CS206888B1 - Surface treatment method of glass and mineral fibres - Google Patents

Description

The invention relates to a surface treatment method. glass and mineral fibers.

For surface treatment of inorganic fibers as well as for further textile processing and application in the plastics industry, electrical engineering and polymers; subtly, a mixture of chemically diverse (organic) compounds, both low and high molecular, is used. The most commonly used substances in this field are various types of starches, glues, fats and oils, polymers based on poly (vinyl): various homopolymers and copolymers of acrylate, epoxy and polyester resins, as well as poly (epoxyalkanes) and their adducts, organosilicon The surface properties and mechanical properties of these fibers can be varied depending on the qualitative and quantitative composition of the treatments, as well as on the manner and conditions of their application and processing conditions.

Fibers with coatings based on the above-mentioned substances exhibit very advantageous electro-insulating properties, but a specific problem in their processing is in the vast majority of cases an increased tendency to form electrostatic charges, the occurrence of which greatly reduces and sometimes makes it impossible! trouble-free textile processing and subsequent final- | application. This is particularly evident in the group of so-called direct lubricants whose bases are different types of polymers and which do not need to be removed before being applied in plastics. Their surface; the electrical resistance is very high (in the range j 10 ¹¹ to 10 ¹³ Ω), which is advantageous from the point of view of application | in insulating systems in electrical engineering, but also due to the simultaneous influence of the usually increased coefficient i of these treatments and the high level j of the surface resistance, this is very rapid; charge of the fibers, usually a considerable charge density. The use of commercially available antistatic agents does not provide a satisfactory solution in the case of glass fiber in the sense that the effective concentrations of the antistatic agents known today are too high to prevent undesirable physicochemical changes in the treatment film.

The subject of the invention is a method of surface treatment of glass and mineral fibers by treating the glass or mineral fiber with a mixture which, in addition to the components known per se, such as film-forming components, lubricants, wetting agents, binders, emulsifying agents, for the treatment of the substances, it contains from 0.01 to 5% by weight, preferably from 0.05 to 2.5% by weight, of a compound of the formula I

R-COO-CH ₂ -CH (OH) -CH ₂ -N (R ₁ R ₂ ) (I) wherein R represents an alkyl or alkenyl radical of 6 to 22 carbon atoms in the main chain, R) is hydrogen, 2-hydroxyethyl , 3-hydroxypropyl, 1-hydroxy-2-propyl, 2-hydroxy-1-propyl, 1-hydroxy-2-butyl, 1-hydroxy-3-butyl, 1-hydroxy-4-butyl, 2-hydroxy-3-butyl, R ₂ represents the same substituents as R 1 except hydrogen.

; The present invention is based on the finding that: Polar substances are adsorbed onto the surface of the glass fiber oriented. Likewise, the compounds capable of forming: intermolecular hydrogen bridges are oriented, since it is known that a number of reactive surfaces exist on the glass surface ^! of polar groups and, after reaching equilibrium in normal climatic conditions, a certain amount of adsorbed water molecules. This causes failure in the application of conventional antistatic agents, which, due to orientation, are placed in a disadvantageous manner after application to the fiber, i.e. usually a hydrophilic segment towards the glass; and on the outside with its hydrophobic segment of the molecule. and

A substance of formula I according to the invention, i.e. ^1, depending on the chemical composition of the other ingredients of the mixtures to be dispensed so that it leads to formation of molecules orientated laminar structure of this substance on the surface of the film of the other components. Depending on the dry matter content, the dosage of the compound of formula I is in the range of 0.01 to 5% by weight, based on dry matter of the other components. The pH at application is optimally in the range 5.5 to 7.0;

An advantage of the invention is furthermore the fact that the compound of the formula I simultaneously has the function of a lubricant, significantly reducing the coefficient of friction and of a surfactant and a surfactant which significantly improves wetting | of the mixture with all commonly used solvents and resins, and promotes perfect homogeneous film distribution.

In the following, the invention is explained in more detail in the examples.

Example 1

An aqueous mixture of the following ingredients was prepared in the weight ratio indicated

Ί.

Compound of formula I 0.02 to 0.3

Deionized water 93,42 to 87,70 '

The mixture is prepared by diluting the epoxy resin dispersion with deionized water so as to make up to 10 wt. parts of the dispersion takes 40 wt. parts of water: and stir with a high speed stirrer for 5 minutes. In a separate vessel, a mixture of a type I lubricating component and an organosilicon wetting agent is prepared. 1a, emulsifies with water at 70 to 80 ° C so that the ratio of lubricant to water is 1: 7; the resulting emulsion is added to the dispersion of the diluted epoxy resin and mixed well. To the mixture was added a 10% aqueous / lubricant solution of type II and a compound of formula I dissolved in ethanol / water (5: 2). After thorough mixing, the organosilicon binder hydrolysates are separately added in water acidified with acetic acid to a pH of 5.5 to 6.0; make up the mixture with deionized water to 100% and rot. and the pH is adjusted with acetic acid; ammonia, to 6.0 to 7.0; lifetime;

The mixtures thus prepared for chemical treatment are prepared ^. the fiber surface is 72 hours. This mixture is used to treat the glass fiber with a rubber or graphite applicator directly in the drawing process. Before further processing. with a wound coil of fiber; allow to stand at 23 to 26 ° C / 40 to 50% relative humidity for 24 hours; the treated fiber can then be processed by conventional textile operations such as twisting, twisting, cording, warping, weaving and weaving. The obtained textile products of various forms can also be used for laminating, varnishing, wire wrapping, resin spraying or chopping and extrusion; with polymers without the need to remove this surface treatment or further refine the chemistry; physical or physical way. The strength of the fibers thus treated varies depending on their; a mean over the range of 0.41-0.80 N / tex compared to 0.35 to 0.60 N / tex for conventional; types of adjustments. The electrostatic charge, measured on a laboratory apparatus under standard instrument and climate conditions, is shown in the table below for efficiency comparison:

Folder Weight parts

The aqueous dispersion of epoxy resin modified with fatty acids (C ₂₀ to C _L0) in 30% aqueous dispersion EPOX. equivalent to 10 thousand, hydroxyl. numbers 90 to 110 mg of KOH 600-800 emulsion lubricating component (type I) based on a mixture of mono- and diesters of fatty acids (C ₂₀ to C _lo) and glycerol and their products oxlranem containing 5-12 ethyleneoxy units 0.25 1.5

Cationic Grease (Type II) based on condensation of higher fatty acids (C _w to C ₂₀ ) with diethylenetriamine or tetraethylenepentaamine 0.1 to 0.8

A wetting agent based on an organosilicon compound and a poly (epoxyalkane) 0.01-0.3

Organosilicon binder based on 3- (2,3-epoxypropoxy) propyltriethoxysilane 0.1 to 0.7

Film binding agent based on silylated polyamide 0.1 to 0.7

Adjustment Intensity elst. field (kV.m- ¹ )% Release rate ‘charge% Textile finish standard. 350 78 Epoxy-polyester silane finish standard. 970 50 Epoxy treatment according to the invention 10 98

Antistatic efficacy; calculated from 100 (1 - g / y), cde E (2) and E (1) are the electrostatic field strength values of the treated and untreated fibers, for the combination of Example 199.5%. The charge velocity can be calculated from the same relation, where E (2) is the elst intensity. field after 5 min. discharge, E (l) elst intensity. field after 'charge'.

Example 2; The composition of the composition and the application according to Example 1, except that instead of the dispersion of the epoxy resin, an adduct of low molecular weight epoxy, dian-type resin and imidazole resulting from the reaction of diethylenetriamine or tetraethylenepentanamine with fatty acids (C10 to C20) vegetable oil dispersed in water; this treatment is particularly suitable for low-titre glass silk and exhibits high tensile strength and gives the fiber a higher degree of flexibility.

EXAMPLE 3 Composition of the mixtures according to Example 2, except that type I lubricant components based on a mixture of monoesters. of fatty acids with glycerol, an emulsion of a hydrogenated vegetable oil stabilized with poly (ethyleneoxy) ether-sucro esters is used. Application as in Example 2.

Example 4

i. The composition of the compositions as in Example 2 except that a blend of fatty acid esters of higher fatty acids with aliphatic alcohols stabilized with ethyleneoxy ethers of monoesters and fatty diglycerides is used instead of the type I lubricating component based on a mixture of monoesters of fatty acids with glycerol. acids (containing ₁₀ to ₂₀ carbon atoms in the aliphatic chain and 5 to 12% ethyleneoxy units). her ; This mixture has a low coefficient of fraction and a very good processability of the treated fiber in the demanding textile supports over the entire width and range of glass silk.

EXAMPLE 5 Composition of the mixture according to Example 4 except that instead of glycidoxypropyltriethoxysilane, 3% is used ^. [-aminopropyl-triethoxy-silane. Such treated; the fiber is suitable for use as reinforcement of polyester resins and lacquers.

Example 6 '

The composition of the composition of Example 4 except that a styrylated cationic silane, ob; containing an amino group in the molecule. Edit it; This type shows high strength and abrasion resistance host over the full range of fiber titers and minimal. electrostatic charge; moreover, it is suitable for all types of resins and lacquers.

Example 7

A mixture of the following components is prepared:

Organosilicon binding agent, type A '

3-Aminopropyltriethoxysilane 0.1 to 0.80

Organosilicon binding agent, type B

3- (triethoxysilyl) propyl methacrylate 0.1 to 0.85

Compound of Formula I 0.015 to 0.35

Acetic acid 0.01 to 0.25

Water deionized_ 95,615 to 80,200

The mixture is prepared by mixing the solutions of the individual components as follows: dilute the poly (vinyl acetate) dispersion with twice the amount of water, gradually to this diluted dispersion; adding 10% solutions of polyoxirane, type II lubricant and binding agents prepared by hydrolyzing the organosilicon preparations in acetic acid-acidified water to pH 4.9-5.5; finally, a 10% ethanol solution of the compound of formula (I) is mixed into the mixture by slow pouring with constant stirring. After stirring for 10 minutes using a low speed stirrer, the mixture is ready for application to the fiber. Application is carried out with graphite rotating rollers at room temperature. Depending on the ratio of the components, the fiber is suitable for co-processing into a roving form, which can be used to wind, chop or weave into roving fabrics. The treatment shows an increased wettability of the resin compared to the treatment without the use of the compound of formula I.

Example 8

The composition of the mixtures according to Example 7, except that a dis-. Linear and low molecular weight epoxy resin blends, stabilized ^; cationic surfactant. Glass silk treated with this blend is suitable for co-processing and for the production of roving fabrics with high wettability by epoxy and polyester resins. ,

Example 9

The composition of Example 7, except that a mixture of poly (vinyl acetate) and epoxy resin dispersions and a higher molecular weight of at least 600 is used in addition to the poly (vinyl acetate) dispersion.

He did

The composition of Example 7 except that a linear polyester resin dispersion formed by polycondensation of 4,4-isopropylidenebisphenol with sebacic acid and maleic acid is used instead of the poly (vinyl acetate) dispersion. Glass silk treated with this mixture exhibits a higher degree of wettability with polyester resins.

Example 11

A coating mixture of the following components is prepared:

Ingredients parts

Poly (vinyl acetate) dispersion, 40% dry matter, softened 10 to 20% dibutyl phthalate 4.0 to 15.0%

Polyoxiran of mol. wt. 300—400 000 0.1 to 1.8

Type II cationic lubricant (see Example 1) 0.06 to 0.85

Ingredients parts

Amyloz fraction of starch 0.5 to 3.0

Oxidized potato starch 0,5 to 2,5

Polyoxiran molek. wt. 300 0.05 to 1.0

Hydrogenated vegetable oil temperature 30 to 40 ° C 0.3 to 1.5

Emulsifying agent based on poly (epoxyalkyl) ethers of sugar esters 0.03 to 0.20

Type II cationic lubricant formed. by condensing tetraethylenepentamine with a higher fatty acid (Cm to C20) of 0.05 to 0.870

Acetic acid 0.01 to 0.20

Compound of Formula I 0.01 to 0.358

Deionized water 98.550 to 90.372 i Both starch components are dispersed in water 1 and boiled at 70 to 120 ° C. The amount of water for the dispersion is chosen such that the resulting starch sebum concentration is 6% by weight. Polyoxide is added to the sebum so formed. wound and 10% cationic lubricant solution! II in water and allowed to stir for 5 minutes. Then; a hydrogenated oil emulsion, stabilized with an emulsifying agent, prepared by mixing! melt of oil and emulsifier and water at a ratio of 10: 1: 100 at a temperature of 70 to 80 ° C, homogenized by passing through a colloid mill and a homogenizer. After the resulting mixture is made up to 4/5 of the resulting volume with water, a 10% solution of the compound of formula I in ethanol-water 5: 4 is added with stirring; the mixture is applied to the fibers at a temperature of 50 to 60 ° C, the fiber is dried for 24 hours at 23 to 26 ° C and 50% relative humidity and processed by conventional textile operations. The adjustment shows:

Claims (1)

SUBJECT A method of surface treatment of glass and mineral fibers, characterized in that the glass or mineral fiber is treated with a mixture which, in addition to the components known per se, such as film-forming; ingredients, lubricants, wetting agents, binders, emulsifying agents, pH adjusting agents, contain from 0.01 to 5% by weight, preferably from 0.05 to 2.5% by weight of the compound of formula I, excellent textile properties and the fiber treated with this mixture is can be processed in various ways into various textile molds. Example 12 The composition of the compositions of Example 11, except that a mixture of paraffin waxes and oils is used instead of hydrogenated vegetable oil. The application is then carried out at room temperature. Example 13 The composition of the blend according to the example is pressed except that a mixture of mono and diesters of fatty acids with glycerol and oxirane (containing 5 to 12 ethoxy units) of poly (epoxyalkanes) vegetable oils is used instead of hydrogenated vegetable oil. By combining the known compositions of the compositions with the compound of formula I as described above in the individual examples, an antistatic effect of 87-100% is achieved, while at the same time the mechanical and textile parameters of the glass silk treated with the compositions are substantially increased. A significant effect is also a favorable shift of the wettability parameter of the fiber surface with polar and non-polar organic solvents and various types of polymers, which has a positive effect on the technology of preparation and mechanical properties of reinforced plastics. OF THE INVENTION R-COO-CH ₂ -CH (OH) -CH ₂ -N (RJR ₂₎ wherein R represents an alkyl or alkenyl radical having 6 to 22 carbon atoms in the main chain, R is hydrogen, 2-hydroxyethyl, 3-hydroxypropyl, 1 hydroxy-2-propyl, 2-hydroxy-propyl-l, l-hydroxy-2-butyl, - l-hydroxy-3-butyl, l-hydroxy-4-butyl, 2-hydroxy-3-butyl, R ₂ represents the same substituents as Rj excluding hydrogen.