DD300535A5 - SUSTAINABLE SURFACE TREATMENT FOR FIBER TREATMENT - Google Patents

Abstract

The invention relates to a surfactant-containing sizing agent for treating fibers and relates to a sizing agent for treating glass fibers or polymer fibers which can be used immediately after the fiber-forming process without additional treatments of the fiber. The agent consists of 0.2-5 * anionic surfactant, 0.5-10 * water-soluble cationic polyelectrolyte and / or polymer having a ratio of anionic surfactant to polyelectrolyte such as * Alkyl carboxylic acids / salts, salts of acidic sulfuric acid esters and / or salts of true C + were used as the anionic surfactant. Sulfonic acids used. In addition to the sizing effect, the chopped glass / polymer fibers show immediate spreading on contact with aqueous medium {surfactants; Plain; Fiber sizing; Polyelectrolyte, cationic; Polymeric, cationic; Asbestos substitution}

Description

Field of application of the invention

The invention relates to an agent for treating glass and polymer pulps in or after the fiber forming process, which advantageously affects the surface properties of the fiber for the further application of the fibers with respect to composite formation in conjunction with a matrix material. The invention is applicable to glass fiber spun yarns, short glass fibers and mineral wool, as well as to organic polymer fibers such as polyacrylonitrile, polyvinyl alcohol.

Characterization of the known prior art

The preparation of the glass fibers is usually carried out with a spin finish or Schmälze, depending on the intended application of the fibers are treated for the different applications Glasseidenspinnfäden with purpose-composed sizing agents for glass fibers. The spin finish contains in principle a binder in aqueous dispersion or emulsion for bundling a plurality of filaments, aids for the production of slip properties for the processability of the threads in the technological process and with regard to the production of glass fiber reinforced plastics suitable adhesives (Loewenstein, KL "The Manufacturing Technology of Continuous Glass Fibers ", Elsevier Scientific Publishing Company, Amsterdam-London-New York, 1973).

Originally, pure surfactants were only used in the production of separable inorganic-non-metallic fibers according to the basically different types of wet-spinning technology, since this technology does not require the use of sizing. Accordingly, DE-2605633 proposes the production of water-dispersed mineral fibers wherein, to avoid adhesion between the fibers and associated lumping, the mineral fibers are slurried in water in the presence of a surface-active compound containing at least one cationic group.

Specifically for the preparation of aqueous glass fiber dispersions, again using the wet spinning process, it is proposed for the production of uniform glass mats by the wet application method according to DE-2847334 to treat the fibers in an aqueous medium with a surface-active tertiary amine oxide.

In contrast to wet-spinning technology, there have already been proposed sizing agents for the treatment of glass fiber spun yarns and a process for producing individualized glass fibers which contain water-soluble film-forming polymers and cationic surface-active compounds or water-soluble film-forming polymers and nonionic surface-active compounds and optionally further typical additives in an aqueous medium. On the other hand, sizing agents in the form of polydimethyldiallylammonium chloride alone or mixtures thereof with alkali silicate solutions have been proposed / claimed as sizing agents for treating glass fiber spun yarns for spontaneous fiber singulation on contact with water and improving the dispersibility of glass fibers in an aqueous medium.

Furthermore, sizing was proposed for glass fiber coatings, which includes the same objective from an aqueous medium, the order of one or more Katior.tenside. Due to the negative charge of the glass surface, it has not hitherto been possible to effectively use commercially available anionic surfactants, which are widely used, as fillers for the production of individualized glass fibers.

Analogous experiences have also been made in the production of fiber reinforced composites using organic polymer fiber fabrics which have a negative surface charge.

Object of the invention

The aim of the invention is the provision of processed fibers with reinforcement-relevant morphology for further use in the production of composite materials.

Explanation of the essence of the invention

The invention has for its object to develop a means for the treatment of glass in fiber form, which allows the production of good dispersible individualized glass fibers for fiber composite material formation, in particular with the concern that when cutting the spun yarns or Glasseidenrowings firmly adhering glass staple fiber bundles of 23mm fiber length arise and on contact with water or an aqueous medium spontaneously pass into the individual fibers. Another object of the invention is to have available in an analogous manner such agents according to the same principle of action also advantageous for the treatment of organic polymer fiber materials.

The use of the often used in practice Aniontunside according to this task proved to be ineffective, obviously be caught by the fact that both the glass or polymer surface and the surface-active group of the anionic surfactant are negatively charged.

Surprisingly, it has been found that aqueous anionic surfactant solutions can be advantageously used if they are suitable for the task according to the invention in combination with water-soluble cationic polyelectrolytes, and / or water-soluble cationic polymers, eg. As polypropylene triamine, are used. In this case, the proportion of cationic polyelectrolytes between 0.5 and 10 parts by mass in%, based on the total solution.

According to the invention, the anionic surfactants are compounds from the homologous series of alkylcarboxylic acids and their salts, the salts of acidic sulfuric acid! and / or the salts of true C-sulfonic acids, compounds of the homologous series of sodium salts of alkylcarboxylic acids and aminocarboxylic acids, the sodium salts of fatty acid sulfates, of sulfates of fatty acid esters and amides, of primary and secondary alkyl sulfates, of sulfates of oxoalcohols, of sulfates substituted polyglycol ethers , sulfates of acylated or alkylated alkanolamines, of primary and secondary alkanesulfonates, of sulfonates of fatty acids, their esters and amides, and of alkylbenzenesulfonates.

The inventive composition contains in aqueous solution, the anionic surfactants in the concentration range of 0.2 parts by mass in% to 5 parts by mass in%, preferably from 0.4 to 1 parts by mass in%.

The ratio of anionic surfactant to polyelectrolyte is generally between about 0.1: 1 to 1: 1, preferably between about 0.2 to 0.5: 1, based on the total solution

Preferably used as anionic surfactants are sodium salts of alkyl-Cg-Cie monocarboxylic acids; Sodium salts of fatty acid sulfates: sodium salts of sulfates of low-chain (C, -C ₄ ) fatty acid esters and amides; Sodium salts of Cg-Cn primary and secondary alkyl sulfates; Sodium salts of sulfates from oxoalcohols; Sodium salts of water-soluble sulfates substituted polyglycol ethers; Sodium salts of sulfates of acylated or alkylated alkanolamines prepared from (di) -ethanolamines and fatty acid chlorides; Sodium salts of Cg-C12 primary and secondary alkanesulfonates; Sodium salts of sulfonate of fatty acids, their esters and amides; and sodium salts of Cg-Cij alkyl benzene sulfonates. Particularly preferred are, for example, alkylbenzenesulfonates and alpha-dodecyl-omega-sulfatofoxyethylene).

As cationic polyelectrolytes according to the invention, in particular those having medium to high degrees of polymerization are used.

Preference is given to polyvinylpyridines whose quaternization products with alkyl halides or alkyl sulfates; Poly-N-vinylimidazoles, their quaternization with dimethyl sulfate, p-toluenesulfonic acid isobutyl ester and / or p-toluenesulfonate, quaternized copolymers of vinylimidazole with diethyl maleate, acrylonitrile, styrene, acrylamide or vinylpyrrolidone.

Particularly preferred examples thereof are polypropylenetriamine, dodecylpolyvinylpyridinium chloride and the quaternary ammonium compound of poly-N-vinylimidazole and isobutyl p-toluenesulfonate.

The aqueous mixture according to the invention is used in the glass fiber spinning process in front of the grain diameter of the plurality of elementary glass fibers on a conventional coating device in a known manner. The coated, dried and cut glass fiber filaments of the glass fiber rovings spontaneously disintegrate upon contact with water or an aqueous or aqueous medium, so that the staple fiber composite is dissolved instantaneously.

As glass silk, those based on customary, suitable glasses can be used, for example based on alkali / alkaline earth aluminoborosilicate glasses and zirconium-containing glasses.

The size according to the invention thus fulfills two functions: it allows the use of the commercially widespread and often inexpensive anionic surfactants as sizing agents, and leads to the immediate spreading of the cut glass or polymer fibers on contact with an aqueous medium, which is suitable for use in cement instead of Asbestos fibers is particularly important.

The invention will be explained in more detail by examples.

embodiment

Example 1

In the process of producing glass silk by the die-drawing method, the molten glass typically passes through a plurality of noble metal dies to form the endless filaments which are excessively coated with a sizing agent prior to collecting the filaments to the filament by means of the coating means. The size which gives the glass oxide and in particular its die cut form the properties according to the invention can be obtained by simply mixing the size constituents according to the invention as an aqueous solution.

Example 1.1

E 30 (alkyl benzene sulphonate, Leuna-Werke Kombinat) 1.0M-%

Dodecylpolyvinylpyridinium chloride 5.0Ma%

Water ad100,0Ma-%

Example 1.2

Sodium dodecyl sulfate 1.5Ma%

quaternary ammonium compound of poly-N-

vinylimidazole and isobutyl p-toluenesulfonate 5.5% by mass

Water ad 100.0%

Example 1.3

Sodium salt of dodecanoic acid 1.5Ma%

Dodecylpolyvinylpyridinium chloride 5.0% by mass

Aminopropyltriethoxysilane 0.5Ma%

Water ad 100.0%

Example 2

Polyacrylonitrile (Dolanit 10, dtex 30 / 6mm) fibers were finished with an agent of the following recipe, also obtained by simple mixing of the components in aqueous solution.

ct-dodecyl-ε-sulfato (oxyethylene) 1.0% by weight

Dodecylpolyvinylpyridinium chloride 8.0 Ma-%

Water ad100,0Ma-%

In all cases there was a good separation effect of the light after the fibers had been wound up, i. h., The fibers were easy to rewind. Upon contact with water, the cut fibers exhibited an immediate release effect so that no fiber agglomeration occurred.

Claims (5)

Surfactant-containing sizing agent for treating fibers of glass or organic polymers, characterized in that the composition contains between 0.2 and 5% by mass of one or more of the anionic surfactants from the homologous series of the alkylcarboxylic acids and their salts, the salts of acidic sulfuric esters and / or or salts of true C 1 -C 4 sulfonic acids and between 0.5 and 10% by weight in% of a water-soluble cationic polymer and / or water-soluble cationic polymer in an aqueous medium. 2. Composition according to claim 1, characterized in that the size of one or more anionic surface-active compounds of the homologous series of sodium salts of alkylcarboxylic acids and aminocarboxylic acids, the sodium salts of fatty acid sulfates, sulfates of fatty acid esters and amides, of primary and secondary alkyl sulfates, of sulfates of oxo alcohols, sulfates of substituted polyglycol ethers, of sulfates of acylated or alkylated alkanolamines, of primary and secondary alkanesulfonates, of sulfonates of fatty acids, their esters and amides and of alkylbenzenesulfonates. 3. Composition according to claim 1, characterized in that it comprises one or more water-soluble cationic polyelectrolytes and / or water-soluble cationic polymers in an aqueous medium selected from the group of polyvinylpyridines whose quaternization with alkyl halides or alkyl sulfates, from the group of poly-N vinylimidazoles whose quaternization products with dimethyl sulfate, isobutyl p-toluenesulfonate and / or p-toluenesulfonic acid methyl ester, and quaternized copolymers of Viny'iimidazols with diethyl maleate, acrylonitrile, styrene, acrylamide or vinylpyrrolidone, from the group of acylated polyethyleneimines. 4. Composition according to claim 1 to 3, characterized in that the ratio of anionic surfactant to polyelectrolyte is between about 0.1 to 1 to 1, preferably between about 0.2 to 0.5 to 1. 5. Composition according to claim 1 to 4, characterized in that the content of anionic surfactant in the range between 0.4 to 1 parts by weight in%.