DK142584B - Extrudable glass fiber reinforced resin based on a vinyl chloride or vinylidene chloride polymer. - Google Patents

Description

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(11) PUBLICATION REPORT 1 ^ 2584 DENMARK (ευ int.ci.3 c os l 27/04 § {21) Application No. 4092/75 (22) Filed on the 12th ββρ. 1975 (24) Race day 12. gep. '1975 (44) The application presented and. on the petition published on * * luv '

DIRECTORATE OF

PATENT AND TRADEMARKET (3 °) Priontet requested from the

Sep 15 1974, 7450989, PR

OD PRQDUITS CHIMIQUES UGINE KUHLMANN, 25 boulevard de 1'Amiral Brufx, "Paris 16, ER.

O2) Inventor: Alain Hermet, 4 rue Chateaubriand, 60100 Somewhere sur 01be, PR. "(24) Plenipotentiary in the proceedings:

Hofman-Bang & Bout Engineering Company (54) Extrudable fiberglass reinforced resin based on a vinyl chloride or vinylidene chloride polymer.

The present invention relates to an extrudable resin based on a homo or copolymer of vinyl chloride or vinylidene chloride or of post-chlorinated polyvinyl chloride and containing mineral filler, glass fiber and lubricant. The present resin may be extruded directly in the form of a powder.

The principle of reinforcing thermoplastic and thermosetting resins by means of glass fibers is well known. The incorporation of fiberglass significantly improves certain mechanical properties, such as the modulus of elasticity or heat deformation temperature.

In practice, the reinforced polymers are processed by a discontinuous operation by compression or injection presses, or by impregnation; the products obtained usually have a satisfactory appearance with a smooth surface, and indistinguishable glass fibers and shrinkage phenomena can be reduced or eliminated.

Furthermore, continuous processes are known which enable glass fiber reinforced tubes to be manufactured in two stages, in a first stage extruding a tube of a thermoplastic material under suitable known conditions and in a second step after the outer surface has been treated. to improve the adhesion, an outer winding is made using continuous glass fibers, using a binder to ensure the necessary cohesion between the glass and the thermoplastic material.

This method is used e.g. for making polyester-wrapped polyvinyl chloride tubes.

Apart from the fact that this technique comprises two steps and thus entails further processing, a heavy and complicated winding equipment is also used. The final mechanical properties of the tube are also significantly affected by the characteristics of the binder.

French Patent Specification No. 2,141,998 discloses fiberglass-containing polyvinyl chloride compositions, however, not intended for extrusion, but preferably for thin films for use as coatings. The films are made by extrusion, comminution and final lamination or extraction. The initial extrusion is intended solely to homogenize the constituents prior to the final lamination or extraction. The products referred to in the above patent also contain more than 300 parts by weight of mineral filler per kilogram. 100 parts by weight of vinyl resin, while the glass fiber content is less than 5% and preferably less than 1% of the total amount of material. Furthermore, the products contain from 22 to 66 parts by weight of a plasticizer, which is necessary for the high content of filler.

3 14258Λ

The products mentioned in the patent are not suitable for continuous extrusion.

Numerous attempts have been made to produce continuously extruded sections of fiberglass-reinforced thermoplastic mats.

rials. In all cases, regardless of the nature of the thermoplastic material, the sections have a rough surface condition which is easily distinguishable by touch and inspection, so that they are commercially unacceptable.

Furthermore, the sections inside are very porous, which means that the products obtained have some fragility in impact.

An extrudable resin has now been found which allows homogeneous reinforced articles having a satisfactory appearance and excellent stiffness to be manufactured in a single operation. This resin is obtained by a careful combination of the following four basic components: vinyl resin, fiberglass, mineral filler and lubricant.

The present invention thus relates to an extrudable resin which is characterized by the characterizing part of claim 1.

As used herein, "vinyl resin" means chlorinated polymers such as polyvinyl chloride, polyvinylidene chloride and post-chlorinated polyvinyl chloride as well as copolymers obtained from a chlorinated monomer and at least one copolymerizable monomer. The viscosity index of the vinyl resin according to ISO standard R 174 is between 50 and 180, especially between 70 and 120.

Useful mineral fillers for the present compositions are preferably calcium carbonate which may be precipitated and / or. surface treated, colloidal silica, hydrated alumina, minium oxides, calcined clay and aluminum silicates. The mean diameter of the elemental particles in the mineral filler should be 0.5-50 µm, preferably 0.2-10 µm.

The lubricants used can be selected from known lubricants, especially the group of fatty alcohols and acids, as well as esters of fatty alcohols 4 U2584 and acids, paraffinic waxes and low molecular weight polyethylenes which may be oxidized. Their melting points are preferably 50-140 ° C.

The glass fibers used are those which are recommended by the manufacturers because of their specificity in relation to the vinyl polymer used, and in particular are glass fibers cut to a small length, preferably 4-6 mm. This length provides a reasonable compromise between the efficiency of the fibers as a means of reinforcing the resin and its suitability for processing. If the fibers are too short, they only act as a filler without contributing to the strength of the finished material, and if they are too long, they are difficult to process by mixing and extrusion, and can result in irregular surfaces on the finished product.

The quantities in which to combine the various constituents of the resin are as set out in the claim: to 100 parts by weight of vinyl resin are added: a) 10-60 parts by weight, preferably 15-30 parts by weight of mineral filler with average particle diameter of 0.2-10 yun. This large amount of filler with a very fine granulometry, intimately mixed with the resin, improves the cohesion of the resin-glass fiber blend, with the further not unimportant advantage of lowering the cost of the product; b) 5-40 parts by weight, preferably 15-30 parts by weight of glass fibers. The addition of glass fibers to the product increases the modulus of elasticity of the base vinyl resin by 50-100%, and c) 1-5 parts by weight, preferably 1.5-3 parts by weight of lubricant. A single lubricant can be used, but preferably a mixture of two or three lubricants as defined above, at least one of which has a low melting point, which mixture must be compatible with the vinyl resin.

Although this large amount of lubricant is unacceptable by the known methods for extruding vinyl resins alone or with added fiberglass because it prevents any friction between the resin grains and thereby makes it impossible to obtain a homogeneous and complete melting, it has surprisingly been found, that this large dose of lubricant is needed in the present blend.

Such an amount of lubricant allows to intimately incorporate into the resin an amount of filler which is unusual for a product which does not contain plasticizer.

To the constituents of the present composition can be added the additives commonly used in classical extrusion methods, such as dyes, modifiers, stabilizers, etc.

The nature of the stabilizers incorporated in the product used to protect the resin from thermal degradation is immaterial. These stabilizers, which are used in appropriate amounts for each type of extruder, can e.g. be lead, barium or calcium soaps, derivatives of tin or phosphorus-containing products. It is also possible to incorporate plasticizers into the products, although not necessary.

The various components can be homogenized among each other in the usual way to prepare mixtures by extrusion. The order and addition of these components is not important. Nevertheless, it is preferable to pre-mix the various components apart from the glass fibers. In a quick mixer, the various components are stirred at a temperature below 130 ° C. After the mixture is preferably cooled to a temperature below 50 ° C in a slow mixer, e.g. a tape mixer, the glass fibers are incorporated into the resulting powder. This method achieves optimal homogenization and minimal mixing time.

The present resin allows for extrusion and in a single operation to produce reinforced articles such as profiles, tubes and other articles having improved properties, which may be mentioned to be free of internal porosity and have excellent stiffness and a smooth surface.

The invention is further illustrated by the following examples in which the parts used are parts by weight. Examples 1-5 are comparative examples, while the other examples illustrate the invention.

6 U258A

EXAMPLES 1-6

The composition of the product and the results obtained are given in the table below. Apart from the glass fibers, the various components are mixed together in a quick mixer for a sufficient time to obtain a homogeneous mixture while allowing the temperature to rise to 120 ° C.

The glass fibers are then incorporated into the mixture, which is cooled to 40 ° C in a slow tape mixer (Examples 3-6). Glass fibers are not added to the products referred to in Examples 1 and 2, but the products are otherwise processed in the same way as the products referred to in Examples 3-6. .

The mixture is extruded between 160 and 190 ° C in a single screw extruder with a diameter of 60 mm and a length of 1200 mm, the extruder being provided with a tool enabling the production of a tube with an external diameter of 32 mm and a thickness of 2.6 mm. The cooling means following the nozzle has a length of 300 mm and the calibration is carried out in vacuum.

EXAMPLE 7

Proceeding as in Examples 3-6, a mixture of the following composition is extruded: polyvinyl chloride, viscosity index 75 100 parts of dibasic lead phosphite 3 n dibasic lead stearate 1 "glass fibers, length 6 mm 20" calcium carbonate (average diameter 0.5 µm) 20 " 1,2-hydroxystearic acid 0.5 "

oxidized polyethylene wax, m.p. 105 ° C

0.5 "calcium stearate 0.5"

A porous-free tube having a smooth surface is obtained, with a Young's modulus at bending of 55-000 kg / cm and a heat deformation temperature of 81 ° C.

'ν' · /. EXAMPLE 8

Analogously to Examples 3-6, a mixture was prepared with the following composition extruded: polyvinyl chloride, viscosity index 105 100 parts tinbutyl mercaptide 1.5 "modifier" PLASTIFLO A01 "1": glass fibers, length 6 mm 20 "- in calcium magnesium aluminosilicate ( 0.2 "20" liquid paraffin 0.6 ", glycerol monostearate 1.2"

oxidized polyethylene wax, m.p. 105 ° C

0.3 "

A tube with a smooth outer surface and a Young's 2 module were obtained at bending of 60,000 kg / cm 2.

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