glass fiber surface and the further sheathing / occupation with other (co) polymers is based estimated on experimental investigations as the optimal variant.

In the production of reinforcing materials with a thermosetting sheath / protective layer for the textile-concrete use, the dry, modified glass fibers are reactively reacted as hydrolysis-stable and alkali-resistant polyelectrolyte complex A with amino and / or ammonium groups on the surface in the first stage directly in the pultrusion process. As duromer (co) polymers, for example: - Epoxy resins or

 - Polyurethane materials (PUR / Polyurethane) or

 UP resins, vinyl ester resins or SMC resin mixtures, wherein the UP, vinyl ester or SMC resin mixture comprises a reactive component having at least one reactive functional group for coupling with amino groups on the polyelectrolyte complex A modified glass fiber surface and having at least one olefinically unsaturated double bond for reaction with the unsaturated matrix component (s) (such as glycidyl methacrylate (GMA) and / or (meth) acrylic anhydride and / or (meth) acryloyl chloride and / or allyl glycidyl ether and / or tetrahydrophthalic anhydride and / or maleic anhydride and / or Itaconic anhydride) was added.

In the case of the surface modification of the glass fibers with polyelectrolytes with quaternary ammonium groups, which are not capable of chemically reactive, ie covalent coupling, as in the case of polydimethyldiallylammonium chloride (PolyDAMDAC), in a second process step for (re) activation of this polyelectrolyte complex A is a specially modified anionic polyelectrolyte or a specially modified anionic polyelectrolyte mixture attached to the polyelectrolyte surface with quaternary ammonium groups and formed a further polyelectrolyte complex. The anionic polyelectrolyte or the anionic polyelectrolyte mixture, which may also be modified with special functional groups and / or olefinically unsaturated double bonds for reaction and / or compatibilization with matrix materials and / or optionally with functions such as for improving the sliding properties, are commercially available, for example as (meth) acrylic acid copolymer derivatives and / or (modified) maleic acid (anhydride) copolymer derivatives and / or (modified) itaconic acid (anhydride) (co) polymer derivatives and / or (modified) fumaric acid Copolymer derivatives and / or styrenesulfonic acid (co) polymer derivatives and / or anionically-treated acrylamide (co) polymer derivatives are widely available. The skilled person can fall back in this case on a variety of commercial products, which are not listed here in detail. The essence of this invention is that the glass fiber surface without using sizing and / or silane in the first step with a mono (macro) possible molecular layer of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex is provided with an excess of cationic charges with a layer thickness in the nanometer range, and after the (polyelectrolyte) complex formation on the glass fiber surface a hydrolysis-stable and alkali-resistant polyelectrolyte complex A prepared and coupled by ionic bonds to the glass surface is present, wherein at least one further (Co) polymer is the Polyelektrolytkomplex A at least partially covered and coupled to the polyelectrolyte complex A via ionic and / or preferably covalent bonds.

Surprisingly, it has also been found that the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures formed on the glass fiber surface form a very stable polyelectrolyte complex A and the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures are no longer conventional Dissolution and / or extraction process can be separated from the glass surface.

A partial to almost complete removal of the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges from the glass fiber surface would be conceivable and possible only with a strong anionic polyelectrolyte in that, in an equilibrium reaction in an aqueous medium, the cationic agents from the glass surface, as it were, by the formation of a separate polyelectrolyte complex in the solution, combine with this strong anionic polyelectrolyte and thus "rearrange". Analogously, partially or completely, a weak cationic compound deposited on the glass surface can be exchanged for stronger cationic agents with, for example, quaternary ammonium groups, if an excess of strong cationic polyelectrolyte or cationic polyelectrolyte mixture is used in the exchange reaction.

In the context of the present invention, polyelectrolytes are understood to mean water-soluble compounds of large chain length (polymers) which carry anionic (polyacids) or cationic (polybases), dissociable groups (Wikipedia, keyword polyelectrolytes).

Adsorption of such polyelectrolytes on the glass fiber surface occurs by adsorbing dissolved cationic agents onto the oppositely charged anionic glass fiber surface. The adsorption is driven, inter alia, by the electrostatic attraction between the charged monomer units of the polyelectrolytes and oppositely charged dissociated surface groups on the glass fiber surface, for example SiO groups on silica surfaces. But the release of counterions or the formation of hydrogen bonds allow adsorption. The conformation of the polyelectrolyte in the dissolved state determines the adsorbed amount of substance. Elongated polyelectrolyte molecules adsorb as thin films (0.2 to 1 nm) on the surface, whereas nucleated polyelectrolyte molecules form thicker layers (1 to 8 nm) (Wikipedia, keyword polyelectrolytes).

In contrast to the prior art, in the first stage prior to the further modification of the glass fiber roving, a stable cohesively bonded surface modification of the glass fibers is achieved with a preferably complete coverage of the glass fiber surface, and stable compounds dissolved in water are used which do not age during application Furthermore, it is not necessary to use sizing mixtures or sizing dispersions, and it is not absolutely necessary to use silanes for coupling to the glass fiber surface, which change chemically over time in water. With the invention, in contrast to the prior art, non-alkali-resistant glass fibers, such as the cheaper E glass fibers can be used after the surface modification of the invention and the cohesive coating as a reinforcing material for textile concrete.

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

The production and modification of glass fibers especially as roving (glass fiber bundles) to reinforcing materials for use in textile concrete is carried out in the examples on an E-glass spinning plant on a pilot plant scale for spinning and online surface modification of glass fibers. The plant has finishing stations, which can be used downstream of the multi-stage order immediately after the spinning process, and a Direktrovingwickler.

After cleaning the sizing station, the sump is filled with an aqueous solution of various hydrolysis-stable, preferably unmodified and alkali-resistant cationic polyelectrolytes and / or of various hydrolysis-stable, preferably unmodified and alkali-resistant cationic polyelectrolyte mixtures. Depending on the take-off speed, filament yarns of 50 to 200 tex can be spun with the machine.

example 1

In the glass fiber spinning system, E glass fibers are spun at 100 tex and surface-modified in the "finishing station" which is filled with an aqueous 1.0% PEI solution as cationic polyelectrolyte (PEI = polyethyleneimine, Aldrich, M _n = 10,000) , wound up and dried (Glasrovingmaterial-1).

The pH-dependent zeta potential measurements on the glass fibers treated in this way demonstrate the adsorption of PEI on the surface. With the fluorescamine method, the detection of coupled amino groups on the surfaces and the uniform coverage of the glass fibers was performed.

Example 1 a: Surface sealing with epoxy

The dried surface-modified glass roving material-1 is drawn through an impregnating bath with thermosetting epoxy so as to be impregnated with the epoxy resin for surface treatment, the excess adhering epoxy is separated by passing over rubber rollers, and thereafter after forming, this epoxy-treated glass fiber roving material is passed through a heating section , in which the material is partially cross-processed into a cohesive, compact prepreg strand and wound up after a cooling section (prepreg strand material-1).

 A cohesively, with a thicker epoxy resin layer surface-modified prepreg strand material-1 is further processed in this form as a reinforcing material for textile concrete as follows:

 The prepreg strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and cross-laid in a heated press on a 2 mm thick HNBR plate, on which a 0.125 mm PTFE peel-off film as a release layer is placed placed at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this prepreg reinforcement material is cured for 1 hour at 165 ° C., the partially crosslinked epoxy resin of these strands forms a stable handling compound at the points of intersection during the consolidation process. After cooling, a lattice network is ready as a reinforcing material for use in textile concrete.

Example 1 b: Surface coating with thermoplastic polyurethane

The modified glass fiber roving epoxy resin seal prepreg strand 1 produced in Example 1a is passed through a die in a second stage and coated / wrapped with a melt of thermoplastic polyurethane (TPU). During the coating, in addition to the thermal Curing of the partially cured epoxy resin in the interface between epoxy resin and TPU coupling reactions instead. Under formation of covalent bonds is the

TPU with the epoxy resin chemically coupled as cohesive composite before. After a cooling section, the TPU strand material-1 is wound up.

 This TPU strand material-1 is further processed as reinforcing material for textile concrete as follows:

 The TPU strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and cross-laid in a heat press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been laid as a release layer placed at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 30 minutes at 190 ° C, the strands form a stable for handling at the crossing points by melting the TPU for handling. After cooling, this lattice network is used as reinforcing material in textile concrete.

Example 1c: Surface coating with maleic anhydride-grafted polypropylene

The prepreg strand material-1 prepared in Example 1a is passed through a nozzle in a second stage and coated / enveloped with a melt of maleic anhydride-grafted polypropylene (PP-gMAn). During the coating, in addition to the thermal curing of the partially cured epoxy resin in the interface between epoxy resin and PP-gMAn coupling reactions take place. Forming covalent bonds, the PP-gMAn is present with the epoxy resin as a cohesive, chemical composite. After a cooling section, the PP-gMAn strand material-1 is wound up.

This PP-gMAn strand material-1 is further processed as reinforcing material for textile concrete as follows:

The PP-gMAn strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been applied as a release layer. placed crosswise at intervals of about 4 cm. Then one will second 0.125 mm PTFE peel sheet also positioned as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 30 minutes at 160 ° C, the strands form at the crossing points by fusing the PP gMAn a sufficiently stable for handling compound. After cooling, this lattice network is used as reinforcing material in textile concrete.

Example 1 d: Surface sealing with UP resin and coating with PP-gMAn

The dried surface-modified glass roving material-1 is pulled through an impregnating bath of UP resin to which 5 mass% of glycidyl methacrylate (GMA) has been added, so as to be impregnated with the UP resin for surface treatment. The excess UP resin is separated by passing over rubber rollers and subsequently, after shaping, this UP resin-treated glass fiber roving material is passed through a heating section in which the material is crosslinked into a cohesive, compact strand and wound up after a cooling section.

 In a second process step, the strand is passed through a die in which the strand is coated / wrapped with a melt of maleic anhydride-grafted polypropylene (PP-gMAn). During coating, coupling reactions take place in the interface between the GMA-modified UP resin and the PP-gMAn. Forming covalent bonds, the PP-gMAn with the UP resin surface is a cohesive, chemical composite. After a cooling section, the UP-PP-gMAn strand material-1 is wound up.

This UP-PP gMAnStrangmaterial-1 is further processed in this form as reinforcing material for textile concrete as follows:

The UP-PP-gMAn strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm thick PTFE peel-off film as a release layer was placed, arranged crosswise at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 20 minutes at 160 ° C, wherein the strands at the crossing points by fusing the PP gMAn one for the Handling sufficiently stable composite form. After cooling, this lattice network is used as reinforcing material in textile concrete.

Example 1 e: Surface sealing with PP-gMAn

The dried, surface-modified glass roving material-1 is extrusion-coated and enveloped by pultrusion directly with a low-viscosity, maleic anhydride-grafted polypropylene (PP-gMAn) and made into a narrow tape. During infiltration and coating, coupling reactions take place in the interface between the glass fibers of glass roving material-1 and the PP-gMAn. Forming covalent bonds, the PP-gMAn is present over the polyelectrolyte complex A with the glass fibers as a cohesive, chemical bond. After cooling, the material is wound up as a narrow PP-gMAn tape material-1.

 This PP-gMAn tape material-1 is further processed in this form as a reinforcing material for textile concrete as follows:

 The PP-gMAn tape material-1 is cut into strands of 0.5 m for a demonstrator test and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been applied as a release layer. placed crosswise at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 15 minutes at 160 ° C, the tapes at the crossing points by melting the PP-gMAn form a sufficiently stable for handling handling. After cooling, this lattice network is used as reinforcing material in textile concrete.

Example 1f: Surface sealing with PP-gMAn and coating with PP

The dried, surface-modified glass roving material-1 is coated by pultrusion directly with a low-viscosity, maleic anhydride grafted polypropylene (PP-gMAn) by infiltration and enveloping (as in Example 1 e). During infiltration and coating, coupling reactions take place in the interface between the glass fibers of glass roving material-1 and the PP-gMAn. Under Formation of covalent bonds is the PP-gMAn on the polyelectrolyte complex A with the glass fibers as cohesive, chemical composite before. In a second coating plant, this strand is then passed through a nozzle and coated with a viscous PP material, wherein the two polypropylenes merge in the interface. After a cooling section, the PP-gMAn-PP strand material-1 is wound up.

 This PP-gMAn-PPStrangmaterial-1 is further processed in this form as reinforcing material for textile concrete as follows:

 The PP-gMAn-PP strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm thick PTFE peel-off film as a release layer was placed, arranged crosswise at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 30 minutes at 170 ° C, wherein the strands form at the crossing points by fusing the PP material of the outer layer sufficiently stable for handling. After cooling, this lattice network is used as reinforcing material in textile concrete.

Example 2:

In the glass fiber spinning line E-glass fibers are spun at 100 tex and in the "finishing station" which is filled with an aqueous 0.25% polyDADMAC solution as cationic polyelectrolyte (PolyDADMAC = polydiallyldimethylammonium chloride, Aldrich, M _w <100,000, very low molecular weight) is, surface-modified, wound up and dried.

 The pH-dependent zeta potential measurements on the glass fibers treated in this way demonstrate the adsorption of polyDADMAC on the surface.

Since the polyDADMAC as a strong cationic polyelectrolyte possesses only quaternary ammonium groups and otherwise no further olefinically unsaturated double bonds and / or reactive functional groups which are relevant for chemical radical, addition and substitution reactions, direct reactions are not possible. In this case, for further modification, the PolyDADMAC surface-modified glass fiber is treated with an anionic polyelectrolyte having a further functional group other than the anionic group for chemical coupling and / or compatibilization with the matrix material or at least one component of the matrix material, and a polyelectrolyte complex "glass fiber surface / PolyDADMAC / anionic polyelectrolyte "

Modification variant via the Polyelektrolytkomplexbildung is preferably used for polyDADMAC surface-modified glass fibers.

In a second step, therefore, the polyDADMAC surface-modified glass fiber roving in a technically analogous apparatus such as the sizing station by rewinding by means of a roller with a 0.5% old propen-maleic acid-N, N-dimethylamino-n-propyl-monoamide Solution (prepared from alt-propene-maleic anhydride by reaction with N, N-dimethylamino-n-propylamine in the ratio of anhydride to primary amino group of 1 to 0.4 in water) to form the polyelectrolyte complex "glass fiber surface / PolyDADMAC / an ionic polyelectrolyte" treated , wound up and dried (Glasrovingmaterial-2).

Example 2a: Surface sealing with epoxy and coating with PA12

The dried, surface-modified glass roving material-2 is drawn through an impregnating bath of thermosetting epoxy so impregnated with the epoxy resin for surface treatment, the excess adhering epoxy is separated by passing over rubber rollers, and thereafter, after molding, this epoxy-treated glass fiber roving material is passed through a heating section , in which the material is partially cross-processed into a cohesive prepreg strand and wound up after a cooling section (prepreg strand material-2).

This prepreg strand material-2 is passed through a nozzle in a second stage and coated / encased with a melt of PA12. During the coating, in addition to the thermal curing of the partially cured epoxy resin in the interface between epoxy resin and PA12 coupling reactions take place. Forming covalent bonds, the PA12 is chemically coupled to the epoxy resin as a cohesive bond. After a cooling section, the PA12 strand material 2 is wound up. This PA12 strand material 2 is further processed as reinforcing material for textile concrete as follows:

 The PA12 strand material-2 is cut into strands of 0.5 m for a demonstrator experiment and placed crosswise in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been laid as a release layer placed at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 30 minutes at 190 ° C, the strands form at the crossing points by fusing the PA12 a stable for handling compound. After cooling, this lattice network is used as reinforcing material in textile concrete.

Example 2b: Surface sealing with UP resin

The dried surface-modified glass roving material-2 is pulled through an impregnating bath with UP resin to which 5% by mass of glycidyl methacrylate has been added, so as to be impregnated with the UP resin for surface treatment. The excessively adhering UP resin is separated by scrapers. After shaping, this UP resin-treated glass fiber roving material is passed through a heating section in which the material is partially cross-linked to form a cohesive, compact strand and wound up after a cooling section (prepreg strand material-3).

 This prepreg strand material-3 is further processed as reinforcing material for textile concrete as follows:

The prepreg strand material-3 is cut into strands of 0.5 m for a demonstrator experiment and cross-laid in a heat press on a 2 mm thick HNBR plate, over which a 0.125 mm PTFE peel-off film has been laid as a release layer placed at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 20 minutes at 180 ° C, with the partially crosslinked UP resin of these strands at the crossing points during the consolidation process forms a stable for handling composite. After cooling, a lattice network is available as reinforcing material for use in textile concrete.

Example 2c: Surface coating with ABS

The prepreg strand material-3 is passed through a nozzle in a second process step and coated with an ABS melt. During coating, coupling reactions take place in the interface between the partially crosslinked UP resin and the ABS, and the UP resin continues to harden. Forming covalent bonds, the ABS with the UP resin surface is a cohesive, chemical composite. After a cooling section, the ABS-UP resin strand material-2 is wound up.

 This ABS-UP resin strand material-2 is further processed as a reinforcing material for textile concrete as follows:

 The ABS-UP resin strand material-2 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate, onto which a 0.125 mm PTFE peel-off film as release layer was placed, arranged crosswise at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 15 minutes at 200 ° C, whereby the UP resin of these strands hardens and the strands form a stable for handling by fusing the ABS at the crossing points. After cooling, a lattice network is available as reinforcing material for use in textile concrete.

Example 3:

Analogous to Example 1, E glass fibers are spun at 150 tex in the glass fiber spinning plant and in the "sizing station", which is treated with an aqueous 1.0% PEI / polyallylamine solution as cationic polyelectrolyte (PEI = polyethyleneimine, Aldrich, M _n = 10,000, polyallylamine, Aldrich, M _w ~ 15,000, PEI / polyallylamine = 2/1), surface-modified and wound up (glass roving material-3). The pH-dependent zeta potential measurements on the glass fibers treated in this way demonstrate the adsorption of PEI / polyallylamine on the surface.

With the fluorescamine method, the detection of coupled amino groups on the surfaces and the uniform coverage of the glass fibers was performed.

Example 3a: Sealing with epoxy and coating with PA6

The dried, surface-modified glass roving material-3 is pulled through an impregnating bath with thermosetting epoxy and so impregnated with the epoxy resin for surface treatment. The excessively adhering epoxy is separated by passing over rubber rollers and subsequently, after shaping, this epoxy-treated glass fiber roving material is passed through a heating section in which the material is partially cross-linked to a cohesive, compact prepreg strand and wound up after a cooling-down path (prepreg). strand material-3).

 This prepreg strand material-3 is passed through a nozzle in a second stage and coated / encased with a melt of PA6. During the coating, in addition to the thermal curing of the partially cured epoxy resin in the interface between epoxy resin and PA6 coupling reactions take place. Forming covalent bonds, the PA6 is chemically coupled with the epoxy resin as a cohesive bond. After a cooling section, the PA6 strand material-3 is wound up.

 This PA6 strand material 3 is further processed as reinforcing material for textile concrete as follows:

The PA6 strand material-3 is cut into 0.5 meter strands for a demonstrator experiment and cross-stacked in a heated press on a 2 mm thick HNBR plate, over which a 0.125 mm PTFE peel-off film is placed as a release layer placed at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. This reinforcing material is pressed under moderate pressure for 10 minutes at 230 ° C., the strands forming a stable bond at the points of intersection by fusion of the PA6. After cooling, this lattice network is used as reinforcing material in textile concrete. Example 3b: Epoxy sealing and coating with PE-coAAc ionomer

The dried, surface-modified glass roving material-3 is processed into a prepreg strand material-3 (as in Example 3a).

 This prepreg strand material-3 is passed through a die in a second stage and coated / encased with a melt of PE-coAAc ionomer (polyethylene-co-acrylic acid ionomer, Surlyn, DuPont). During the coating, in addition to the thermal curing of the partially cured epoxy resin, coupling reactions take place in the interface between the epoxy resin and the PE-coAAc ionomer. Forming covalent bonds, the PE-coAAc ionomer is chemically coupled with the epoxy resin as a cohesive bond. After a cooling section, the PE-coAAc strand material-3 is wound up.

 This PE-coAAc strand material-3 is further processed as reinforcing material for textile concrete as follows:

 The PE-coAAc-strand material-3 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been applied as a release layer. placed crosswise at intervals of about 4 cm. A second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. This reinforcing material is pressed under moderate pressure for 15 minutes at 120 ° C., the strands forming a stable bond for handling at the points of intersection by fusion of the PE-coAAc ionomer. After cooling, this lattice network is used as reinforcing material in textile concrete.

Claims

claims

1 . Surface-modified concrete reinforcement glass fibers at least partially coated with at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant polyelectrolyte polyelectrolyte complex and / or with a hydrolysis-stable and alkali-resistant polyelectrolyte complex, and formed via (polyelectrolyte) complexation by ionic bonding to the glass fiber surface of the hydrolysis-stable and alkali-resistant polyelectrolyte complex A, wherein at least one further (co) polymer at least partially covers the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A via ionic and / or covalent bonds.

2. Surface-modified glass fibers according to claim 1, in which a hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present, which by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or

 by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or

 by (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges which have been prepared before application to the glass fiber surface,

originated.

3. Surface-modified glass fibers according to claim 1, in which the hydrolysis-stable and alkali-resistant polyelectrolyte complex A has formed on the glass fiber surface and essentially completely or completely covers the glass fiber surface and / or the further (co) polymer essentially completely or completely covers the polyelectrolyte complex A. ,

1

4. Surface-modified glass fibers according to claim 1, wherein as hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture

 Polyethyleneimine (linear and / or branched) and / or copolymers and / or

Polyallylamine and / or copolymers and / or

 - Polydiallyldimethylammoniumchlorid (PolyDADMAC) and / or copolymers and / or

 - Polyvinylamine and / or copolymers and / or

 - Polyvinylpyridine and / or copolymers and / or

 - Polyamideamine and / or copolymers and / or

 Cationically modified poly (meth) acrylate (s) and / or copolymers and / or

 Cationically modified poly (meth) acrylamide (s) with amino groups and / or copolymers and / or

 Cationically modified maleimide copolymer (s) prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or

 Cationically modified itaconic imide (co) polymer (s) prepared from itaconic acid (anhydride) (co) polymer (s) and N, N-dialkylaminoalkyleneamine (s)

available.

5. Surface-modified glass fibers according to claim 1, wherein as functionalities of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture

 Unmodified primary and / or secondary and / or tertiary amino groups which have no substituents with a further reactive and / or activatable functional group and / or olefinically unsaturated double bond at the amine nitrogen atom, and / or quaternary ammonium groups which have no nitrogen atom Have substituents with a further reactive and / or activatable functional group and / or olefinically unsaturated double bond, and / or

2 Amino groups and / or quaternary ammonium groups which are at least partially chemically modified on the nitrogen atom by alkylation reactions with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond,

and or

 Amino groups and / or quaternary ammonium groups and amide groups which are chemically modified by acylation reactions of amino groups for the amide with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond,

available.

6. Surface-modified glass fibers according to claim 1, wherein at least one anionic polyelectrolyte or an anionic polyelectrolyte mixture without and / or with at least one other, of the anionic, as functionalities on the attached to the glass fiber surface hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte Group of different reactive and / or activatable functional group and / or present with at least one olefinically unsaturated double bond.

7. Surface-modified glass fibers according to claim 6, wherein as anionic polyelectrolyte or anionic polyelectrolyte mixture

 (a) (meth) acrylic acid copolymers which are present without and / or with at least one further reactive and / or activatable functional group which has been introduced via the copolymerization, and / or which are at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of the (meth) acrylic acid group, are present, and which are preferably water-soluble, and / or

 (b) modified maleic acid (anhydride) copolymers which are preferably present in the acid and / or monoester and / or monoamide and / or water-soluble imide form and / or which are present without and / or with residual anhydride groups and / or which have no and / or at least one further reactive and / or activatable functional group introduced via the copolymerization,

3 and / or which are present with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of maleic acid (anhydride) groups, and which are preferably water-soluble are, and / or

 (c) modified itaconic acid (anhydride) (co) polymers which are preferably in the acid and / or monoester and / or monoamide and / or water soluble imide form and / or those which have no and / or residual Anhydride groups are present and / or which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of itaconic acid (anhydride) groups, are present, and which are preferably water-soluble, and / or

 (d) modified fumaric acid copolymers which are preferably present in the acid and / or monoester and / or monoamide form and / or those which have no and / or at least one further reactive and / or activatable functional group which exceeds the Copolymerization is present, and / or, which are present with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of fumaric acid groups, and which are preferably water-soluble, and or

 (e) anionically modified (meth) acrylamide (co) polymers which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization and / or which have at least one another reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of the (meth) -acrylamide group, are present, and which are preferably water-soluble, and / or

 (f) sulfonic acid (co) polymers, such as styrenesulfonic acid (co) polymers and / or vinylsulfonic acid (co) polymers in acid and / or salt form, which can be reacted with at least one further reactive and / or activatable polymer functional group introduced via the copolymerization, and / or containing at least

4 a further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of sulfonic acid groups such as sulfonic amide groups, and which are preferably water-soluble, and / or

 (g) (co) polymers having phosphonic acid and / or phosphonate groups which are present, for example, bound as aminomethylphosphonic acid and / or aminomethylphosphonate and / or amidomethylphosphonic acid and / or amidomethylphosphonate and / or which are at least one further reactive and / or or activatable functional group which has been introduced via the copolymerization, and / or which are present with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which via a polymer-analogous reaction / modification (Co) Polymer are present, and which are preferably water-soluble,

available.

8. Surface-modified glass fibers according to claim 1, in which the hydrolysis-stable and alkali-resistant cationic polyelectrolytes or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture have a molecular weight below 50,000 daltons, preferably in the range between 400 and 10,000 daltons.

9. Surface-modified glass fibers according to claim 1, in which as further (co) polymer at least one, at least difunctional and / or difunctionalized, oligomeric and / or macromolecular (co) polymer having functional groups and / or olefinic unsaturated double bonds are present.

10. Surface-modified glass fibers according to claim 9, in which as a further (co) polymer thermoplastics and / or duromers and / or elastomers are present.

1 1. Surface-modified glass fibers according to claim 9, wherein as thermosetting (co) polymers polyester resins (UP resins), vinyl ester resins and

5 Epoxy resins, and as thermoplastic (co) polymers polyurethane, polyamide and polyolefins such as polyethylene or polypropylene, and PVC be present, wherein the polyolefins are present grafted with (meth) acrylic acid derivatives and / or maleic anhydride.

12. Reinforcing materials for textile concrete with surface-modified glass fibers in which a hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present on plain and silane-free glass fiber surfaces having at least partially covering functional groups and / or olefinically unsaturated double bonds, and after reaction with functional groups and / or olefinically unsaturated Double bonds via chemical covalent bonds coupled with other (co) polymers present.

13. reinforcing materials for textile concrete with surface-modified glass fibers according to claim 12, wherein as further (co) polymers at least one, at least difunctional and / or difunctionalized, oligomeric and / or macromolecular (co) polymer having functional groups and / or olefinic unsaturated double bonds is available.

14. reinforcing materials for textile concrete with surface-modified glass fibers according to claim 12, in which (thermoplastics) and / or thermosets and / or elastomers are present as (co) polymer.

15. reinforcing materials for textile concrete with surface-modified glass fibers according to claim 12, wherein as functionalities of the adsorbed, coupled via ionic bonds hydrolysis-stable cationic polyelectrolyte amino groups, preferably primary and / or secondary amino groups, and / or quaternary ammonium groups.

16. A process for the production of surface-modified glass fibers, wherein during or after the production of glass fibers on the glass fiber surfaces from an aqueous solution with a concentration of at most 5 wt .-%, a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and or

6 a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, at least partially covering, wherein hydrolysis and alkali-resistant cationic polyelectrolytes and / or hydrolysis and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges are used, and subsequently at least one further (co) polymer is applied to the resulting on the glass surface hydrolysis-stable and alkali-resistant polyelectrolyte complex A at least partially covering.

17. The method according to claim 16, are used as the hydrolysis-stable and alkali-resistant cationic polyelectrolytes polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation, or used as hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures Polyelektrolytgemische according to the Preparation are not subsequently alkylated and / or acylated and / or sulfamidated, are used.

18. The method of claim 16, wherein as hydrolysis-stable and alkali-resistant unmodified cationic polyelectrolyte

 Polyethyleneimine (linear and / or branched) and / or copolymers and / or

Polyallylamine and / or copolymers and / or

 - Polydiallyldimethylammoniumchlorid (PolyDADMAC) and / or copolymers and / or

 - Polyvinylamine and / or copolymers and / or

 - Polyvinylpyridine and / or copolymers and / or

 - Polyamideamine and / or copolymers and / or

 Cationically modified poly (meth) acrylate (s) and / or copolymers and / or

 Cationically modified poly (meth) acrylamide (s) with amino groups and / or copolymers and / or

 Cationically modified maleimide copolymer (s) prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylamino

7 alkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or

 Cationically modified itaconic imide (co) polymer (s) prepared from itaconic acid (anhydride) (co) polymer (s) and N, N-dialkylaminoalkyleneamine (s)

as a pure substance (s) or in a mixture, preferably dissolved in water, are used.

19. Method according to claim 16, wherein the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in a concentration of not more than 5% by weight in water or in water with the addition of acid, such as carboxylic acid, for example formic acid and / or acetic acid and / or mineral acid, without further sizing or sizing ingredients and / or silanes are used.

20. Process according to claim 16, wherein the hydrolysis-stable and alkali-resistant cationic polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures which are not subsequently alkylated after preparation and / or or acylated and / or sulfamidated, are used in a concentration <2 wt .-% and particularly preferably <0.8 wt .-%.

21. Process according to Claim 16, in which hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons, preferably in the range between 400 and 10,000 daltons, are used.

22. Method according to claim 16, wherein a modified hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture which are partially alkylated and / or acylated and / or carbonated after production in a subsequent reaction.

8th Derivatives are reacted and / or sulfamidated and so equipped with a substituent with reactive and / or activatable groups for a coupling reaction, subsequently with the reactive and / or activatable groups of the covalently coupled substituent without crosslinking of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is reactively reacted via at least one functional group and / or via at least one olefinically unsaturated double bond with other materials to form a composite material.

23. The method of claim 16, wherein the partial alkylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture with introduction of substituents having reactive groups by haloalkyl derivatives and / or (epi-) halohydrin and / or epoxy Compounds and / or compounds are realized, which undergo a Michael-analogous addition, such as advantageously acrylates and / or acrylonitrile with amines.

24. The method of claim 16, wherein the partial acylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture with introduction of substituents with reactive groups by carboxylic acids and / or carboxylic acid halides and / or carboxylic anhydrides and / or carboxylic acid esters and / or diketenes , or a quasi-acylation by isocyanates and / or urethanes and / or carbodiimides and / or uretdiones and / or allophanates and / or biurets and / or carbonates is realized.

25. The method according to claim 16, wherein the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complexes are used with an excess of cationic charges in water, preferably as ammonium compound, dissolved, being in the case of primary and / or secondary and / or tertiary

9 Amino groups to the aqueous solution of carboxylic acid (s) and / or mineral acid (s) are added to convert the amino groups in the ammonium form.

26. The method of claim 16, wherein the modified glass fiber surfaces comprising at least partially, and preferably completely, at least one of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges are reactively reacted immediately after their preparation and coating / surface modification and / or later with other materials to form chemically covalent bonds.

The method of claim 26, wherein the modified glass fiber surfaces are wound and / or temporarily stored as rovings, and subsequently reactively reacted with other materials to form chemically covalent bonds.

28. The method according to claim 26 or 27, wherein the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges reactive groups in the form of functional groups and / or olefinically unsaturated double bonds, which are reactively reacted with functionalities of the other materials to form chemically covalent bonds.

29. The method of claim 16, wherein on commercially produced and sized glass fiber surfaces or plain and silane-free glass surfaces, an aqueous solution having a concentration of at most 5 wt .-% of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic Polyelektrolytgemisch and / or from a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic

10 At least partially covering charges, using cationic polyelectrolytes or cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons.

11