DE2158667A1 - Coating compound for coating glass fibers and their manufacture and use - Google Patents

Description

Dr. Michael Hann

Patent attorney 635 Bad Nauheim

Bunpllte 12 b TeWon (0 60 32) 62 37

26. flbveuber 1971 H / E A (398) 4830

PPG Industries, In., Pittsburgh, Fa., 15222, USA

tnuQtzuoemsei züh coating of fiberglass ^ uism your

HSRSTKLWJJiG TJWD XIBE TTERVElIDUIiG

! Dl · Srfiaduag relates to a koabinierte Sehlieht © - and übersugsaasse door Glasfaaern. Ia particular concern si · «la · itabiliei« rt · wäaerige S «abin & tion & ms« iner 8 «bJ.i« kt «mad« ia «r übernesaass«, di · »xigleicJa. sna Schlich · * · & and in Über # riieh «n or coating tor sux» • laatoMMX «r product · b« etiaat «n Glaef aearn v« rd «a β · 11. ti · also concerns eia Verfakrea Heretellwag of the co-ministerial plain · uad aas ·· «ad s« r TerweaduBe this hatred · at Glaefaeern.

£ ia Ua "fa4er" ylaafad "a ordered on" a 7i * l * e & l feiner Glaafaaera, who aaa "often advises the way that they, as generally described by the US patent law 3 122 23S, ait higher speed roa skittles sv" g @ selia @ lzenea glass that can be seen at the spitson of the small openings in a buonse. Vfikread their Entatehmas ^ are the fibers at high speed ait a Sohliohte About Absorbed · · The simplicity is an aqueous formulation which enthilt usually a Bisdeaittel, daait the thread look leg Verswiraen, Doubliere "wt & weaving can be handled well. Ver ^ the fiberglass threads,

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di · Garm · from or di · au "this produced tissue sur gain to be used by resinous or elastomeric materials, Ban setst represents. Sehlicht · usually ain coupling agent" is alna finish su _t the hydrophobic or Oberfläake of the glass fibers with dam material vertrlglieh with which they are used in the manufacture of reinforced cartridges and elastomeric products.

Venn glass sur gain τοη elastomeric products are used, you know it, you naokdem already with a size, di · contains a coupling agent has coated susitulieh in a further process stage with a coating of a Hebst off door rubber bsw. Contains rubber, hereinafter referred to as chewing glue or rubber glue. The one for this, in Hegel together with a vinylpyridiapolyner or a bucket of termepeljmeren latex, the most rewea & ete rubber adhesive is the & es »rain-? Ormaldehyde-lajrs. In the US Patentsokrift 2,617,616 the use of these rubber adhesives such as rayon, viscose, polyamides or polyesters smr gain τοη Kautsehuk or rubber with natural fabrics, "Is cotton, and samthetisohen Teactilien described.

Since then there has been a desire to use glass fibers that are used for reinforcement. in a single step with an oversug of a combined oil and liquid mass su Terseken. Up until Jetst, however, it was difficult to implement such a process.One of the reasons which has hitherto prevented a combination of a size containing a coupling agent is the general transparency that the coupling agents used in the Kamtsciiukklcbetoife decaltive overMJSma ^ oea, &»&&&. · splclswelse it comes with Xusats elmes g« br & mekli @ li @ m • mino-ftuxktienellen kjdroljrabaren

BAD ORIGINAL 20982 5/0731

the Silaareihe sm bucket Eesoroim-formaldehyde Hars and a Timylpyridimpolymeriiat or buckets terpolymer latex enthaltemden wässrigea coating composition often means that the entire Amsats in the form eiaes lumpy, unusable precipitate aas EER solution "herausgeworfen'wird ^1?. Against this difficulty it has been characterized To help rersuoht that maa the kembimlerten sizing and coating mass has set water to a large extent. However, this was not a satisfactory reading, since aaa a fairly high overspill weight must be expected, which is on dry glass, for example at least about 15 to 20 wt. must be at% and is% increase to about 25 to 30 wt.. in an excessive Terdttmmung the combined sizing and coating composition can be such a high coating weight are not achieved, se that maa the Wet in two or more "Tauohungen""of the coatings must muster.

Ia the US Pateataeaeldmmg 814 731 is a Torriehtmng beaaarüMa, Ia the Liaselclasfasern with buckets oversug aas bucket keabimiertea Sehliohte- and Obersagsaasse rerseaem are, weraaf the fibers in the threadfora dried and the getreekaetem thread s on a spool. In this peat honor, the glass fibers are coated on the same side as the Schlicht- und Übersugsaasse in eimea einsigea Tejtfahremsgaag. This not only involves a strong time storm, but also a greatly reduced amount of apparatus. In Greßaneitien or in Ftllea where sam eiaea tJbereohuß rerwendet of formaldehyde in the combined sizing and coating composition, it is Jedoom old Sohwierigkeitem Tcrbundem, _f hersustellen an aqueous Lösang from dea lars, dea latex mnd the Kupplmmgsmittel without substantial portion of the latex precipitates . There is therefore a need for a coordinated Sehlichte- and Obersugsaasae, which can be prepared in Greßaaettsen and remains stable during their manufacture and when applied to the glass fibers.

The invention is therefore directed to peat sweeping dea glass fiber, the sar reinforcement of elastomeric products

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be used. ropes to be provided with a coating A novel combined sizing and coating compound is used as the coating, which is a rerforoin-formaldehyde resin, a terpolymeric styrene-butadiene-vinylpyridene latex, an amino functional silane coupling agent, Ammonia «ad an ammonia-soluble carboxyl content Contains polymeric acid as a stabilizer. You overdone Fibers are combined into a multitude of svinnfids, kept separately, and dried. The dried ones Threads can su reinforcement asweoken in an elastomer * Material to be incorporated. Vie was found, receives by adding the ammonia-soluble, Oarbe ^ y -lhaltligen polymers stabilized, prehydrolyzed amino-functional silane coupling agent to form a ßesorcin-formaldehyde resin and a terpolymer vinyl pyridine latez containing aqueous coating mass a stable aqueous preparation, with the glass fibers in a single The course of the process was simultaneously covered with a coupling agent and covered with a skin adhesive can be.

Piping and other advantages and features of the invention and the ways in which to get to them or to make them usable are in the following in connection described in more detail with the accompanying drawing.

BATH ORIGINAL

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2153667

The drawing shows in

FIG. 1 shows a device in a schematic elevation for making, overseeing and Drying of a glass silk thread as well as the. Procedure;

FIG. 2 shows the production on a larger scale

and the covering of the glass for the device and the procedure according to Figure 1 and

FIG. 3 shows the arrangement of the glass fibers in a side view in their passage through the production and inspection stage of the method according to FIG 1.

In the drawing and especially in Figure 1 of the drawing is sohematieoh a device for producing and sub Coating ron glass fibers shown, the one producing the fibers Part of the device is generally indicated by the number IO. A premelting device is installed in the device or a sole box 12 τοη a supply line 14 from supplied with glass furniture. The supply of the glass furniture to the Sohmelzkasten 12 is carried out by suitable means automatically controlled «In the melting box 12 the glass marbles are melted. The molten glass flows through openings into one firmly attached to the underside of the Sohmelzkaatena 12 Bushing 16. Made of cones of molten glass, which in the bottom of the bushing 16 from the tips in the openings hang down, glass fibers 18 are peeled off. The socket 16 can, for example, have 40 pairs of rows with 25 tips each be equipped so that about 1000 fibers can be pulled off simultaneously τοη the tips of the socket 16 · From each of the 40 pairs of rows, about $ 2 fibers can be removed, so that you see, denoted by the number 20, about 40 filaments or groups of threads. The ones kept separate from each other

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2153667

Threads or groups 20 are passed through drying ovens described elsewhere. Sa, the fibers 18 are withdrawn from the £ aser-forming apparatus, it assigns the hopper 14 and the Schmelzk & eten zweekmäBig 12 at the upper end of the Vorriehtungsteiles designated in Figure 1 by the numeral 24 at.

The lathering fibers 18 run across a socket opposite the socket 16 arranged kenrentionelle applicator roller 22 on which they be coated with the sizing and coating compound to be described elsewhere. Do their coating with the combined sizing and coating mass, the fibers 18 become threads or groups 20, each approximately 25 glass fibers 18 contain, combined. The ones from the coated Fibers of existing filaments 20 are then passed down through a first heating zone or oven 26, for example a dielectric furnace. In this first heating system 26, the threads, as shown, are spaced apart are brought together, the water is removed and the ammonia contained in the applied layer evaporated. When they enter the furnace 26, the Groups or threads 20 are spaced about 1.27 em from one another. Even during their drying in the oven 26, the Threads 20 held at a distance from one another. When passing through the one on a second floor 28 directly below the The furnace, which is arranged on the top floor 24 of the device, runs the threads srnsasnen, whereupon they can be found in a bucket of fawns or composite thread 30 cleaned by the through two guide organs made of graphite 32 lead back.

The composite thread 30 is then passed through a second hot zone or an oven 34 wherein the coated fibers are re-heat treated to further cure the coating be subjected. The thread 30 leaves the oven 34 in the form of a strand of glass silk. The thread or fiberglass * - * strand 30 runs over suitable rollers 36 uad 33 sew a ViokelTorriehtumg 40 for fiberglass threads. Viokel- ▼ orriohtungen of this type are in U.S. 3 041 662, 3 151 963 and 3 256 079 described,

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winding device 40 iat with elnar lifting device 42 provided that you see a spool of thread 44 ait more open Winding forms.

On the other hand, the threads kept separately 20 After passing through the furnace 26, without further hardening, a composite thread or (Ilasseidenstrang be united. or the hardened composite thread can, rather than winding up the winder 40, strands of irregular arrangement flow be cut up.

As shown in FIG. 1, the lower part of the furnace 26, the guide elements 52 and a part of the second furnace 34 are arranged in a lower level 46. The different floors are separated from each other by an unmarked concrete floor. The lower part of the furnace 54 and the winding device 40 located on the bottom floor 52. "To reduce the height of the building further below, the apparatus, the coating · and the device" must accommodate for manufacturing the composite yarn or fiber glass strand, it is possible that Change the running direction of the thread before it enters the second heating zone 54 from the vertical shown in the drawing to the horizontal.

It is useful to replace the composite thread 30 of the spools of thread 44 in the winder 40 to be held under tension to prevent the separated Threads 20 and composite thread 50 are drawn into the oven 26 and must be rethreaded. For this purpose 40 pull wheels 48 are mounted on one side of the winder, which the Composite thread or fiberglass stretcher 50 to a waste bin ^ O feed.

In Figures 2 and 5 is the upper part of the device

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enlarged for the presentation and coating of the fibers shown. The individual fibers 18 are combined to form groups of inverted prramids. These Fiber groups designated by the number 52 contain between 10 and 50 fibers. In the groups (52) are the Fibers 18 spaced apart. the Fibers 1fi_JLrafen over an orphan 54 of the application roller 22. Orphan 54 is appropriately read on a carrier 56 stored, which also has a container for the combined sizing and coating mass. When the single fibers 18 over the surface of the roller 54 slide, they initially move towards each other while forming a ribbon of thread, whereupon they move when they leave the coated roller 54, place one on top of the other. On the roller 54, the fibers 18 take a layer of the type indicated by the number 58 in FIG Sizing and coating mass, which adheres firmly to the fibers and these form a uniform group or a thread 20 with an oral cross-section.

They provide groups or threads 20 for drying of the coated glass fibers 18 in the furnace 26 have a much larger area than they are used for. Would be available if the Fibers 18 and filaments 20 would be combined to form composite filament 30 after drying. In the case of the one described Procedure is the TrocknungsgeeehwiaAlfke-it with the separate threads 20 in a smaller oven larger than it is with a composite thread of the type of the composite thread 30 would be.

BATH ORIGINAL 209825/0731

The description and claims include the The expression "combined nominal light weight and coating mass" is a aqueous mixture containing chemicals used as coupling agents as well as chemicals used as rubber adhesives contains and is used sur coating of glass fibers, which in coated form as a reinforcing agent are intended to serve in elastomeric * materials.

"Xautsohukklekle" or "Gummiklebet off" is understood in general the combination of a conventional reserein-formaldehyde harses with a conventional polymeric Katutsohukklebetoff Latex with buckets of polymers or copolymers of vinyl pyridines and the like. As examples of such latiees be the mixtures or copolymers », of Polyviaylpyridins with chlorobutene, isoprene or chloroprene as well as the acrylonitrile,

Butadiene-styrene-Cepelymere and the butadiene-styrene-copoly-

called mere in latex form. In the U.S. Patent specification 2,817,616 are formulation of chemicals for automotive adhesives called which are suitable for the purposes of the invention

A commercially available terpolymer is preferably used Latex of the styrene-butadiene-vinylpyridine, made by the General Tire and Rubber Company under the dull "GenSa ©"; from Goodyear as "Plielite VP-1OO"; from Firestone as "FR-S 220 "and sold by Goodrich as" Goedrite 2518 ".

Amino-functional hydrolyzable silane coupling agents of the type suitable for the invention are those of general formula

«-Κ ₃

-Si - / qr7

η R-

⁵ m

in which R _{1 is} hydrogen, an alkyl radical with 1 to 5 carbon atoms or HZSHOK ₂ -OH ₂ Z _x werija χ far a number

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from 1 to 5, R _{2 is} hydrogen or an alkyl radical with up to. 5 carbon atoms, H ^ a divalent group from the group of lower alkyl radicals with less than 5 carbon atoms and preferably less than 5 carbon atoms and H ^ and E ^ alkyl radicals with 5, or preferably 1 to 2 carbon atoms, ad in the m one whole number from 0 to 1 and η is a whole number Tön 1 to 3, Tersugsweiee 1. Typical examples are gamma- iiminopropyltriethezysilane and similar silanes, the preparation of which is described in US Pat. No. 2,832,75.

Under anmeniak-löeliehen, car boxy! Containing polymers from of the kind suitable for the invention is understood to mean solohe polymeric substances which contain carboxyl groups in such an amount that they are soluble in aqueous ammonia solutions especially in buckets with a pH of around 10 to 12. Typical examples are earbexylated tea Polyvinyl acetate, polystyrene, polyethylene and aeryl polymers as well as carboxylated Jälastomere, such as carboxylated Styrene-butadiene copolymers and styrene-butadiene-aeryl nitrile polymers, which are soluble in ammonia, called.

Particularly suitable ammonia lösliohe carboxy! Aoryleopolymere containing polymers may be mentioned containing about 1 to about 20 wt.% By weight of a Hydrexyalkylesters of acrylic acid, methacrylic acid Eder another alpha, betK äthylonisohungesättigten-carboxylic acid. Han can produce solehe Seter by one Dafi a Alkyleaglyeol with the acid or the acid with alkylene oxide is reacted · The Bydroxyalkylester is then reacted with about 1 to about 20 wt.% Of an unsaturated carboxylic acid and at least one other äthyleniseh unsaturated and the acid and the Ister polymerizable monomers are polymerized.

The acrylic copolymer can contain hydroxyalkyl esters, for example esters of acrylic acid and methacrylic acid, in which the hydroxyalkyl group holds up to 5 Kehlenst ^ ffatos®. 2-Hydroxyäthylaerylat, 2-

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acryl ** J-Hydroxypropylaerylat, 2-Hydroxyethylmethycry1at, 2-hydrexyprepyl methacrylate, 5-hydroxypropyl methaorylate, 4 — Hydroxybutyl methyl aorylate and mixtures of these compounds. Suitable aimd auoh di · esters of other unsaturated satires with about 6 carbon atoms, many ethaerylic acid and Crotonic acid.

In addition to the esters of unsaturated monocarboxylic acids, one can use also the ester or ester of unsaturated dicarboxylic acids use, for example, shark acid, fumaric acid and the itaeenic acid, in which at least one of the reesterifiable Groups contains a hydroxyl group Examples of such esters are mono (2-hydroxyethyl) maleate, aeono (2-hydroxyethyl) fumarate, Bis. (2-hydroxyethyl) maleate, mono (2-hydroxypropyl ) maleate, such as (2-hydroxypropropyl) maleate. Mono (2-hydroxyethyl) itaoenate, Bis (2-hydroxyethyl) itaoonate and 2-hydroxyethylbutyl maleate called·

The best of the aoryl copolymers is made up of another Ethylenically unsaturated monomers which can be polymerized with the acid and the ester or from several of these monomers As examples of such monomers, alkyl metal aerylates and alkyl metal aorylates with up to about 20 carbon atoms are selenium in the alkyl group, such as methyl, ethyl, propyl, butyl, Hexyl, ethylhexyl and lauryl aylate and methyl, ethyl, Propyl, butyl, hexyl, ithylhexyl and lauryl methaorylate, as well as other allyl esters τοη alpha, beta-äthyleniseh-unsaturated Called carboxylic acids. Also rinyl-arenatic hydrocarbons, such as styrene, alpha-alkyl styrene and tinyltoluene can be used in the copolymer.

The copolymers are prepared under the conditions known for the preparation of aoryl polymers. Also the catalysts are the same as in the well-known peat honors. Usually one works with a catalyst which forms free radicals. lOrmalcrweisc the polymerization is at a temperature of about 65 swischen umd 140 ⁰ O through. The carboxylated polymer can β · Β. a molecular weight up to about

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BATH ORIGINAL

Have 20,000.

Vi · Described, dl · formulations after, the Erfimduag keabiaierte Schlicht- wheel Übersugaaassen represent that al · egg-like coating can be applied to glass fibers • Ham. However, it is also possible to use the old one of the erf imaungsgeaaficm Hassan coated thread when winding avf the bobbin or when unwinding from the bobbin suaatiliahen ttaarsmg from a guaaikleff «u rers see. Veaa aaa ea wuaaaht, kana aaa on the glelone Velae too A suaitslioaea cover from one of the inventions Apply Haasea.

One can use one suitable for the purposes of the invention Schllaate- and Obersugaaaaee according to the following recipe formulate:

% Heiorcin-yeraaldehj-d-Har »a ·· 20 - 70 wt. % Styrel-Butadiene-Vinylp7Tidine-LAtex (MiBehung« -

rernahmnia 15:70:15) in fora of a 41 % Feetoffe containing Wasarigon dispersion

0.01 - 3 ft # w. % Onea Kupplungaaittela 0.1 -. 6% by weight, a β-aaaoniak löeliohen, carboxy lhalt strength

Polyaers

0.2-15 wt.% Of a 28 wt.% Aaaoniax solution and 60-85 ow. % Vasaer

The following three examples show the extent to which the Stability ren combined sohliahte and Üoersugaaaaeen the invention is compromised «They describe experiments on a small scale. Example 1 shows the simple addition of a size and an oversize.

example 1

Prepare three gallons (11,355 liters) of latex solution as follows:

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Mu gives

3 351s Vaster

15 β 28% ammonia and
492 g of an acid-catalyzed resorein-formaldehyde norolak containing 75% solids (HelTermältnie 1id, 6), for example the Penaeelite from the Koppers Company _t «u

5 490 g of an i »Tarkältni · 15i7Ot15 1ι · χ * ·· * β11« · η «AA 41 * J« et * toff · eatfeftltcaAMt ltyrol-Bmta4i «n-yijaylpyridin-Lat» x, b «i« pl «le« «i« e Aas (J «ä Sao'eder G« n «ral S« bb «r Coapany and

1 830 β · 1η · * 41 % fuel · anthaltendtn Styrene-ButaAiaa-Kautechuke, Baiapialawais · d «a GenevaIo's of Osnsral Rubber Ooapany

and miseht 10 minutes lukewarm w * ä> set the Gsaisoh then

222 s 37% 1β> iormaldehyde

xu. Urine takes up about 3 gallons of a latex overturn or latex meluMUis, which has a pH τοη about 8.5 and a solid cold about 30%.

One issues equally

1 al Gaama-aainopropyltriäthoxysilaa as a coupling agent

1 si 28% laaoniak and
18 al water

a sole remedy. Han misunderstood the two components meanwhile, 10 al of the bohliihteamittel slowly su 100 al der coating compound there. It occurs immediately with clumping a separation of the components, which proves that the mixtures are impregnable.

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Example a Han exhibits «in stabilizing · * mixture

31 al of an ammonia-soluble, carboxyl-containing polymer made from 62 % butyl aylate, 22 % styrene and 16 % methacrylic acid, which is composed of 43 % butyl cellulose and 57 % butane ·! existing solvent contains 80 % solids and has a Yiekoeitit ren approximate 75 000 Cp,

30 al 28JiIgOB iBBomiak
10 al butyloellulese and
29 ml of water

and a BshliohtoBittol from

1 Bl asBBa-aBinopropyltriathozysilane as coupling agent,

2 al of the stabilizing mixture, 1 Il 28 ftigOB. Ammonia and

16 Bl water

here. Han gives 10 ml of the slippery agent produced in this way slowly su 100 ml of the coating composition according to Example 1 Binsu. Han gets a Geaiseh τοη gleiehaafiigea texture, «η dem no signs of clumping or instability can be seen.

Example 3 A stabilizing genius is exhibited

33 ml of an ammonia-soluble, carboxyl-containing polymer made from 49 % butyl ethylate, 25 % styrene, 16 % methacrylic acid and 10 % 2-hydroxyethyl ethylate, which is made up of 7% ethyl cellulose, 18.5 % m- »butyl

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ether and 7.5% isopropyl alcohol Ldsungsalttel dissolved, contains 75.5% test substance and has a viscosity τοη approximately 50,000 Cp,

30 al 28% ammonia,
10 al BmtyleelloselTe and
27 al water

and «in ßchliehtemittel ams

1 al ftaama-aainopropyltriathoxysilane

as a coupling agent,

2 al of the stabilizing Geaisehes, 1 al 28% ammonia and

16 al Vasser

here. One sets 10 al of the solute agent thus produced slowly 100 al of the ÜDorsugsasse after Example 1 see below The mixture has a uniform structure and does not allow the formation of lumps and recognize intactivity.

In the following five examples (4 to 8), combinations τοη Sehllehteaeinrichtungen and oversaassen of the invention geaiAen Irt mad their manufacture described. Also examples τοη Koabinatienen τοη Sohliohteaetzen and Übersugsaassen, which no carboxyl-containing polymer as a stabilizing Means sugesetst are called to suit what problems occur in the absence of the stabilizing agent «Although these examples specific embodiments of the invention describe, the invention should not be limited to them

Example 4

To produce an eorcinol formaldehyde resin, 15.9 kg of water, 16 g of xalium hydroxide and 1,440 g of resorcinol are added to a reaction vessel and the mixture is stirred until the components have dissolved in a runny manner, according to 2000 g bucket of 37% aqueous dermaldehyde solution iu mad IaSt dme Seaisch age 3 hours at 23.9 to 25.6 ° ß

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Ham gist la a "wide reaction vessel 35 kg GenTao, •! Asm τοη 4 · ρ General Tire and Rubber Company in trade gebrachtem synthetic rubber in Latexforn, the 41 wt.% Of a T 15t 70s 15 is nil τοη of styrene, butadiene and vinylpyridine existing terpolymers', add the reserein-fermaldehyde resin mixture prepared according to paragraph 1 of this example with gentle stirring, stir the mixture for a further 5 minutes, add 1000 g ammonia, cover the mixture and leave it with gelimdem Stir. Age 16 to 20 hours.

Han puts 2400 g of water, 160 g in a third reaction vessel Ammonia and 160 g of an ammonia-soluble acrylic resin, the rome of Union Carbide under the name π.C. Aerylie LESB prepared and driven as a 55% by weight aqueous Gemisoh the Gemisoh until solution has occurred. Then 160 g of the coupling agent gamma-aminopropyltriethoxysilane added. The stirring of the solution is continued until a clear solution has formed. Then the clear solution becomes that containing the coupling agent stybilized with the acrylic resin according to the invention slowly to the aged one explained above The mixture is added with stirring, and it is then stirred for a further 15 minutes.

One can observe Dafi no Zusammezigeben d @ s the Xupplung "- medium-containing mixture and the Resoroin-Formal ·" hyde resin and the Vimylpyridinlatex part containing non w Misehungskempenemtem "thrown out" or be precipitated lumpy. The Gemisoh also contains 28% by weight of solids. If the mixture is applied to glass fibers with a custom orphan rom the usual way, satisfactory eyesight is obtained.

Example 5

Example 4 is repeated in the absence of the ammonia solution added there in the third reaction vessel in an amount of 160 g Acrylic resin, but in the presence of the coupling agent and stir the Gemisoh as described. You give them

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the coupling agent, but not an Aerylhars stabilizer containing solution su dam Gemisoh made of latex and resins. This forms a lumpy, rubbery precipitate, is unsuitable as a coating for glass fibers is.

Results similar to those of Example 4 are obtained with other aeryl hareses which can be drained with water, for example with the aeryl hareses commercially available under the name Staley A 700. Han, the acrylic resins by the ammonia-lösliohen replace oarbexylierten polyvinyl acetates, for example by the commercial Hars HSCO ASB 516, the 10-20 wt.% Orotemsaure contains, and the reindeer VR Gracie and Cempany in trade brought Hars DlBiSAK 78L.

Example 6

Follow example 4, but with the rom of the sew Corning operations sold under the designation Z-6O5O Eupplungsmittel instead of the Qamma-aminopropyltriethoxysilana as a coupling agent, another sizing and oversugging compound. Z-6050 is a partially condensed or polymerized hydrolyzable aminoalkylsilane. Results similar to those in Example 4 are obtained, i.e. Here the latex does not fall if the stabilized reading of the coupling agent with the Hari-Latex-Oemisoh is put together, results are obtained also with other amino-functional hydrolyzable substances Silane series coupling agents such as that commercially available under the designation A-1120 the Unien Carbide, which is the Tormel

and the coupling agent of Permel

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Example 7

Kan "divides" in a combination of a visual aid and a bucket of coating compound on the following / iron

One gives 1,700 parts by weight of Vaaeer mad 155 parts by weight of ammonium hydroxide, this in a bucket of normal concentration with about 28% ammonia, in the "in" rat "" heating vessel has stepped in. Suitable is the commercially available Iorolak B 2170 from the Koppers Company, which contains about 75 % solids and about 25% Vas β er.

In a iweiten vessel it will stall from 3 550 weights parts GenTao, buckets commercial synthetic Ia "ts" huklatex the General Tire and Rubber Company, is as Jeststoff 41 wt.% Dee approximate ratio 15t70t15 of styrene, butadiene and vinylpyridine existing terpolymers amt holds, and 1 183 weight parts GenTlew, a likewise hamdelsüblichen synthetic rubber latex is General Tire and rubber Company Aar 41 wt.% containing about relative 50t 50 »usammengesetstem styrene-butadiene polymers al · solid, a latex ago, this session is the Hexslösung ame dam susammem first vessel, the Gemlseh stirred for about 10 Minutan, then 268 Sheet formaldehyde old Gewiehtsteile a solids content τβη about 37 wt.% iu, eet "as t · da · Hühren Gemisehes continued and then allowed to age over mn power.

The coupling agent is then placed in an imam djrf-th vessel har that one can get 700 parts by weight of Vaasor and 40 fail a standard solution of immonium hydroxide, the Mixture 40 parts by weight «in ·· under the Beseiehmumg U.O. 203 «1« 55% by weight aqueous solution commercially available Amaoniak-soluble Aerylhanes still required 45 parts by weight with 1-1100 eeseiehnetes eamma-aminopropyltriltnoxysilane al coupling amittol suaetst and taemiealn stirs, until «im · klar · LSaumg has formed.

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Haa «« tit di ···, da «ait stabilized the Aorylhars Coupling agent «at kai tend · solution laagsaa dea agedea teaiseh au · d «a resin« ad d «a latex with stirring, uad continues stirring for 15 hiautea.

Even if the foraaldehjd content of the resin latex is very high, the latex is not "thrown out" or precipitated, especially as the hars-latex system is added to the clutch. The mixture emtkilt 30 oew. % Solids. The lorolak is made up of latex in general, about 15 % and 100 parts by weight of the two substances.

With> iel β

Haa «shares maek Beiapi ·! Λ la separate vessels a eia resin uad elaea latex rea der there besohriebeaen her, wekei aaa eiaea ia v «seatliek« a gleiekea Obereehuß aa Joraaldehyd renfendet vi «ia Hars naefe B« iapi ·! 1, gives daa Ears -αϊ the latex sueaaaea, stirs the Oeaiach aindeateaa 10 minutes uad ISBt ·· over Haoat altera · Ia puts aaa vi · ia example 7. But oka · the Aerylkars used there ia a quantity of 40 parts by weight A coupling device here. Veaa aaa this coupling device which does not contain aorylhars as a stasilizer, daa Hars-Latex-Geaisoh sueetit, eatstekt ia the solution eia firm plumage, roa latex ia fera a lumpy, gumai-like hatred, the sua Be'ohi "Hten von Glasfae" ra is unsuitable.

Haa cleaned the sizing uad oversaassen aaok example Λ and 4 uad rerweadet the cold coabiaed hats sua Sohlichtea and Besehehten roa about 1,000 "£ ^M glass fiber, rom each of which has a strength of 0.00035 to 0.00040η. They are Ctlasfaaera τοη the Buchs uad abgesofen "the illustrated ia the drawing performing * ufge" ekwindigk «lt coated at Terkaltaisatiig high l with an applicator roll. is based on the weight of the fibers ren each ϊadengruppe 20 EIA coating τοη about 50 wt. accommodated%. the coated Tadeagrupp «A

2098 25/0731

BATH ORIGINAL

are then sucked through an oven 26 in which essentially all of the water and HH are farmed from the coating by means of tar steam. The thread groups 20 are then combined into buckets of composite thread 30. This is made tack-free for a partial hardening of the coverings through a “wide oven ” , so that it is wound up into a cylindrical spool of thread with an open Vicklungsart “and then unwound again, when it can be used as a door reinforcement means fftr loudsanuk attached en wants. On the weight of the fibers, the dried, coated thread has an average of 15 mmd 30 (lew, % upper mass.

The specified TtdoA have a satisfactory "H" bond strength and flexural strength. They are also, in elastomeric » Products used as a reinforcing agent, fatigue-resistant against pressure (compression fatigue resistance). To the Yerstlrkumg τ · η rubber is used a cord or fabric manufactured as described and, if necessary, provided with a "far over" ug from a loudspeaker adhesive or fiberglass strings 30. The cord or the Fabrics can easily be impregnated with a susceptible chewing adhesive to improve their moisture properties are · .As elastomeric materials for which the coated. VerbuneXiAsm or Olasseidenstrange with good Xvgobnis as Extended middle can be used sejLom more natural Rubber, synthetic rubber based on butadiene, chloroprene, isoprene and the like, the Cepelyeeren des Butadiene, chloroprene or isoprene with amdorom in dor manufacture of synthetic rubber known substances and the vulcanizable and curable modified forms of the above Substances mentioned for example. The Auedrmek "Elastomeres" and "elastomeric material" should therefore be natural and synthetic Include rubber in both the uncured and uncured and the cured and vulcanized states.

The invention is in the previous Bosohreibumg and in the Examples »based on preferred formulation quantities of the combined

209825/0731 bad ORIGINAL

Sahlicht · - and tfrersugmittel ie with regard to the currently the best Yegfahremetechnik: has been explained. the end However, the description shows that other than the named teramations can be used. Bas means that the invention does not, of course, apply to the specifically mentioned formulations and procedures is deserved.

BAD ORIGINAL 2 0 9 3 2 5/0731

Claims (1)

Process sub covering τοη glass fibers, di sum Tor- strengthen tob elastic fabrics r «nr« nd «t should * characterized in that »an GesehBlscaes Glas su fibers looks, au «a Besercia-Poraaldehyd-Hars _t « iaem Butaditn- Styrene-TlBylpyridlix-TerfalTBaramlat · »,« la · »Kapoppela- ■ ittal der lmim # tilaDJr »ih ·, leeonlak« ad an aaaoziialclöeliakea, earkexylhaltigen Pelyneren elae keabinierte wiesrlg · 8 «mlioht · - Had Übersiigsaais · k« rsttllt, di · einieliiea Olaef turn ait the combined «watery Sohliekt - mad Obemugsaaes die eiaselaea Glaef asern su one Tielsahl ren roa each other getreaatea 8piaaf & dea cleansed, the Übersegeaea fibers in Torah of these roaeiaaader getreaatea Spiaaf ädea dries and the filaments of the dried fibers amfsaavelt. 2. Terfahren naok laepruch 1, thereby gekeaaseieaaet that »an the superior Glaefasera after their Troekxaag in elasteaere Steffe works and eats it up aeehaaisehe «ad physical property arerleiat. 3 · Process "naoh laaprmeh 1, by the fact that aaa sees the glass fibers with an amount of about 50% of their weight in the amount of the combined watery Sckliehteuad Obersagsaasse. 4. The method aaeh claim 3, characterized in that aaa the glass fibers aaeh dea dry with a swisohea 10 "ad 30 % of their weight amount of the amount of solids contained in the combined aqueous sizing and Ubereugemaase are coated. 5 · The · combination of a composite body consisting of glass fibers and a slastoaerea material ait eia®r 209825/0731 ^BAD ORfGfMAL the surface of the glass fibers coated combined Semllehte- mad coating composition _t dadmreh in that 41 · combined sizing "ad coating composition contains in solution imaemlak mad" la ammsslak-löallchss _f earbexylhaltiges polymer which the aqueous LSeiuBg au "dee B" s "r" iA-T * rmald «lqNl <-Hars, d« a Lat «z xm & dta imlnoeilan-Kappl« acMd.tt «l la der kemblaiertea Soalicht« - mid transitions aaia rta ^ li ^ rt, - daft the latex la LSeuag remains and there · Impplaafaalttel, that · Hare «ad the latex am · ilirer geaelA ·« »·« waesrie «a LSamaf as a matter of fact on the · Glaefa • erm« afs «can be tea ** t. 6. Sine kembiai «rte wlsaris · Sehlieht ··« nd characterized by the content τοη a Beeorein-rormaldekyd-Har *,
a »Timylpyrldinpolymerenlatex an amimo-functional, hydrolyzable capping stomach agent from the silane series,
Immemiak mad
an ammonia oil borrowed _t carboxyl content ?. A kembimlierte aqueous · Sehlieht · - mad Übersugsaa ··· after laeprueh 6 _t admreh that the yinyl pyridine polymer latex is a termopolymer on · butadiene, styrene and Tlnylpyridln. 8. A coagulated, watery visual skin · - and according to lneprmeh 6, dadureh known that the "alnofunctional part." ßilane coupling agent Gaiiea-amiaopropyltriathoxy-βilen 1st. 9 · A · combined watery visual skin · and · overbug · after Aasprueh 6, dadmreh marked that dag earWzylhaltige Polymer · an acarbesylated polyrinylaoetate polymera or a water-thinnable Aerylhars. 10. A combined water-based visual coating compound Claim 6, dadmreh known that the amim * -functional part, 209825/0731 BATH ORIGINAL hydrolyzable silane coupling agent a compound of formula ¹ V NR ₃ Λ ' -Si - η R