CS271972B1 - Glass fibre with increased alkali resistance - Google Patents

Abstract

The fibers contain 0.5 to 2% by weight a coating composed of an aqueous composition containing about 2% to about 8% of wooll polymers and / or olefinic monomers, 0.05 to 5% Wernor chromium chloride complex with 3 to 20 carbon atoms; 5% epoxy adducts and alkanol amines adducts and / or polyamines eolubilized in water soluble acids.

Description

The present invention relates to glass fibers with increased alkali alkali resistance.

Virtually all types of natural, synthetic, glass, mineral, metal fibers and their combinations are tested as asbestos substitutes. Most attention is paid to the composition am based on Portland cement and glass fibers with increased alkali resistance, most often with zirconia content (Japanese Pat. No. 49 40 126, U.S. Pat. No. 3,040,379, British Pat. 1,243,973, U.S. Pat. No. 236,653).

A key problem in solving glass-cement compositions is that the glass fibers used are sufficiently resistant to alkalis, because in cement, under the influence of alkalis, especially calcium hydroxide, reactions take place which cause the silicon-oxygen skeleton of glass fibers to break down, resulting in a sharp decrease in their mechanical properties. , mainly tensile strength.

Increasing the resistance of glass fibers is most often solved, especially for economic reasons, by a combination of a suitable glass composition and surface treatment. The improvement of alkali resistance is achieved by means of various inorganic and organic additives. Of the organic additives, the best known is the use of aromatic monocyclic or polycyclic compounds with at least three hydroxyl groups, mainly esters of trihydroxybenzoic acid (Czech Pat. Nos. 178 822, 212 211) acids such as oxalic acid (Swedish Pat. No. 398 495) alkylsulfamidocarboxylic acids ( NSR Pat No. 29 45 119). Of the polymer dispersions, acrylate-based copolymers such as vinyl acetate-alkyl acrylate (MSC, Decree No. 224314) and terpolymers such as styrene-acrylate-acrylic acid (MSc No. 249 961), polyisobutylene aut. osv. USSR no. 906 958), vinyl acetate-ethylene copolymer (Japanese Pat. No. 54 106 626), fluoropolymer (Japanese Pat. No. 55 156 152). The most common inorganic additives are compounds of zirconium (Japanese Pat. No. 55 085 437, 53 143 732), titanium (Japanese Pat. No. 54 156 835), zinc (Japanese Pat. No. 55 020 235, 54 139 650). Among the lesser known additives, water glass, colloidal silica and its spit derivatives are recommended (Japanese Pat. No. 58,060,644, 56,060,643, 54,070,333).

The wide range of compounds used to increase alkali resistance is mainly due to the technology of fiber production, the method of their treatment and, last but not least, the application processing of treated fibers and the technology of glass-cement composition production. In the case of the production of fibers used for the technology of production of glass-cement compositions by chopping and spraying, the fibers must, in addition to being resistant to alkalis, allow their use for the given processing technology.

The use of pyrogallol and trihydroxybenzoic acid derivatives, which also. there are a number of other solutions representing the world's best, It is considerably neglected and demanding on the technology of glass fiber treatment. In the case of the most commonly used technologies, workers come into direct contact with the lubrication. The use of these substances results in a strong, difficult-to-wash skin color in a purple to brown-red shade, which has a negative effect on the use of lubricants of this kind.

The glass fibers according to the invention eliminate these disadvantages and solve the problem. The essence of the invention consists in that the glass fibers contain 0.5 to 2% by weight of a coating composed of dry matter of an aqueous composition which contains 2 to 8% by weight of dry matter of a dispersion of polymers based on vinyl and / or olefinic monomers, 0.05 to 5 % by weight of a Werner chromium chloride complex in which trivalent chromium is coordinated with a monocarboxylic saturated or unsaturated aliphatic acid having 3 to 20 carbon atoms, and 1 to 8% by weight of epoxy resin adducts with an average molecular weight of 300 to 900 with alkanolamines and / or aliphatic polyamines with 2 to 9 carbon atoms and 1 to 5 nitrogen atoms solubilized with water-soluble acids. The textile properties of the fibers and the stability of the composition can be regulated, if necessary, mainly according to the technological equipment used, by adding 0.05 to 5% by weight of at least one additive.

CS 271 972 B1 from the group comprising lubricants, wetting agents, pH regulators such as ammonia or acetic acid, antistatic agents, e.g. lithium chloride or substances of amphipathic character. The dispersions used can be plasticized with customary compounds such as phthalic acid esters, polyesters or oils in an amount of 2 to 50% by weight. Many dispersions are already commercially available in plasticized form.

The coated glass fibers according to the invention can be produced using gray types of glasses with increased alkali resistance, but even in the case of using glasses with poor resistance as E-glass, a significant increase in alkali resistance is achieved, which also allows these fibers to be used in compositions. It has been found that by a suitable choice of glass fiber coating, a number of application properties can be controlled. The increase in alkali resistance allows a synergistic effect of the combination of Werner chromium complexes, which are capable of interacting between the eeb, the ecla and said adducts based on epoxy resins which surround the hydroxyl group in their structure.

The raw materials used to make the fibers of the invention are known and a variety are commercially available. From polymer dispersions! copolymers of vinyl acetate, vinyl chloride, ethylene and acrylic acid esters are of the greatest importance. In their committee, it is necessary to take into account the fact that Werner complexes are acid and ionic saliva, ie. alkaline diapers cannot be used. Of the available Werner chromium complexes, complexes of methacrylic acid and fatty acids, mainly stearic acids, which are available as solutions in organic, water-dilutable solvents, eu oxide resin adducts prepared by their action and alkanolamines such as monoethanolamine, diethanolamine, ethylenedilamine , diethylenetriamine, tetraethylenepentamine followed by STolubilization with water - soluble acids such as acetic, glycolic, hydrochloric and phosphoric.

The invention is further illustrated by the following examples in which the composition is given in a concentration by weight.

Example 1

Inclined fibers e with an average thickness of 13 .mu.m with 200 fibers in strand a and treated with a scientific composition and containing 5% dry matter of vinyl acetate-alkyl ester copolymer diaper dispersion, plaetified with 7% dibutyl phthalate, 1% dry matter methacrylic chloride, 3% epoxy resin adduct with an average molecular weight of 380. solubilized with acetic acid and 1% 3-aminopropyltriethoxysilane. After drying at 125 ° C, the fibers contained 1.4% of the coating. Alkalivzdornoet was evaluated by the SIC (strand-in-cement) method. The essence of the method is the crosslinking of the tensile strength of a lubricated strand of glass fibers, the latter section of which is built into a cement matrix, which is exposed to accelerated etching in water at a temperature of 80 ° C for 96 h. Glass composed of 4.2% by weight of calcium oxide, 5.7% of barium oxide, 2.1% of magnesium oxide, 14% of sodium oxide, 12.9% of zirconia and 61.1% of silica was used for the production. In the same way, aa also evaluated some known solutions by determining the tensile strength according to SIC 96 h, 80 ° C. Untreated fiber low strength 290 MPa, fiber treated according to or. osv. no. 224 314 male strength 340 MPa, fiber modified according to the base, aut. osv. no. 249 961 low strength 395 MPa, fiber modified according to MS. pat. no. 178 822 low strength 430 MPa and fiber according to the example 560 MPa.

Example 2

The glass fibers were treated as in Example 1, except that the compositions contained methacrylochlor chloride 3% chromium complex based on an equimolar mixture of palmitic acid and stearic acid. A mixture consisting of 7.2% by weight of calcium oxide, 7% of barium oxide, 4% of alumina, 10.5% of sodium oxide, 5% of zirconia and 66.3% of silica was used for production. The untreated fiber has an SIC strength of 96 h 80 ° C 175 MPa. Fiber after drying little 1.2% of the coating and strength 360 MPa SIC 96 h 80 ° C.

CS 271 972 Bl

Example 3.

An aqueous composition comprising 7% dry matter of vinyl chloride-acrylate copolymer, 0.5% aethacrylic chloride and 5% opoxide resin adduct with an average molecular weight of 750 and diethanolamine eolubilized with hydrochloric acid was used to treat the fibers and was made using Example 2 · The treated fibers e contain 1.8% of the coating after drying, low strength 430 MPa, SIC 96 h 80 ° C.

Example 4

An aqueous composition was used to treat the ea fibers as in Example 3, except that the vinyl chloride-acrylate copolymer was coated with a wool acetate-vinyl laurate copolymer, 0.3% lithium chloride antistatic agent, and 1% quadonized oxyethylated etearylamine antistatic and wetting agents. Fibers were uekutočnená using ekla to Example 2, The vlékna much Obeah 1.6% of the coating after drying aali ¹ pevnoet SIC 435 bar 96 h 80 ° C.

I

Example 5 *

She used an aqueous composition as in Example 1 to treat ea, except that it circulated the opoxide resin adduct with diotylenetriamine and diethanolamine. Fibers bole ueku- _w of točnoná USING ekla to Example 2. The modified fiber of 1.3% obeahon minor coat strength of 490 MPa SIC 96 hours 80 ° C.

Claims (3)

OBJECT OF THE INVENTION 1. Glass fibers with increased alkali resistance, characterized in that they contain 0.5 to 2% of their glass fiber fibers of a coating composed of an aqueous coaposition, which comprises 2 to 8% of the weight of a polyether-based and / or olefin-based polymer matrix. monoaers, 0.05 to 5% by weight of Werner chromium chloride complex; in which trivalent chromium coordinated with a monocarboxylic or unsaturated aliphatic acid having 3 to 20 carbon atoms, and 1 to 8% by weight of adducts based on epoxy resins having an average molecular weight of 300 to 900 alkanolains and / or aliphatic polyanines of 2 to 9 carbon atoms; and 1 to 5 dueic acid atoms enolubilized with water-soluble acids. 2. Glass fibers according to claim 1, characterized in that the aqueous coaposition contains 0.05 to 5% by weight of at least one additive from a group of lubricants, wetting agents, binders, pH regulators and antistatic agents. 3. Fiberglass fibers according to claim 1 or 2, characterized in that the die dispersions of polyols based on vinyl and / or olefinic ionizers are plaquetized with 2 to 50% by weight of a plasticizer such as euethers, polyethers and oils.