DE1569551A1 - Glass fiber reinforced plastic product of high strength and process for its manufacture - Google Patents

Description

Glass fiber reinforced plastic product of high strength and process for its manufacture. The invention relates to a glass fiber reinforced plastic product high strength and is based on known products of this chain, the have less than about 70% by weight of glass fiber. In addition to the bF, the Invention of a method for producing such a product has so far been successful There are only high strength values in such glass fiber reinforced plastic products achieve gu if the glass fiber content is at least 70 wt .-% be. wearing. For the most technologically advanced However, it is of particular importance that such products are used height.

Strength and relatively low. Manufacturing costs. to draw. The price of such plastic products is primarily based on the price of glass fibers and only secondarily after the price of plastic.

The invention is therefore based on the object of the production costs such glass fiber reinforced plastic products by reducing the glass content reduce it without compromising its strength; the increase in strength is another object of the invention.

The invention consists in that the glass fiber reinforced plastic product from about 0.33 to 0.60 wt .-% glass, from about 0.08 to 0.33 wt .-% filler @ b and Composed of the real heart O The fillers used are those based on silicate and / or those based on oxide of aluminum, titanium and / or zirconium.

Particularly favorable properties are achieved when after a further development of the invention, the @@ as and filler components together about 2/3 of the total product and the resin content is preferably 1/3 of the weight. Among the resins to be used see be. ' special epoxy resin, hydrocarbon resin and polymetine acrylic resin proved to be very suitable. The strength is then special large if boving strands are used as the glass fiber component. The grain size of the filler should be less than 10 / u if possible.

Combining glass fiber with epoxy resin to form laminates is essential at already known. Glass fibers are pre-impregnated with silanes. The strength however, such products leave something to be desired.

The inventor makes use of this known state of the art, in that the fillers used in the invention are mixed with the resin cover with a silane coating @erden. Vinylsilane is particularly suitable for this. This ensures that there is a very good bond between the filler and the resin comes about.

The invention allows with relatively low manufacturing costs relatively high-strength plastic products, for example in the form of drilling or Plates that are manufactured0 are particularly suitable for a silane pretreatment good silicate-based filler that has been obtained naturally or artificially are. Debei comes in @ special ground quartz in question. But other minerals are also possible suitable, which have a high Sio2 content, It is also possible to use vinylsilane esters to be entered directly into the resin.

In addition to @illkatischen substances, substances based on aluminum can also be used. So aluminum oxide or silicified minerals of aluminum can be used. To be added Substances such as titanium dioxide or zirconium dioxide, or substances containing such compounds.

Allc fillers are in particular with a solution from a sclmell volatile solvents, e.g. toluene or acetylacetate, which are organic Liquid no particularly 0.1 to 10 parts by weight of vinylsilane ester be @ given are.

Product A 172 has been approved for use with polyester resins proven by Union Carbide USA. For the epoxy resins, the A 1100 from the same company.

For 100 grams of the fillers there is usually 50 gz of the mixed solution applied. Here, the filler is mixed with the solvent by an agitator stirred and then the solvent is evaporated.

In some cases, especially when the grain size of the fillers is below 10 microns; it has been shown that the solvent can contain up to 10% vinyl silane ester to be added so that a particularly good adhesion is achieved.

It is also advantageous to add up to 30% of the respective solvent to the solvent add resin to be used. That Solvent must then be suitable for the respective resin type geo, for materials containing hydroxyl groups Eats it furthermore of particular influence when the solvent or the iron ore in addition Isocyanates are added. Here, especially the solid DESMODUR TT, DESMODUR R in liquid form or similar isocyanates from BAYER-Werke, Levarkusen, suitable.

The fillers prepared in the above manner are treated with dsm Resin mixed and then processed in the usual technique.

For the strength of the material to be manufactured, the exact Wetting of the glass fiber with the rz is of decisive importance. The best materials are manufactured with the following process: 1.) In the manufacture of pipes runs the boving thread through a drinking trough 1, which is only a resinous bottle without filler contains. The boving then runs through a soaking tub 2 which contains the resin mixture With the pre-treated fillers it contains excellent impregnation of the roving strand, the can contain up to 60 single threads, and at the same time, its surface becomes reactive with the filler in the 2nd impregnation bath Condition and the resin provided.

27) In the production of panels or moldings of any kind The mats or fabrics are first made from fabrics or mats in a watering tub soaked with the prepared resin mixture without filler and then is the fabric or the mat in a second containing the filler and resin Give away the bath a second time with the resin filler mixture.

Rs is also possible after soaking the filler in the first bath mix between two lengths of fabric or mats. to delete.

The further processing of the panels or moldings prepared in this way takes place in known technology.

The particular advantage of the double impregnation process is that one Faster machine production for drilling, profiles, plates and containers by the preparation of the filler and the type of impregnation process the highest mechanical strength with reduced @ Gl @@ - fiber content guaranteed lot While with cheap manufacturing and good mechanical Data always used the cheapest resin material to date, such as polyester resins It has now become possible by saving on roving or other glass thread material, although expensive; but to use high-quality resins for this. These include the epoxy resins already mentioned, as well as the cabbage enwas hydrogen and polymethacrylate resins.

The technician stands by the pre-treatment of the special fillers and the preferred method to be used Another advantage has been found that bodies produced in the winding process, in particular Pressure hulls can withstand increased pressures because the pretreated fillers are in between the boving strands or glass threads form solid bridges that close any pores and are mechanically stronger than the solid resin alone.

For example, the procedure is as follows: Example 1 Tränkwanns 1: Epoxy resin "Araldit 533" (CIBA) 40 parts by weight of polyamide "Versamid 125" (Schering) 60 parts by weight of N-aminoethylpiperazine 4, 4.5 parts by weight That N-Aminoäthylpiperazin (supplier: Brenntag, Mühlheim-Ruhr) is added to the Versamid, With this product the viscosity can be adjusted, the product works also as an accelerator, of course other acceleration systems can also be used and extenders, such as Cardolit 513, supplier: Lehmann & Voss, Hamburg Mod-Epox, supplier: W. Köhnk, Hamburg DMP 30, supplier: O, Krahn, Hamburg.

Instead of Araldit 553, other epoxy resins, such as Epikote 815, 828 from Shell-Chemie Frankfurt or similar products from other companies will.

Soaking tub 2: Component A epoxy resin "Araldit 553" 40 parts by weight Polyamide "Versamid 125" 60 parts by weight @ N-aminoethylpiperazine 7.5 parts by weight vinylsilane ester A 1100 1 part by weight of component B quartz powder 100 parts by weight of toluene 50 parts by weight of vinylsilane ester 1100 7.3 parts by weight for component B well mixed, the solvent evaporated and thnn in component A of the impregnation bed 2 registered. After good stirring, the final viscosity will be determined by the chemical Auxiliary center @ and the temperature are set. @s when winding pipes If the roving in the soaking tub 1 is already absorbing resin, a check is carried out to determine whether the intended Mixing ratio, in particular 1/3 resin, 1/3 glass, 1/3 filler is reached.

The final setting can either be achieved by wiping between Drinking tub 1 and drinking tub 2 are regulated or by a higher proportion of Component B in component A.

Example 2 With some types of resin it is impossible to use all filler to be accommodated in the drinking trough 2. Because of this, it has been found to be beneficial proven to distribute the filler with resin over several soaking tubs, whereby also can be worked with increasing filler content and the last tub at most Should contain 20 «of the entire filler @ close.

The use of several drinking troughs is also advantageous because because, for example, the boving cords, especially with more than 10 threads, have a soaking time of need at least one minute and the prescribed for fast-working machines Soaking time in several tubs can be adhered to better.

Example 3 In this example, the mixture from example 1, drinking trough 2, all of which are used for wetting mats in order to produce panels or hollow bodies. By increasing the reactive thinner and by making the appropriate setting the temperature can adjust the viscosity so well that the mats are full are soaked and then ka @ thärtend c the hot-pressed to work further are. in eresem example that the vinylsilane ester can serve as an extreme simplification is entered directly into the low-viscosity epoxy resin-polyamide mixture and that Quartz flour. is used without preprocessing. Overall, the mechanical ones remain Strengths lower than when using a double soaking process.

The technical progress of the process is undoubtedly in his Simplicity under evaluation of all knowledge, on the commercial and technical GRP products sector.

-Patent claims-

Claims (1)

P a t e n t a n s p r ü c h e 1. Glass fiber reinforced plastic product high strength with less than about 70% by weight glass fiber content by approximately the following composition: 0.33 to 0.60% by weight glass, 0.08 to 0.33% by weight Filler on a silicate basis and / or on an oxide basis of aluminum, Titanium and / or zirconia, the rest resin. 2. Kunstatoffprodukt according to claim 1, characterized in that the glass and filler content. add about 2/3 of the total product, 3. Plastic product according to claim 2, characterized by approximately the following composition: 1/3 part by weight of glass, 1/3 part by weight. Filler, 1/3 weight resin. 4 ¢ plastic product according to any one of the preceding claims, characterized characterized in that epoxy heart is used. 50 plastic product according to any one of the preceding claims, characterized characterized in that hydrocarbon resin is used. 6. Plastic product according to one of the preceding claims characterized in that polymethacrylic resin is used 70 plastic product according to a of the preceding claims, characterized in that boving strands are used as the glass fiber portion are used. 8. Plastic product according to one of the preceding claims, characterized characterized in that the grain size of the fillers is less than 10 @ u act 9 process for the production of glass fiber reinforced plastic products according to one of the preceding Claims, characterized gekennzichnet that the fillers before mixing itt the quarrels one. Silane coating can be provided. 10. The method according to claim 9, characterized in that the fillers covered with vinylsilene. 11. Verfabr @ 2 according to claim 9 or 10, characterized in that about 2 parts by weight of fillers are impregnated with one part by weight of solvent. 12. The method according to any one of claims 9 to 11, characterized in, that a rapidly volatile solvent, such as Toluo, is used as the solvent and this is added up to 10 wt .-% vinyl silane ester. 13. Method according to one of claims 9 to 12, characterized in that that up to 30% by weight of the resin used in each case is added to the solvent will. 14. Process for the manufacture of glass fiber reinforced plastic products according to one of claims 1 to 8, in particular according to one of claims 9 to 13, characterized in that when using hydroxyl groups containing Materials are added to the solvent or the Har @ isocyanate. 15 .. Process for the manufacture of glass fiber reinforced plastic products according to one of claims 1 to 8, in particular according to one of claims 9 to 14, characterized by the fact that the basic elements that consist of glass fibers, such as roving strands, Mats or fabrics, first with the mixture of hearts, which still kedne Contains fillers, and then soaked with a resin-filler mixture will. 16. The method according to claim 15, characterized in that the from Glass fibers existing basic elements are passed through several soaking tubs, the Geg @@ each have a higher proportion of filler above the previous drinking trough.