DE2225611A1 - Fiberglass reinforcement, as well as processes for their manufacture - Google Patents

Description

DR-INQ. OIPL.-ltMG. M. SC. L) IPU.-PH i S. L) R. OIPL.-PHYS.

Ö - LEGAL RIGHTS- ERLESSBACH - HAECKER

PATENT LAWYERS IN STUTTGART O O * "i E" Γ »1 1

22256 ι ι

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Owena-Corning Fiberglas Corporation TOLEDO, Ohio / USA

Glass fiber reinforcement, as well as processes for their manufacture

The invention relates to a glass fiber reinforcement for a glass fiber / elastomer product, consisting of a bundle with a large number of glass threads, with a first coating the glass fibers for protection against mutual abrasion and with a second, an elastomeric composition Coating, wherein the first and second coating can react with one another. -

The invention relates generally to the treatment of glass fibers used in the manufacture of glass fiber reinforced elastomeric products, for example rubber belts. Rubber tires and the like can be combined with the elastomeric materials. These For example, elastomeric materials are natural or

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synthetic rubber or rubber, its strength, toughness and dimensional stability can be significantly enhanced and improved due to the presence of glass fibers.

«If glass fibers are used to reinforce elastomeric systems, Then glass threads are sized immediately after they have been formed

ψ ' ■■■■■. _f -

* or coated with a protective material and converted into a glass fiber

■ bundled or stranded together. These bundles can unchanged t 'be left or can weiterverar- • ^ beitet be in the desired shape, to use as a reinforcement, they can; for example twisted, pinned or other processing

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. tung steps in the formation of cord, woven rovings, etc. are subjected to f, furthermore, it is possible for the strands to "- ■ chips and then into the continuous fiber ^elastp-; mers system, such as in tires, belts, hoses Ί Incorporate.

Before the sized glass fibers are incorporated into the elastomeric system to be reinforced, it is necessary to

■; ' Treat or impregnate glass fiber bundles with one or more mixtures that separate the fibers from each other

; · Ϊ and the adhesion between the treated bundles' (Cord, Ge ..

i weave and the like) and improve and promote the elastomeric system. The separation of the glass fibers and threads within the bundle is necessary to prevent the glass threads from being destroyed by .. _? . avoid mutual abrasion. The adhesion between. '. /

the "glass fiber bundles and the elastomeric system is necessary.. ,, _?

■ to the strength and strength of the glass fibers to the elastomer To lend end product.

The term "elastomer" as used in this more often ^{environmentally:} includes, in addition to neoprene nor such other synthetic elastomers or rubber or rubber-like materials such as

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Butadiene, chloroprene, isoprene and the like, or copolymers thereof with acrylonitrile, styrene and the like, and in particular such elastomers Materials that are cured or hardened by means of a reaction through peroxide or through sulfur bonds State hardenable or vulcanizable; the term elastomer also includes a natural rubber and modifications of the ^ - same as, for example, chlorinated rubber and the like.

The preferred elastomer for impregnating glass fibers is however the one in the. U.S. Patent 3,567,671 is described in more detail. This elastomeric impregnation mixture comprises an aqueous one System having the following solids distribution, 2-10 parts by weight of resorzinol-formaldehyde resin, 20-60 parts by weight of one Butadiene-styrene-vinylpyridine terpolymer, 15-40 parts by weight of a latex, selected from a mixed polymer of vinyl chloride-vinylidene chloride, a carboxylated butadiene-styrene * copolymer and a group comprising a polyethylene methacrylate resin, and 5-30 parts by weight of an incompatible microcrystalline Paraffin wax.

It is true that the term "glass fibers" or threads is preferably used to define continuous glass fibers in the form of Threads, strands, yarns, bundles, cords and fabrics made therefrom have been used, but it is intended that in this term also discontinuous glass fibers in the form of glass wool fibers and yarns and fabrics made therefrom to include fibers of the continuous or discontinuous Kind that have been cut, shredded or otherwise cut into shorter pieces, these pieces being but are generally longer than 0.3 cm.

In general, the glass thread is applied at the time it is drawn from a molten glass supply, or

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a first immediately after their formation into glass threads Mixture applied. This first mixture usually contains a material which is known in the art as a coupling agent, for example as an organosilane, in addition in addition, the mixture generally also contains film-forming agents and lubricants. The mixture serves to protect the glass fibers against mutual abrasion and also offers a better coordination of the glass fibers not only with the subsequent one impregnation mixture still applied, but also with the continuous elastomeric phase reinforced by the glass fibers will. The individually coated glass fibers are combined into bundles. These bundles can be twisted, pinned, woven into cords and fabrics or left unchanged. The bundles, cords or fabrics are then added in a processing process that is separate from the glass fiber forming process an impregnating agent based on an elastomer, which during the formation of the final product, for example, reacts with the continuous phase of the elastomer during the vulcanization of the reinforced elastomer or this appends. It is common to add over 8 percent solids by weight based on the weight of the glass fiber and generally between 8-30 percent solids by weight of an elastomeric compatible masterbatch on top of that previously treated glass fibers to achieve fiber separation and adhesion.

The first mixture is applied to the glass threads at a time at which they are pulled out of the melted glass supply or immediately after the formation of the glass threads; this mixture was generally a liquid material until recently, but newer mixtures are more pseudo-plastic or thixotropic. Often a special manufacturing process or a special end product determines which these are processed Glass fibers used, whether a liquid or a pseudo-plastic,

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ie malleable, pliable size is used. However, significant problems have previously been encountered with the use of these materials in that liquid layers of glass are wasted and run away in the molding process, as well as wandering of the size from the glass strands as the strands are wound into a package; Furthermore, problems with the further processing properties occurred with the earlier pseudo-plastic visual layers (namely fraying, the strands running out of the pack once formed, etc.), and the glass fiber reinforced product also had low tensile strengths and adhesion values. Therefore, in order to form suitable glass fiber reinforcements for elastomeric systems, attempts have already been made to fully load and impregnate glass fibers, so to speak, during the molding process. The processing properties of these fully "loaded" fibers, however, in turn resulted in problems / during the subsequent processes (namely bundling, twisting, twisting and weaving), due to the bulkiness and the greater mass of the threads, which, as already mentioned above, had between 8 to 30% solids, so were loaded or contaminated in this way. To avoid this problem, it is switched over to a three-stage process, so that one could avoid the full impregnation during the molding operation necessarily, these _s three-step process includes the following steps: 1. applying a portion of the impregnant in the molding process, said part a coupling mechanism included. 2. The bundling of the fibers and the further treatment of these bundles to produce the desired shape and 3. the application of the remaining impregnating agent coating in order to bring the now treated bundle so far that the necessary solids content of impregnating agent is achieved to achieve good adhesion is. But this method also has disadvantages, since there are between

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the first and second impregnating agent coatings form a boundary layer or a precisely distinguishable layer effect, so that only a relatively weak bond can be made between the two coatings. In addition, revealed the disadvantage that these layers reinforced when the processed bundles (cord, yarn, fabric, etc.) Product were put under tension, would be separated. If this were to happen in a tire body, for example, then would the reinforcing fibers become detached from the continuous elastomeric phase of the tire and lose their connection with it, which would result in their no longer being able to use the high strength properties of these continuous elastomers Phase to be communicated.

In order to counter these disadvantages, the invention is based on the object of creating a size mixture which is based on the Glass fibers can be applied. This object is achieved by the measures of claim 1, with the advantage that that due to this sizing mixture according to the invention when the coated glass thread is embedded in an elastomer Matrix extremely uniform and high tensile and adhesion values can be achieved. In addition, the inventive Sizing mixture essentially problem-free further processing of the glass thread after the molding process. \

The size mixture applied to the sized glass fibers thus withstands the stresses that the further processing operations following the forming process on the fiber optic bundle and gives the subsequently processed and further treated glass thread durability, In addition, there is the essential effect that, as already mentioned, the tensile and adhesion values of the glass fiber reinforcement are considerably reinforced in the elastomeric system.

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The size mixture according to the invention is applied to the glass fibers in an extremely precise manner using suitable apparatus, in such a way that a measured proportion of the size mixture is supplied to each of the glass fibers.

The size mixture itself is reversible under shear forces Properties having gel mixture or a pseudoplastic mixture and is during the molding process on a Applied to a large number of advancing glass threads. The size mixture according to the invention is therefore its properties after thixotropic. The number of glass threads that are continuously produced during the molding process is in Range between 204 threads (G150's) to 408 threads (G75's) up to 2040 threads (g15's). The preceding letter refers G in the brackets refers to the diameter of the glass threads formed. The preferred diameter of glass threads that are used as reinforcement in elastomeric systems, lies approximately between G to M, where M represents the largest diameter value. In this connection it should be pointed out that coarser threads are cheap and also have good performance have, but that preferably finer threads can be used, unless their economic considerations Limit usage. -

Another particular advantage of applying the inventive Sizing mixture on the drawn glass threads during their forming process consists in obtaining extremely uniform strand solids per unit length of the glass filaments achieved, this is extremely important in the subsequent process steps, in which, for example, a large number sized strands or bundles, for example by twisting, plying, bundling and the like. Changes . the proportion of the size mixture on the glass threads is

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In an essential way, then they change in the same way Properties of the glass threads in the reinforced matrix so that the quality of the reinforced product decreases. There is also the advantage that there is essentially no migration of the Size mixture occurs on the glass fibers or from the glass fibers when these are wound up to form a package; this is therefore of considerable importance if the glass fiber bundle is still being impregnated with an elastomeric material is, and the then impregnated fiberglass bundle in an elastomer Basic material is incorporated. Here, if the uniformity of the properties varies per unit length of the glass fibers / the quality of the reinforced elastomer is adversely affected, especially when the reinforced elastomer is subjected to dynamic stresses and strains, which is particularly true for tires, belts, hoses and the like.

In using the size mixture of the present invention, the problem is migration of the size from the formed package essentially eliminated ^ as the sizing after it has been applied to the glass fibers, but has sufficient time before they have been wound into a package, to return from the liquid form to the gel form, the liquid form is the result of shear forces acting on the Mixture of sizes can be exercised. The processing properties of such sized glass fibers are compared to existing handling options considerably improved? these arbitrated Glass fibers have a uniformity in their properties that could not be achieved until now. In particular are such prevalent problems as strand fraying, difficulty of sized glass strands in making Leakage on the pack and the like are now completely eliminated when using the size mixture according to the invention. Furthermore are the physical properties of the fiberglass

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reinforced elastomers significantly and considerably improved, in particular, as already mentioned, the tensile and adhesion values of the reinforced elastomer.

It is believed that this is due to the use as well as the type and Way is due to which the size mixture on the Fiberglass is applied.

The size mixture according to the invention can be used in the coating of glass fibers, these being further treated as reinforcement in a resinous matrix for the final disposition. "'- ....". " .- '-

A size mixture for a textile material, such as, for example, glass threads, which are used as reinforcement in elastomeric products and materials, must be able to give the glass threads a sufficient service life, flexural strength and the like so that they are able to to withstand the operations following the formation of the glass filaments, such as impregnating the glass fiber bundle, twisting, twisting, weaving and bundling. In addition to these requirements, properties such as tensile strength and adhesion of the glass fiber strand and durability of the impregnated glass fiber strand, in particular with regard to aging under the influence of moisture (more
borrowed.

(more than 50% relative humidity at more than 22 ° C) required

The size for glass fibers according to the invention is capable to react chemically with a subsequently applied elastomeric impregnation agent and / or with the elastomeric matrix which should be reinforced by embedding the treated glass fibers

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Description of preferred exemplary embodiments

Example I.

Components
Polyethylene glycol
Polyamino Functional Silane Gamma-aminopropyltrimethoxy Silane Thjxotropic Ingredient Lubricant

Solid emulsion of polypropylene Deionized water Percentage by weight O.05 - 1.50 0.08 - 1.30 0.08 - 1.30 0.10 - 2.00 0.05 - 1.50 1.5O - 17.OO to one hundred

Example II

Components

Polyethylene glycol
Polyamino-functional silane Gamma-aminopropyltrimethoxy silane Cross-linked polyacrylamide polymer Long-chain fatty acid derivatives Solid emulsion of polypropylene Deionized water Percentage by weight 0.12 0.20 0.50 0.30 0.39 3.60 to one hundred

Example III

Components

Polyethylene glycol
Gamma-aminopropyltrimethoxy silane Cross-linked polyacrylamide polymer Long-chain fatty acid derivatives Solid emulsion of polypropylene Deionized water Percentage by weight 0.05 - 1.50 O.O5 - 2.00 0.10 - 2.00 0.05 - 1.50 1.50 - 17.00 to one hundred

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Example iV

Ingredients _s ' percentages by weight

Polyethylene glycol Ο «12

Garama-aminopropyltriraethoxy silane 1.00

Cross-linked polyacrylamide polymer Q »30

Long-chain fatty acid derivatives 0.39

Solid emulsion of polypropylene 3.60

Deionized water .. by the hundred

The size mixtures correspond to Examples I-IV are manufactured according to the following process. A mixing vessel and Homogenisatox is made with fresh deionized water rinsed to remove any trace of contamination. Then with the help of a suitable tool, preferably with a high speed mixer, the polyacrylamide polymer dispersed in the deionized water and the dispersion then expanded to a volume of about 227 l « The mixing process is continued for at least 30 minutes with stirring and agitation. Then the gamma-aminopropyltrimethoxy Dilute the silane with approximately 9 liters of deionized water and add this solution to the mixing vessel. If that polyamino-functional silane in connection with the gamma-aminopropyltrimethoxy If silane is used, this is dissolved in approximately 4.5 liters of deionized water and added to the mixing kettle. Then the long-chain fatty acid derivatives and the polyethylene glycol mixed and diluted with about 9 liters of water and the diluted solution added to the mixing kettle. The polypropylene emulsion is then added to the mixing kettle and the remainder of the 100 deionized water is added. The mixture of the'- 'contained in the mixing vessel The components are continued for at least 30 minutes before the mixture is homogenized. The homogenized material is then made into a collapsible polyethylene, stainless steel

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At

Steel or glass fiber reinforced container filled for later use.

The homogenized mixture should have a viscosity range of about 120 to 180 cps. If the viscosity of the size is below 120 cps, then this tends to to drip off the applicator and form non-uniform strand solids. Is the viscosity higher than the size 180 cps, then a non-uniformity in the solids stirs the strands because the applicator develops dry spots, i.e. it releases the glass threads that run past of simplicity.

The polyethylene glycol preferably used has an average Molecular weight of about 300, but the molecular weight can range between 200 to about 1500; the polyethylene glycol is commercially available from Union Carbide Corporation under the designation "CARBOWAX".

The preferred polyamino functional silane is of the type such as it is described in U.S. Patent 3,560,543; it is commercially available from Dow Corning Corporation under the trademark] ±> ezeichen "Z-6O5O". Other polyamino-functional silanes are commercially available available from Dow Corning Corporation under the trade designations "C-600", "Z-6O2O", "Z-6O26" and "Z-2-2023" and from Union Carbide Corporation under the designation

The gamma-aminopropyltrimethoxy silane is commercially available from Union Carbide Corporation under the designation "A-ILOO" and from General Electric Corporation under the trade designation "SC-3900".

Although preferred mixtures of silanes from Z-6O5O / A-11OO are

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have different silane mixtures than theirs Mode of action proven to be satisfactory; these include Z-6050 / Z6O2O and Z-6050 / C-600, all commercially available from Dow Corning Corporation.

The cross-linked polyacrylamide polymer is a gel agent or a thixotropic agent and is commercially available from the Dow Chemical Company under the designation "XZ-13OO". Other gel remedies that work in the same way and that are found to be satisfactory include methyl cellulose sold under the trade designation "METHOCEL" by Dow Chemi- ■ car company, as well as under the trade name "NATROSOL", a hydroxyethyl cellulose, commercially available from Hercules Corporation. Additional thixotropic agents that found to be useful in the sizing composition of the present invention include "CARBOPOL", a carboxyvinyl polymer commercially available from B.F. Goodrich Chemical Company and "AVICEL", a microcrystalline cellulose commercially available from F.M.C. Corporation.

The lubricant is preferably ¹¹ TWITCHELL 7440 "commercially available from Emery Industries Inc. This material acts as a processing aid for post-molding operations. Other materials that have been found suitable for these purposes include" TWEEN 85 "and" TWEEN 65 ", the former being a polyoxyethylene sorbitan trioleate and the second being a polyoxyethylene sorbitan tristearate, which can be used alone or in combination. Also" X-1104 ", commercially available from * Quaker Chemical Company and stearic acid work as desired.

Various types of polypropylene are commercially available as an aqueous solution Manufacturers available. ^

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If glass fibers are treated with those according to the invention during the molding process Compositions, then this leads to processed glass fibers that have only low losses on ignition, which in the Of the order of 0.1 to 1 percent by weight. The preferred range of ignition losses or losses is applied Strand solids at 0.24-0.32. The glass threads or fibers forming the strand can, if they are combined with the inventive Sizes are coated, easily separate so that better and more complete penetration of the fiberglass strand in the subsequent treatment steps an impregnation or coating of the strand with neoprene is possible, so that in this way a fiberglass strand filled with neoprene can be produced. The size mixtures according to the invention result, after their application on the glass fibers, a strand on which rubber rubber or other elastomeric compounds attach firmly.

After sizing and drying, the glass fiber strand has a coating, the components of which are expressed in percent by weight With reference to the weight of the fiberglass and the coating, the following are:

Example V

Components

Polyethylene glycol Polyamino functional silane Gamma-aminopropyltrimethoxy silane Thixotropic ingredient Lubricant Solid emulsion of polypropylene

Weight percent O.006 - O.06 O.OO5 - 0.05 0.005 - 0.05 0.015 - 0.15 0.019 - 0.19 O.O5O - 0.50

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Example VI

Components

Polyethylene glycol
Polyamino-functional silane Gamma-aminopropyltrimethoxy silane Cross-linking polyacrylamide polymer Long-chain fatty acid derivatives Solid emulsion of polypropylene

Example VII

Components

Polyethylene glycol
Gamma-aminopropyltrimethoxy silane Cross-linked polyacrylamide polymer Long-chain fatty acid derivatives Solid emulsion of polypropylene

Weight percent

.006 - 0. 06 .01 - 0. 10 .015 - 0. 15th .019 - 0. 19th .050 - 0. 50 0.0160 0.0135 0.0135 0.0405 0.0517 0.1350 Weight percent 0 0 0 0 0

Examples VIII

Components

Polyethylene glycol
Gamma-aminopropyltrimethoxy silane Cross-linked polyacrylamide polymer Long-chain fatty acid derivatives Solid emulsion of polypropylene Percentage by weight 0.0160 0.0270 0.0405 0.0517 0.1350

The unique combination of a polypropylene emulsion with an organosilane or a mixture of organosilanes in the Mixing of sizes leads to unexpected results which have not been achievable until now. As the elastomeric impregnation agent is highly alkaline (a pH of about 11.0) it counteracts destroying the bare, i.e. unsized glass fibers.

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However, if the glass fibers are coated with the size prior to application of the elastomeric impregnating agent, then the glass fibers are protected. Moreover, it is believed that the sizing mixture play a major role in obtaining an enhanced compensation or balance with regard to the tensile and adhesion values in the reinforced elastomeric matrix. In some circumstances these phenomena can be elucidated by the fact that the size controls the behavior of the various effects that can occur at the glass-size-elastomer interfaces.

Admittedly, the behavior of the size on the glass fibers does not completely covered, but theoretically it is assumed that the size not only with the rubber or. Rubber impregnation agent, but also with the rubber or rubber matrix to be reinforced reacted.

Furthermore, with reference to the results that were not to be expected when using the size mixture according to the invention it can be determined that the durability and service life of the subsequently still impregnated glass fiber bundle are essential Compared to other impregnated bundles in which the same elastomeric impregnation agent but different Finishing was used. The life and durability, as mentioned above, relates in particular on signs of aging and the storage life of impregnated glass fiber bundles under humid conditions.

If one speaks of unexpected results and results, one must not overlook the fact that the mixture of sizes gives the sized strands, bundles or yarns made of glass fibers an extremely high processing efficiency. For example the new sizing means that fraying, fraying as well as breaking and rubbing during the educational

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Process of glass fibers eliminated after the following processing operations, in addition, physical properties were found to be extremely uniform per unit length of the treated Glass fibers, especially with regard to the tensile strength and the adhesion of the glass fibers.

Although, instead of polypropylene, other resinous materials are used can be used as a film former in the size mixture, for example epoxy, polyester, polyolefins, etc., the most balanced ones are obtained due to the use of polypropylene Results related to processing properties and the properties of the end product.

Due to the fact that polypropylene has reactive groups for a subsequent reaction with the elastomeric impregnating agent are absent, the use of polypropylene in the size according to the invention is unexpected and neither is it from either side suggested. Usually the size active hydrogen or amine groups are available to match the methylol groups of the RFL resin to react during vulcanization. Because of the lack of reactive sites on the polypropylene leads to its use in a size mixture to better processing properties and different physical properties than the other film formers.

The nominal strand solids content of the size on the glass fiber bundle should preferably range between 0.24 to about 0.32 percent by weight. Is the solids content greater than 0.32% by weight, this leads to a grain or streaking of the subsequently impregnated strands, which Strands then have a tendency to adopt a flat shape compared to a circular cross-section, the physical one However, properties remain essentially unchanged. If the solids content is less than 0.24%, then this is

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Appearance of the subsequently impregnated strands good, i.e. there is no grain, but the physical properties such as tensile strength and adhesion tend to be to decrease. Nevertheless, the working limits with regard to the solids content of the size on the glass fiber strands can be vary in the range between 0.1 to about 1 weight percent depending on the intended end use.

The sized fiberglass strand is preferably dried to a moisture content of about 0.0 to about 0.20. Drying can be done by means of gas, electrical, dielectric or microwave ovens. Above In this specified range, physical properties such as tensile strength and adhesion will become uneven and decrease themselves in their worth. Nevertheless, it is possible to coat the sized strand with an elastomeric material while it is wet impregnate, i.e. while it has a moisture content of about 0.20% and above, for example, usually however, the physical properties then show a decrease / however this is sufficient for some applications.

The strand of sized glass fibers can be processed with the help of conventional twist arrangements in order to introduce additional twists into the strand and / or it can by means of conventional Cord processing assemblies are treated to make cords or yarns plied from the fiberglass yarns. at the twisting process (twisting) can have a number of entanglements or twists, for example eight twists are introduced per two and a half centimeters, but it is also possible in the twisting process, a number of ends, for example bringing together three or nine ends with or without subsequent stranding or piling in the manufacture of cord. During processing to form cord from the

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The cord can be made of flat or twisted yarns made of glass fibers l-3-strand or l-9-strand or l-9-3-strand can be produced. '

The slaughtered fiberglass strand can also be used without the mentioned mechanical processing operations before impregnation of the strand can be processed with an elastomer.

It is desirable to have such a complete impregnation of the sized strand or bundle of glass fibers as possible. Under these circumstances, he bears extraordinary large proportion of the surface area between the individual glass fibers and the coating of the elastomer Material is defined, to the frictional resistance to relative movements or increases this, in such a way to a large extent that there is sliding between the coating of the elastomeric matrix to be reinforced and the treated glass fibers is encountered. This additional resistance to relative movement acts in addition to the improved Binding relationships that exist between the layer or coating the elastomeric impregnation agent and the sized glass fiber surfaces and which is achieved in accordance with the features of the invention. Therefore affect the treated Glass fibers are essential, the physical and mechanical ■ properties ten of the elastomeric system and ensure extremely good reinforcement in the elastomeric product. Further contributes to the friction conditions just described the twisting and / or the plying, which subsequently has been attached in the glass fiber structure, so that in this way too a sliding of the fiber in the elastomer Shell is fought.

As already stated above, the molding size mixture according to the invention is one that consists of

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are extremely well suited to opening the sized strand or the sized fiber optic bundle in order to to allow a more complete impregnation and penetration, resulting in an improved one with an elastomer coated glass fiber strand, yarn, cord or fabric. The impregnation or coating of the elastomeric Treatment mix can be enhanced by a technique of bending and bending the fiberglass strand or bundle while this is in the bath of the treatment material or while it is still wet from the treatment mixture, whereby one then, for example, lets the fiber optic bundle run over rods, strips or other bending and deflection arrangements. Instead of from this or in combination with it, the impregnation can also be improved and promoted due to the use of printing forms or due to the passage of the fiber optic bundle by molding dies and arrangements that provide pulsations between high and low pressures so that the. mixture is incorporated into the bundle with simultaneous removal of trapped gases, or by removing that from the impregnation mixture running wet and moist fiberglass bundles through a series of shapes that allow for alternate narrowing and expansion of the strand to open it, or by ultrasonic vibrations during the impregnation process and on it uses based techniques to incorporate the waterproofing agent.

It will be understood that the impregnated glass fiber bundle is the final product of manufacture can be used, or as an intermediate in combination with an elastomeric matrix, without Twisting, plying and cording or with twisting, plying and cording to form yarns or cords.

In the structure formed in this way, the fibers are

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Due to the elastomeric material, they are cushioned and cushioned against each other. This allows a high flexural strength or, bending stress, while at the same time destruction and damage of the glass fibers through mutual friction is kept small or eliminated so that it is possible for the individual fibers, in terms of strength, dimensional stability, inertness and any lack of. Contribute to fatigue of the elastomeric product. At the same time, however, the fibers in the system can shift enough to bring more fibers into alignment to bring others, so that tearing or breaking of the glass fiber reinforced product is resisted, so that the Tear and burst strengths can be increased considerably.

If the glass fibers are impregnated or coated with an elastomeric material and used as an end product, for example in the form of a strand, yarn, a textile product or a cast and pressed material produced therefrom, then the elastomeric component can be cured into a or vulcanized state. However, this product is used as a component in conjunction with a matrix an elastomeric material used, such as in the manufacture of coated products, fabrics or Webbing, belt products, tubes, tires or laminates or other elastomeric materials reinforced with glass fibers Products, then it is desirable that the elastomeric component of the coating be in a state just before fully vulcanized or cured state remains, so that it is possible, the elastomeric coating of the fibers with the Elastomer of the matrix during the subsequent curing or vulcanization to produce an elastomeric product to mix or otherwise connect in an integral way,

The treated glass fibers can be used in the manufacture of glass fiber

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reinforced elastomeric products embedded in a matrix of elastomeric material in any desired arrangement will. If the glass fiber component is covered by the elastomeric material, then it is possible to use the individual glass fibers incorporate into the matrix of the elastomeric material with very little or no delimitation between the elastomeric materials Coating of the glass fibers and the elastomer of the matrix, so that there is essentially complete uniformity or homogeneity of the elastomeric material is maintained. The glass fibers can be substantially uniform over the matrix of the elastomeric material, caoutchouc or rubber and the like. Be distributed without a similarity determination with reference to the original shape with which the glass fibers are embedded is possible and in contrast to the usual concentration of glass fibers in bundle form.

Furthermore, instead of cords or yarns of fibers coated with an elastomer, it is also possible to use individual fiber strands to be used as a reinforcing component in the elastomeric system. Instead of having the fibers in a single layer inserted between an Ädhäsionsschicht and an outer cushioning layer, the coated with rubber or rubber Fiberglass components also plied, folded or as a cover or in any other way between other layers of an assembled one elastomeric material are arranged, so that one has a uniform distribution of the reinforcing glass fibers both in terms of the thickness as well as with respect to the cross section of the glass fiber reinforced elastomeric structure produced.

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Claims (12)

A 39 511 m a - 123 May 18, 1972 - 29Γ as patent claims: 1. Glass fiber reinforcement for a glass fiber / elastomer product, consisting of a bundle with a large number of glass threads, with a first coating of the glass threads for protection against mutual abrasion and with a second coating having an elastomeric composition, wherein the first and second coating can react with one another, characterized in that, that the first coating comprises the following components in percent by weight, Components . Weight percent Polyethylene glycol 0.006 - 0.06 Polyamino functional silane 0.005-0.05 Gamma-aminopropyltrimethoxy silane 0.005-0.05 Cross-linked polyacrylamide polymer 0.015-0.15 Long-chain fatty acid derivatives 0.019 - 0.19 Solid emulsion of polypropylene 0.050 - 0.50 2. Glass fiber reinforcement according to claim 1, characterized in that the elastomeric composition comprising second coating consists of an aqueous system, with the following solids, 2-10 parts by weight of resorzinol-formaldehyde resin, 20-60 parts by weight of a butadiene-styrene-vinylpyridine terpolymer, 15-40 parts by weight of a latex, selected from a copolymer of vinyl chloride-vinylidene chloride, a carboxylated butadiene-styrene copolymer and a group comprising a polymethyl methacrylate resin and 5-30 parts by weight of an incompatible one microcrystalline paraffin wax. 209851/1189 A 39 511 m a - 123 May 18, 1972 JM 3. Glass fiber reinforcement according to claim 1 or 2, characterized in that that the first coating comprises the following components in percent by weight, ■ Ingredients percentages by weight Polyethylene glycol 0.0160 Polyamino functional silane O.0135 Gamma-aminopropyltrimethoxy silane 0.0135 Cross-linked polyacrylamide polymer O.O4O5 Long-chain fatty acid derivatives 0.0517 Solid emulsion of polypropylene 0.1350 4. Glass fiber reinforcement according to one of claims 1 to 3, characterized in that the first coating is as follows Comprises components in percent by weight, Ingredients percentages by weight Polyethylene glycol 0.006 - 0.06 Gamma-aminopropyltrimethoxy silane O.Ol - O.10 Cross-linked polyacrylamide polymer 0.015-0.15 Long-chain fatty acid derivatives 0.019 - 0.19 Solid emulsion of polypropylene O.O5O - O.50 5. Glass fiber reinforcement according to one of claims 1 to 4, characterized in that the first coating is as follows Includes components, Ingredients percentages by weight Polyethylene glycol O.0160 Gamma-aminopropyltrimethoxy silane 0.0270 Cross-linked polyacrylamide polymer 0.0405 Long-chain fatty acid derivatives 0.0517 Solid emulsion of polypropylene O.135O 209851/1 189 A 39 511 in a - 123 May 18, 1972 atr «6 6. Glass fiber reinforcement according to one of several of the claims 1 to 5, characterized in that the glass fiber bundle coated with the size is used for subsequent impregnation the sized glass fibers can be opened with an elastomeric material. Ingredients ' percentages by weight Polyethylene glycol 0.006 - 0.06 Polyamino functional silane 0.005-0.05. Gamma-aminopropyltrimethoxy silane 0.005-0.05 Cross-linked polyacrylamide polymer 0.015-0.15 Long-chain fatty acid derivatives 0.019 - 0.19 Solid emulsion of polypropylene 0.050 - 0.50 7. A method for producing a glass fiber reinforcement for a glass fiber / elastomer product with improved mechanical and physical properties according to one or more of claims 1 to 6, characterized in that the glass fibers are provided with a protective layer and the individual coated glass fibers are combined into a glass fiber bundle that the glass fiber bundle with an elastomer Material is impregnated, the first protective coating having the following components, Ingredients percentages by weight Polyethylene glycol 0.05 - 1.50 -Polyamino functional silane 0.08 - 1.30 Gamma-aminopropyltrimethoxy silane 0.08 - 1.30 Cross-linked polyacrylamide polymer. 0.10 - 2.00 Long-chain fatty acid derivatives 0.05 - 1.50 Solid emulsion of polypropylene 1.50 - 17.00 Deionized water rest on one hundred 209851/1189 A 39 511 m a - 123 May 18, 1972 QL 8. The method according to claim 7, characterized in that the first coating is dried at a temperature of about to 150 ° C for a time sufficient for the Coating is essentially dry and an essentially hater-insoluble film on the glass fibers is formed. 9. The method according to claim 7 or 8, characterized in that the first protective coating has the following components having, Ingredients percentages by weight Polyethylene glycol 0.12 Polyamino functional silane 0.20 Gamma-aminopropyltrimethoxy silane 0.50 Cross-linked polyacrylamide polymer O.3O Long-chain fatty acid derivatives 0.39 Solid emulsion of polypropylene 3.6O Deionized water rest on one hundred 10. The method according to claim 7, 8 or 9, characterized in that the first protective coating the following components having, Ingredients percentages by weight Polyethylene glycol 0.05 - 1.50 Gamma-arainopropyltriraethoxy silane 0.05 - 2.00 Cross-linked polyacrylamide polymer 0.10 - 2.0O Long-chain fatty acid derivatives 0.05 - 1.50 Solid emulsion of polypropylene 1.50 - 17.00 Deionized water rest on one hundred 209851/1189 A 39 511 m a - 123 May 18, 1972 11. The method according to claim 10, characterized / that the first protective coating has the following components having, Components . Weight percent Polyethylene glycol 0.12 Gamma-aminopropy1trimethoxy silane l.OO Cross-linked polyacrylamide polymer O.30 Long-chain fatty acid derivatives 0.39 Solid emulsion of polypropylene 3.60 Deionized water rest on one hundred 12. Use of the glass fiber reinforcements according to one or more of claims 1 to 6 for storage and reinforcement in an elastomeric matrix, the first and second coatings being exposed to heat to one another react and the elastomer matrix binds the glass fiber reinforcements to itself during curing or vulcanisation. 209851/1 189.