DE1494887B2 - Aqueous impregnation dispersion for glass fibers to be embedded in elastomeric materials and process for the impregnation of glass fiber bundles - Google Patents

Description

The invention relates to an aqueous impregnation dispersion for embedding in elastomeric materials Glass fibers and a method for impregnating glass fiber bundles with improved composite properties and improved performance of the glass fibers in reinforcing elastomeric products.

Among the term glass fibers as used in the present specification are the following Understand products: 1. Continuous fibers, as they can be obtained by rapidly pulling them off receives many hundreds of individual glass threads; Fiber strands that result when such continuous Glass fibers are grouped together in formation; Yarns and cords through braiding and / or twisting multiple strands;

ίο as well as fabrics and nonwovens made from such strands, Consist of yarn or cord; 2. discontinuous fibers (staple fibers) obtained thereby be that on many individual glass threads emerging from the bottom of a glass melting tank, an im

X5 angle of impacting water vapor or air flow directed downwards will; Yarns obtained by using such discontinuous fibers under the action of Gravity trickles onto a perforated surface, on which it unites to form a fiber strand which is then processed into a yarn; as well as woven and nonwovens made from such yarns discontinuous fibers; and 3. combinations of such continuous and discontinuous Fibers in strands, yarns, cords, woven and nonwovens made therefrom.

With the designations elastomers or elastomeric materials, as they are used here, are materials such as natural rubber in the hardened or uncured, vulcanized or non-vulcanized state, as well as synthetic organic elastomeric materials, such as butadiene-styrene copolymers, Butadiene-acrylonitrile copolymers, chloroprene, isoprene, neoprene, butyl rubber and Similar elastomeric polymers and copolymers, also cured or uncured, vulcanized or not vulcanized state.

The invention is particularly aimed at making better use of the favorable properties of glass fibers, such as their high strength, flexibility, thermal resistance, chemical resistance, inert behavior, electrical resistance and thermal conductivity directed when in conjunction with elastomeric Materials used as a reinforcing or stabilizing agent in the manufacture of drive belts, as reinforcing cords and fabrics to increase strength, durability, and strength Usability of rubber tires, as well as reinforcement and the like in others coated with elastomers Woven fabrics and molded parts made of elastomeric materials are used.

The French patent specification 1 094 829 describes the production of glass fiber reinforced molded parts from certain synthetic resins, preferably polyester resin, known, with the entire mixture for prevention a risk of breakage and, in order to achieve greater flexibility, also a certain proportion of a Natural rubber or synthetic rubber can be added. This addition can be in the form

öo be made from leaves, grains, powder or even in the liquid state. However, the starting material is always a synthetic resin which, reinforced with glass fibers, should have greater elasticity.
The US Pat. No. 3,081,195 describes the use of organosilicon compounds for coating glass fiber surfaces which are to be used in conjunction with synthetic resins.

3 4

Also the French patents 1 132 818 of the glass fibers as reinforcing elements in elasto-

and 1 356 819, more materials that can be used for glass fibers can be used much better.

Anchoring means can be removed if this is the.

Glass fibers are to be embedded in synthetic resins. Further embodiments of the invention are counter

Finally, the patent specification 26 022 of 5 was the dependent claims and laid down in these. Office for Invention and Patents in East Berlin The following are examples of the Ernoch a method for sizing glass fibers found on the basis of the figures in more detail become, in which in two different refined. It shows

NEN processes different materials on glass F i g .1 in a schematic representation of the production fibers are applied. It is in the io of continuous glass fibers and the essentials around anchoring means, the treatment following the setting,

Storage of the glass fibers in synthetic resin materials F i g. 2 shows the treatment in a schematic representation

to serve. of the optical fibers following the merging

In contrast to these known measures to bundles, strands, yarns, cords or straightened the invention relates to the embedding of glass 15 weave them according to the preferred practice of fibers in elastomeric materials, so generally speaking, to impregnate the invention,

in rubber or rubber-like products and F i g. 3 shows a cross section through glass fibers which

serves to achieve improved composite properties according to the method shown in FIG. 1 treated

of the glass fibers with these elastomeric materials. have been and

The invention is therefore based on the object, 20 F i g. 4 a cross section through a glass fiber bundle,

Indicate impregnation dispersions for glass fibers, which according to the in F i g. 2 treated

embedded in elastomeric materials.

and to create a process by which glass- Until now, the function of glass fibers was the

fiber bundles can be impregnated in such a way that neither continuous nor

their advantageous properties also on elastomeric 25 cut fibers to elastomeric materials.

Transfer products. have been given or incorporated into them,

To solve this problem, the invention is more or less based only on that of a filler and not of an aqueous impregnation dispersion for in elasto- those of a reinforcing, elastic-acting or stamer Materials to be embedded glass fibers and dissolve bilizing element. The result of this was this object according to the invention in that the mechanical and physical self-aqueous impregnation dispersion from a natural purchase that could be achieved with products, chuk latex, a resorcinol aldehyde resin and which are made of glass fibers with elastomeric materials If necessary, a silicon-or- had been combined as an anchoring means, only slightly if Ganic connection and a Werner Korn- were generally improved. It can be assumed that plex connection exists, in which the organic 35 the failure of the attempts, some of the very favorable The remainder, which in the case of the silicon-organic compound shows the properties of the glass fiber material better the silicon atom is bonded, or the carboxyl benefit, is to be found in the fact that the glass fibers as ato group around the central atom are not able to interact with the elastomer Chromium of the Werner complex coordinated system to connect to a sufficient extent, contains an amino group or an epoxy group, 4 ° In recent years, numerous sub- and wherein the anchoring means has been carried out with a quantity search with the aim of a proportion in the range between 0.1 and 5.0 percent by weight. Possibility of better utilization of the in elastoin the dispersion is included. mere materials incorporated glass fiber composite

To find a method according to the invention for impregnating in order to thereby be able to of fiberglass bundles is that the top 45 products with better physical and mechanical surfaces to be able to produce the individual glass fibers initially with one see properties. A thin Overlay of a usual, anchoring essential progress in this direction could now agent-containing lubricants are coated, can be achieved by the present invention, such as and that then emerges from a multitude of summarized from the following description. Glass fiber existing fiber optic bundle with a die 50 The invention is based on a new and Components of natural rubber latex described in connection with better impregnation dispersion, which - as a dispersion of a resorcinol-formaldehyde resin originally - as a lubricant for application containing impregnation mixture is impregnated on the glass fibers used in the manufacture or that the individual can become a bundle of glass fibers so that these are then combined into strands Combine glass fibers with a coating of 55 genes, yarns, cords or fabrics the constituents of natural rubber latex are processed, individually a coating from the binding obtained with a dispersion of a resorcinol form impregnation dispersion, whereby both the veraldehyde resin and an anchoring agent whose work and behavioral properties achieved who share 0.1 to 5 parts by weight per 100 parts by weight of the ones used for processing the melted the combination of natural rubber latex and Re- 60 glass fibers into strands and for twisting and sorzin-formaldehyde resin is contained in the braiding of these strands into yarns and cords impregnation dispersion coated and dried. as well as for processing skeins, yarns and

In this way it is possible to achieve the binding relationships between cords and fabrics that are desired as well as the in the case of glass fibers, which are caused in combination with elastomeric behavioral properties, the one Materials for the production of glass fiber reinforced 65 cause good bonding when the melted glass plastics, Laminates or coated fibers in the manufacture of reinforced elastomers weaving used to considerably improve products combined with elastomeric materials furthermore, the high strength properties can be.

In the preferred practical embodiment of the present invention, the formulation is the impregnation dispersion given in the form of an impregnating agent, which is used to treat strands, yarns, Cords and fabrics that have been made from previously melted glass fibers can be used so that this dispersion penetrates the strands, yarns, cords or fabrics in such a way that that the fibers are wrapped individually and thus protected against breakage and mutual abrasion, wherein the dispersion combines with the glass fibers or the glass fiber strands, threads, cords at the same time or fabric penetrates in such a way that the glass fiber system is as completely as possible with the elastomeric materials connects with which the glass fibers for the manufacture of glass fiber reinforced, elastomeric products be combined.

The following examples are intended to reflect the basic concept of such an impregnation dispersion according to the invention and a method of treatment, e.g. B. for impregnating strands, yarns, Explain cords and fabrics made of glass fibers, whereby the fibers are previously used with a conventionally composed mixture have been melted, however, advantageously is modified by the addition of an agent that causes a better anchoring of the glass fibers.

Such mixtures are given below:

8.0 percent by weight of starch partially degraded to dextrin,

1.8 percent by weight hydrogenated vegetable oil,
0.4 percent by weight of cationic wetting agent

(Laurylamine acetate),

0.2 percent by weight non-ionic emulsifier,
1.0 percent by weight of y-aminopropyl-triethoxy-

silane,
88.6 weight percent water.

3.2 percent by weight of saturated polyester resin,
0.1 percent by weight fatty acid amine wetting agent, 0.1 percent by weight polyvinyl alcohol,

3.0 percent by weight pyrrolidine,

0.3 percent by weight of y-aminopropyl-triethoxy-

silane,

0.1 percent by weight glacial acetic acid,
93.2 percent by weight water.

0.2 percent by weight paraffin (solid) in an aqueous emulsion,

1.3 percent by weight of cationic amide poly-

ester resin,

2.3 percent by weight polyethylene glycol (molecular weight 300 to 400),

0.25 percent by weight gelatin,

0.5 percent by weight of y-aminopropyl-triethoxysilane,

0.1 percent by weight diammonium hydrogen phosphate,

0.2 percent by weight glacial acetic acid,
95.15 weight percent water.

In the in F i g. 1 arrangement shown schematically, the glass in a glass melting furnace 10, the bottom of which is provided with a trough-shaped recess 12, made molten. The bottom of the tub-shaped recess is perforated like a sieve, so that the molten glass is under the effect the force of gravity flows down through the many openings in the bottom of the tub 12 and thereby a corresponding number of threads 14 forms, which are quickly drawn out into thin glass fibers 16 by these are wound onto a rapidly rotating drum 20. The fibers 16 are with one of the Melted mixtures given above and then combined to form a strand. For this purpose, an application device 22 is provided, which is shown in the figure as a wiping pad is that is constantly soaked with the melt to be used in the production. The single ones Glass fibers are each coated with the sap for themselves, while they are used to form a strand 18 which is then wound onto the drum 20.

The melted strands are then allowed to air dry; the drying of the thin coating layers can also be achieved by applying elevated temperatures, e.g. B. one in the range between approximately 65 and approximately 120 ⁰ C, are accelerated. The applied mixture forms a very thin coating 24 on the surface of the glass fibers 16, and gives it a balanced degree of lubricity and binding capacity without impairing the fiber character or the appearance of the fibers.

The strand 18 of the fused glass fibers is preferably used together with other strands processed and twisted into yarns, threads or cords, which are used as reinforcing elements for elastomers Materials can be used and for this purpose left in their full length or in Shorter sections are cut up or processed beforehand into woven or non-woven nonwovens can.

After the fibers are made into strands, yarns, cords or fabrics, which are hereinafter generally referred to as Bundles are referred to have been processed, these bundles of melted fibers are according to the invention impregnated with an impregnation dispersion, the general composition of which is given below Example is explained:

B e i s ρ i e 1 1 (

40 to 80 percent by weight of a mixture of natural rubber latex with an aqueous dispersion a resorcinol-formaldehyde resin with a solids content of 38 percent by weight, 60 to 20 percent by weight Water.

B e i s ρ i e 1 2

60 percent by weight of a mixture of natural rubber latex with an aqueous dispersion of a Resorcinol-formaldehyde resin with a solids content of 38 percent by weight, 40 percent by weight Water.

Impregnation with the aqueous impregnation dispersion of Examples 1 and 2 is preferred made with a wiper sleeve; however, it can also be carried out using another conventional impregnation process be carried out, such as B. by dipping the glass fiber bundle in a bath of the aqueous Impregnation mixture. According to the illustration in FIG. 2, the glass fiber bundle 32 is passed over a guide roller 34 deflected downwards so that it gets into the bath of the impregnation dispersion. Then that will Bundles guided around rollers 36, so that there is a sharp bend at which the bundle spreads,

whereby the penetration of the liquid impregnation dispersion into the bundle of the melted fibers is facilitated will. After leaving the bath, the impregnated bundle is passed through a sleeve 38, which excess impregnation dispersion brushes off the bundle before this over as an endless structure a roller is fed to an air drying oven 40, the temperature of which is preferably above temperature of the environment, for example between about 65 and about 175 ° C, in order to remove the To accelerate the aqueous diluent and to set the solids of the impregnation dispersion bring to. The drying only takes a relatively short time, e.g. B. 1 to 30 minutes, among others depending on the temperature of the oven.

It is desirable to impregnate the bundle to such an extent that the individual fibers eventually are separated from one another by a layer of the solids contained in the impregnation dispersion, since the mixture of natural rubber and resorcinol-formaldehyde resin as a coating 42 on the melted Glass fibers act like a cushion and the fibers prevent damage from each other Rubbing protects. The better the impregnation dispersion has penetrated into the bundle, the more effectively it forms The bond between the glass fibers in the bundle and the elastomeric material will later develop which the glass fibers are combined to produce the glass fiber reinforced elastomeric product. In the finished product, the elastomeric material forms the continuous phase. This continuous phase The elastomeric material can consist of the same natural rubber that is used in the impregnation dispersion was applied, or may be different from this. It can be hardened or unhardened, vulcanized or unvulcanized form. The connection between the impregnated Glass fiber bundles and the elastomeric material, which forms the continuous phase, takes place primarily when the elastomeric material is cured or vulcanized in the course of the manufacture of the elastomeric material Product.

Even better protection for the individual glass fibers and more extensive embedding and binding of these fibers by the elastomeric material present as a continuous phase can be achieved by modifying the impregnating dispersions of Examples 1 and 2 so that they are used as a lubricant for glass fibers can, according to the in F i g. 1 to coat the individual glass fibers immediately after their production with it. For this purpose, the formulation of the impregnation dispersions of Examples 1 and 2 by adding an anchoring agent such as. B. modified y-aminopropyltriethoxysilane. Instead of γ-aminopropyl-triethoxysilane, the impregnating dispersion can also contain other organosilicon compounds as anchoring agents. Suitable organosilicon compounds of this type are those in which the organic radical connected to the silicon atom contains an amino group or an epoxy group, such as y-aminopropyl-vinyl-diethoxysilane, y- (triethoxysuylpropylamide) -propylamine, N - (y - triethoxysilylpropyl) - propylamine, β- aminoallyl-triethoxysilane, p-aminophenyltriethoxysilane or a Werner complex compound in which the carboxylato group, which occupies the coordination sites of the chromium (III-ion, which functions as the central atom) contains an amino or an epoxy group, such as in the aminopropylatochrome ( III) chloride, in the glycid chromium (III) complex, in the / 3-alanine chromium (III) complex and the like.

An impregnation dispersion to be used in the manufacture of glass fibers in the form of a lubricant, which takes these additional aspects into account, can be composed as follows:

Example 3

10 to 40 parts by weight of a mixture of natural rubber latex with an aqueous dispersion of a Resorcinol formaldehyde resin with a solids content of 38 percent by weight,

0.1 to 5.0 parts by weight of γ-aminopropyl-triethoxysilane (Anchoring means),

89.9 to 55.0 parts by weight of water.

B e i s ρ i e 1 4

15 parts by weight of a mixture of natural rubber latex with an aqueous dispersion of a Resorcinol formaldehyde resin with a solids content of 38 percent by weight,

3 parts by weight of y-aminopropyl-triethoxysilane,
82 parts by weight of water.

The impregnation dispersion of Examples 3 and 4 can be prepared in the same way as in F i g. 1 and in connection with those initially described for the formation of the fibers Liquor mixtures are applied to the surface of the freshly formed glass fibers. Both Impregnation dispersions of Examples 3 and 4 can be replaced by other aminosilanes for the anchoring agent or epoxysilanes or Werner complex compounds are replaced, which are in the carboxylato group, which is coordinated around the chromium (III) central atom, an epoxy or an amino group contain. The proportion of such anchoring agents in the impregnation mixture used for melting is in the range between 0.1 and 1.0 percent by weight and preferably in the range of 0.15 to 3.0 percent by weight of the total mixture or is between 0.1 and 5.0 parts by weight of the anchoring agent on 100 parts by weight of the total solids present.

If a separate lubricant mixture to be used in the manufacture of the fibers is used, the formed fiberglass bundles are then impregnated with an elastomeric impregnation dispersion, how they z. B. are illustrated by Examples 1 and 2, the recipe is to be used in the production Lubricant put together so that the solids content of the mixture between 0.25 and 3.0 percent by weight and preferably between 0.5 to 1.0 percent by weight in order to be dry weight the lubricant mixture applied to the fibers between approximately 0.5 and 1.0 percent by weight, based on the melted fibers. If, on the other hand, one is involved in the manufacture of the Fibers to be applied impregnation mixture is used, with which also an elastomeric component is to be applied to the fibers, as z. B. is illustrated by Examples 3 and 4, the must Solids content can be considerably higher, in the range between 10 and 50 percent by weight, with it a dry weight of the coating in the range between 20 and 45 percent by weight based on the

209 547/328

9 10

coated glass fibers. Is used for the elastomeric phase in combination with the pre-impregnation of the fiber bundles, in which the delten glass fibers in the cured or vulcanized fibers prior to the production according to the state where the coating or the listed mixtures have been melted, impregnation on the Surfaces of the glass fibers used an impregnation dispersion of the type as described in 5 or the glass fiber bundle, according to the present earths Examples 1 and 2, it is effective in such a way that the glass fibers recommendable, the solids content of the impregnation in adjust the continuous phase of the elastomeric dispersion to 10 to 50 percent by weight, embed the material and bond with it, so that the dry weight of the coating between As a result of this strong bond, a uniform 5 and 25 percent by weight and preferably between io Liches elastomeric product containing the glass fibers than 10 un d contains 15 percent by weight, based on the weight of the integral component,
of the fiber structure. It goes without saying that the impregnation

If the glass fibers are also used during production with a dispersion according to Examples 3 and 4 Mixture of the type described in Examples 3 and 4 to be applied to melted glass fibers melted, the fibers treated in this way can be used persion, since that is detachable in it to strands, yarns, cords and held anchoring means then a stronger one weave or nonwovens are processed, which deal with the bond between the continuous phase of the Let elastomeric materials combine without elastomeric material and the coated glass that this bundle causes a further impregnation of fibers.

require, since the individual fibers of these bundles already 20 From the above description it is clear that

are provided with a coating 50, the desired that the novel and better according to the invention

th components for anchoring the elasto- mixtures for treating glass fibers and

kidney material and bundles made from it for the protection of the glass fibers in the manufacture of

contains. fiberglass-reinforced, elastomeric products into one

The glass fibers or bundles of glass fibers, the 25 particularly good connection between the glass fibers

according to the practical instructions of the present and the elastomeric material.

Invention have been treated, become of course the invention is not limited to grain

Bination with the elastomeric materials these two mixtures of the type described and on the

mixed or in the process intended for the combination of their application for coating

nen arrangement limited to a different type in the elastomeric 30 glass fibers; rather, it extends

Material introduced or inserted, whereupon the application also indicates the use of the,

Order in the usual way by molding or pre-treated or impregnated fiberglass product,

Hardening under the action of heat and pressure or that with particular advantage for combinations with

further processed by vulcanization, the elastomeric materials are used.

1 sheet of drawings

Claims (5)

Patent claims: 1. Aqueous impregnation dispersion for glass fibers to be embedded in elastomeric materials, consisting of made of a natural rubber latex, a resorcinol aldehyde resin and optionally as an anchoring agent an organosilicon compound or a Werner complex compound, in which the organic radical, which in the case of the organosilicon compound is attached to the silicon atom is bonded, or the carboxylato group that acts as the central atom around the chromium of the Werner complex is coordinated, contains an amino group or an epoxy group, and wherein the anchoring agent in a proportion in the range between 0.1 and 5.0 percent by weight is contained in the dispersion. 2. Aqueous impregnation dispersion according to claim 1, characterized in that the resorcinol-formaldehyde resin is contained in a molar ratio of resorcinol to formaldehyde of 2: 1 and that the solids content of the dispersion is between 10 and 35 percent by weight. 3. Process for impregnating glass fiber bundles with improved composite properties and improved performance of the glass fibers in reinforcing elastomeric products, thereby characterized in that the surfaces of the individual glass fibers are initially coated with a thin Coating of a customary lubricant containing an anchoring agent and that then the glass fiber bundle consisting of a multiplicity of combined glass fibers with one of the components natural rubber latex in connection with a dispersion of a resorcinol-formaldehyde resin having impregnation mixture is impregnated or that the individual glass fibers combined to form a glass fiber bundle with a coating of one of the ingredients natural rubber latex in conjunction with a dispersion of a resorcinol-formaldehyde resin and an anchoring agent, its proportion 0.1 to 5 parts by weight per 100 parts by weight of the combination of natural rubber latex and resorcinol-formaldehyde resin is, containing impregnation dispersion coated and dried. 4. The method according to claim 3, characterized in that in the lubricant or the Impregnation dispersion containing anchoring agent an organic silicon compound or a Werner complex compound is in which the to the silicon atom of the organic silicon compound bound organic residue or around the chromium atom of the Werner complex compound coordinated carboxylato group contains an amino or epoxy group. 5. Use of the glass fiber bundle impregnated according to claim 3 for reinforcing elastomers Products.