DE1569468A1 - Sheet of thermoplastic material and process for its manufacture - Google Patents

Description

Turner Brothers Asbestos Company Limited

Plate made of thermoplastic material and process for its manufacture

Flat thermoplastic sheets are used for: deep-drawing processes and as cladding for walls and floors, for example to achieve a chlorine-containing polymer must be used, with polyvinyl chloride has been found to be suitable fire-resistant material which also has the advantage, is cheap and readily available to its This material, however, rigid only in unplasticized state _e

One method of manufacturing rigid, reinforced thermoplastic panels is to produce the thermoplastic material containing the reinforcing fibers in granular form and then to form the panel from the granules. Ideally, it should be possible to manufacture the panel by injection molding; However, the equipment required for the production of the largest panels is extremely expensive, so that in practice large panels and panels are produced by die casting. With this method you get a plate in which the fibers are evenly distributed, but according to aHen ^v

Directions of the hat are aligned. However, all fibers that are oriented perpendicular to the plane of the board, ie in the C-direction, do not increase the strength properties of the board and can in the given ^! Case even ^ worsen the Festigkeitseigenaohaften should ideally ..!, Directed all fibers in'der level of the thermoplastic sheet ■

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be. That being said, panels can be made by injection molding as a result of the uneven flow of the plastic material inside Exhibit tension. It is also impossible to make panels in which the reinforcement is made up of "long strips" because of the inevitable Fiber degradation that occurs during the injection molding process. Plates made from granules by injection molding are satisfactory hence the claims made generally not.

Another method of making reinforced thermoplastic Platten consists of using a cloth or a hat made of pasern impregnated with a solution or dispersion of the thermoplastic material; the final product obtained in this process is for another Deformation is not readily suitable, since the fabric or the mat made of the reinforcement material the necessary flow of the thermoplastic Material opposes a resistance. In addition, there are better properties when the thermoplastic material with individual Pipes, which are evenly distributed in the material, is reinforced, than when a fabric or mat is used. It is inevitable that many of the pasers in a fabric or mat will not be entirely in the Level of a plate, although in this case the alignment of the pairs is generally better than in panels that go through Injection molding of thermoplastic material in granular form.

Another known method of making reinforced thermoplastic Plates consists in the fact that a mixture of the thermoplastic material and Pasern on a multi-roll calender to one Roll out the sheet of the desired thickness. In this way you get a table in which the pastes are evenly distributed and well in the plane of the Chalkboard are aligned. The repeated action of the pressure of the calender rolls, however, often causes damage to the fibers} moreover With this method, too, panels or plates are obtained in which some of the fibers are aligned in the C-direction, since the thick ones Panels that are produced between the first calender rolls still have a significant proportion of pastes in the C-direction} these Part is not completely eliminated in the subsequent treatment between the other calender rolls. Purely the production of the starting j mixture, the reinforcing lines in general have to be

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mean to be mixed into a melt of the thermoplastic material; it can be very difficult to do one that way to obtain a good homogeneous mixture.

It is an object of the present invention to provide flat rigid panels made of a polymer material, which mainly consists of Consists of polyvinyl chloride and which flakes fibers used for reinforcement, where the polymer material is a product that is rigid at skin temperature in the unreinforced state. From such • fiber-reinforced polyvinyl chloride compounds can be used on draw calenders only then produce plates or panels if the polymer material has previously been mixed with a plasticizer} in this case one obtains but no longer rigid plates. On the other hand, it is plasticizer-free rigid polyvinyl chloride when heated only up to a highly viscous one Softened condition, it is impossible to make reinforcing fibers in a more satisfactory manner Way to incorporate into the melt. Such an attempt would severely damage the fibers and glass fibers in general be destroyed. The action of the calender rolls would then the breakdown of the fibers are further intensified, so that in the end, no useful reinforcement of the panel could be achieved. The articles previously made of reinforced polyvinyl chloride, e.g. floorboards (using the method described above) are all flexible, being either polyvinyl chloride together is used with a plasticizer or a priori from a polyvinyl chloride cit low melting point is assumed, which of ITatur is flexible.

The rigid plate according to the present invention consists of a Polymerniateriäl ', whose main component is polyvinyl chloride and which Contains reinforcing fibers. The polymer material used is at rlauoteiaperatur in a non-reinforced state rigid and the ^ jars, which are evenly distributed in the material., lie in the end product essentially all in the plane of the board. Such a board or Plate has good fire retardant properties and is suitable for both further deformation and also suitable for use as a building board.

In the manufacture of the panels or hats according to the invention, the Fibers mixed with the polymer material in liquid form, so that

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receives a dough-like mass. This mass then becomes rigid panels • available> fm ±. Bas polymer material, which is not reinforced at room temperature Condition is rigid, may contain little or no plasticizer. The material can be in the form of a solution or injected into a dispersion or as a mixture of these two forms. Any fibers, including glass fibers, can be incorporated into the polymer material for reinforcement can be incorporated as long as it is in a liquid state. By mixing the fibers with the polymer material in In the liquid state, a better distribution of the former can be achieved than when mixing into a melt of the polymer. The more homogeneous mixture also results from the fact that the fibers when using the polymer material better wetted in liquid form.

To produce the rigid board from the dough-like mass, one produces A thin laminate is continuously placed on a hot calender roll, which is then cut into sheets. The panels are from the Roller removed and solidify on cooling. If it is to be achieved that several successive laminates adhere to one another, it is necessary to that a certain degree of stickiness is retained. For this reason, at least some of the polymer material in solution must be volatile organic solvents are present. However, this poses a new serious problem since rigid polyvinyl chloride is not in any is soluble in common volatile organic solvents. According to the invention this problem is solved in that a part of the Polymer material made from a copolymer of vinyl chloride with another Monomers consists in volatile organic solvents is soluble. This copolymer is then used in solution in this solvent. Some copolymers of vinyl chloride and Vinylidene chloride are soluble in toluene} Such copolymers are preferably used in the context of the present invention. A Copolymer of this type is commercially available, for example, under the trade name “Breon 222”. Other copolymers suitable for The purposes of the present invention can be used are copolymers of vinyl chloride and vinyl acetate} in this case as a solvent, methyl ethyl ketone or a mixture of methyl ethyl ketone used with a hydrocarbon solvent. The "amount of Copolymerisates in the polymer composition for the production of the panels should should be kept to the lowest possible value, as the strength of the

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rigid polyvinyl chloride panels through the. Adding suffers j besides are those Copolymers more expensive than the simple vinyl chloride homopolymer. Pro ^ preferably the majority of the polymer material is in liquid form, as Dispersion or emulsion of the solid polyvinyl chloride in a plus Introduced into the mixture used to make the table, containing only a small amount of the copolymer of vinyl chloride and another monomer in solution in a volatile organic solvent is fed. ·

During this process it is necessary to ensure that one after the other Laminates adhere well to one another on the calender during manufacture, must at the same time for it. Care must be taken that the board formed in this way does not adhere to the calender roll and after completion of the manufacturing process can be easily removed from the roller. A suitable means which prevents the laminates from sticking to the calender roll, is water, which is usually in the dough-like mass that is used to manufacture serves as the liquid phase in the polyvinyl chloride emulsion is introduced. It is very difficult to control the amount of vinyl chloride copolymer to be kept precisely at the minimum which still ensures sufficient adhesion of the successive layers to one another and thus preserves the properties of the rigid polyvinyl chloride, without reducing the stickiness of the mass to such an extent that the Layer lifts off completely or partially from the calender roll, when further layers are applied. To avoid this difficulty, the rigid board is made according to the invention from two mixtures of different compositions. Me first laminates, 'which as Base layer can be called, are made from a mixture, which has a relatively high proportion of vinyl chloride copolymer contains and has such a composition that Adequate adhesion of the thin laminates to one another as well as there is sufficient adhesion of the first laminate to the calender roll, so that the layers are not completely or partially detached from the calender roll during manufacture, but can be removed from the roll without difficulty at the end of the manufacturing process. The remaining layers, which form the actual body of the plate, are made from a mixture which has a relatively low contains gen proportion of the vinyl chloride copolymer. The share in that The latter copolymer should only be so large (for practical

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Purposes as small as possible) that just barely has sufficient adhesion of successive layers on one another is achieved.

In order to avoid the presence of large amounts of water, the vinyl chloride copolymer is used according to the invention in a solution in which at least part of the vinyl chloride homopolymer is dispersed. For example, polyvinyl chloride powder or paste can be dispersed in the copolymer solution.

Sheets made predominantly of vinyl chloride homopolymer are if they are in an uncoated state, or thin enough for vacuum forming are quite brittle. To avoid this difficulty, the yinyl chloride homopolymer can be wholly or partly by one or several vinyl chloride copolymers can be replaced. Sin particularly suitable Material consists of a mixture of copolymers of vinyl chloride with vinylidene chloride and with vinyl acetate. These two copolymers are both soluble in no solvent, so the above for the production of panels from a mass consisting predominantly of polyvinyl chloride exists, the method described can also be used with the same success in the latter case, with a copolymer in solution and the other in dispersion. In a corresponding manner, the panels can be made from any other combination of copolymers in the presence or without the presence of vinyl chloride homopolymers provided that among the monomers making up the polymer mass as a whole. Vinyl chloride predominates and that at least one of the copolymers in a volatile organic solvent is soluble. When producing a board from a copolymer of vinyl chloride and vinylidene chloride and a second copolymer of vinyl chloride and vinyl acetate the copolymer with vinylidene chloride is preferably used as a solution in toluene and the copolymer with vinyl acetate is used in dispersion. Although a single dough-like paste can also be processed satisfactorily, according to the invention it is preferred to use two different pastes, one of which is the base layer and the other other forms the main layer (the so-called body) of the plate, in the same way and for the same reasons as in the above Manufacture of the board from polyvinyl chloride described. - Preferably, the dispersion of the vinyl acetate copolymer in the solution of the

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Vinyl ideiichlorid-His ^ polymerisates produced and separated as water Agents added to facilitate detachment. .. ·

The proportion of fiber material in the plate should be as high as possible seih and be at least 20 = f. The polymer material should be $ 40 to $ 70 the total mass of the plate. These percentages are it is the same as with all other information within the scope of the present invention by weight percent. -

Inorganic fibers give better strength than -organic fibers, so that the fiber material used wholly or predominantly, i.e. too much at least 90 5a, should consist of inorganic fibers.

For further deformation, for example by deep drawing, plates are required that can easily be brought into the desired shape. Since the reinforcement consists of fibers which can move freely in any direction during the drawing or deformation process, there is no obstruction as in the case of the use of fabrics or mats. The ability of the fibers to move freely increases the deformability of the panels. In order to achieve maximum deformability, the fibers should be short; on the other hand, longer fibers produce better strength properties Asbestos fibers can make up 20 to 100% of the total amount of fiber. Glass fibers are also suitable5, a mixture of asbestos and glass fibers can also be used. In general, the use of so-called opened asbestos fibers with a through-going length of 0.38 to 0.51 cm and the use of staple glass fibers with a length of 0.63 to 2.54 cm is particularly favorable. Mixtures of short fibers with longer fibers up to about 5 cm in various proportions can also be used. The use of such fibers achieves a noticeable increase in the strength properties without having to accept a reduction in the deformability of the panels produced. The longer fibers can consist of asbestos fibers, glass fibers or organic fibers. In general, 80 to 100 ψ of the inorganic fibers should be Fibers shorter than 2.5 cm and about 20 to 0 $ of the fibers between 2.5 and 5 cm long.For thin plates, which are then to be further treated in vacuum deep-drawing processes, asbestos fibers of class 5 are used, which are short. and have an average length of 0.15 cm. 109883/1312 'BAD ORIGINAL

Care must be taken in the production of the dough-like or pasty Hasse care should be taken to obtain a homogeneous mixture without degradation of the fibers. Since the polymer material is in liquid form, this can can be reached easily. The fluidizing devices used should not be have violent effects so that excessive degradation of the fibers is avoided will.

A calender of the type used, in which a large steam-heated roller and a smaller one water-cooled roller, which can be moved towards and away from each other, are provided. The pasty mass is in the crevice inserted between the two calender rolls and the distance between the two rolls is increased after each revolution, so that the mass in Form thin layers on the hot roller to the desired thickness is being built. The amount by which the distance between the rollers is Each turn is increased, determines the thickness of the individual layers. It is necessary that each individual layer be sufficiently dried before the next is applied, since otherwise an unusable panel is produced. As a result, each individual layer must be very thin; the thickness is preferably between 0.001 and 0.002.5 cm.

V / ground two different pastes used for the manufacture of the board, a sufficient quantity of the first ilasses is first introduced so that the base layers are formed. This is followed by the second Mass supplied from which the main layers of the plate are formed. Of course, one or more layers are partially made up of one Mixture and partially formed from the other mixture. In general, the layer formed from both mixtures is about 0.078 cm thick} in this case the base layer should be about 0.0075 cm thick and consist of 5 or 6 individual layers.

It is also possible to still use the plate made up of individual layers apply a top coat by making a suitable paste-like mass into the slot between the rollers as soon as the mass for the layers of the plate body is exhausted. This surface layer can from a resin mixture, a resin-fiber mixture or a resin-filler mixture exist. The top layer is used to create a hard one

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smooth surface after pressing and as a well-adhering base for any decorative vinyl covers that are applied during pressing will"

• In the form in which it is removed from the roller, the plate can have defects in the form of voids and residual material which impair the physical properties, transparency and, in general, the appearance of the plate. In this case, it is possible to reheat and press the plate to compact and polish it. This operation is generally carried out on a hydraulic press; however, it is also possible to pass the plate between heated and cold rollers. It is advisable to _: connect several plates produced between the rollers to form a stronger, rigid plate which can then be fed to further deformation. The compaction of the plate and the polishing of the surface can then be carried out together with the joining of the individual plates. "Preferably, four panels produced between the rollers" are layered crosswise on top of one another by means of ice pressing * 'At the same time, decorative coatings can be applied to the surface.

Because the paste hate between the calender rolls to form thin layers of skin is rolled out that are much longer than thick, it is impossible that align fibers of the C-direction; rather 'must all fibers in the practice the plate bsw. Blackboard lying. The minor one that is still there Heating oili ^ -er fibers within the individual layers can-be neglected will. With a sinselfc.ser length of 0.38. cm and a thickness of a * - A single fiber can only have layers of 0.001 cm at an angle of about 9 buoy minutes to the level of the board. This angle can be neglected. '\.

The method of the present invention is particularly advantageous in the processing of polymer masses, the fibers as reinforcement material included, since no degradation of the fibers takes place during calendering, and only a slight alignment of the fibers takes place, so that the strength egg plate is the same size in all directions, on the other hand in a certain direction increased strength can be achieved, so it is necessary, endless glass thread, e.g. monofilament, their. Length "of the whole Length of the plate, together with the polymer mass in the Sohlita

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to be introduced between the calender rolls. Such reinforced panels have a 'somewhat reduced deformability.

Example 1:

The following example serves to explain the manufacture of a rigid plate used both as such for appropriate purposes vein can be deformed in any shape »

68 kg of toluene, 29.5 kg of a copolymer of vinyl chloride and vinylidene chloride which is soluble in toluene, 4.5 kg. an oil solution of a copolymer of styrene and the diester of maleic acid with a CL - alcohol, which is available under the trade name "Alplmnol", 15.2 kg of a powdered vinyl chloride Iioaopolynerisär.tes, 3.2 kg of a mixture of Stabilizers for polyvinyl chloride and 11.3 kg of powdered talc as filler material are mixed together in a suitable sealing device, which ensures aininal damage to the fibers, the mixing process being approximately 45 minutes. is carried out. 15> 9 kg of an aqueous vinyl chloride latex with a solids content of 50 ° p was used as the aqueous phase. To about one third of the solvent phase in toluene, 47.6 kg of a solution of asbestos fibers of classes 3 and 4 were slowly added} this solution was then combined with the remaining solvent phase in toluene, whereupon the mixture 5 to 10 liters. was rested. The aqueous phase was then added, followed by an additional 2 or 3 Hin. mixed. After adding the pigment, the mixture was again 15 to 20 hours. touched. The paste-like mass was then ready for processing on the calender rolls, one; One mass was prepared in a similar manner, but the solvent phase was prepared in toluene by adding 65.0 kg of toluene, 9.1 kg of the vinyl chloride copolymer, 9.1 kg of the vinyl chloride copolymer. ⁴ Ό, 57.2 kg of powdered solid polyvinyl chloride, .5.6 kg of a stabilizer mixture for polyvinyl chloride and 11.3 kg of talc. The pasty mass produced first was introduced into the slot between two calender whales of the type described above and formed into a base layer with a thickness of 0.00 - 6 cm. The outer layer was then placed in the gap between the calender rolls and rolled out into a layer 0.0076 cm thick.

Four aolchor plates were connected to each other, so that a panel of _f 0; received 50 cm thickness, comprising the following 3i _ü enschrften aufwe / is:

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- - ■■ - - '■■ _ 11 -11 - .. ρ, s.i. = » 1569468 ρ 225 kg / cm Compressive strength ^: 1Oo500 kg / cm Tear resistance A direction 10,300 " 758 B-2 direction 19,700 724 Flexural strength A direction 15 200 159 B direction 1.4 χ 10 -
1.5 x 10 ⁶ : »■ 107 Young-Iodule A direction 1.9 x 10 ⁶ = 98 x 10 ^ B direction 1.2 χ 10 ^ö = 91 χ ίο ⁴ Bend I.Iod.ul A direction 134 χ ίο
Λ B direction .Ibs / i'nch B4.3C.10 ⁴ Notched impact .lbs / inch lceit (Edge) 1.6 ft 52 "000 psio - (Area) 5.2 ft

(Α and B refer to the corresponding axes of the sheet plane)

The aqueous phase of both pasty *! Mixtures may contain small amounts of other latices, although such admixtures reduce the strength of the board. The styrene-di- ^tt Alphanol ^u-maleate Mischpolyinerlsat dor.Lösungsphase is added which is used to form the base layer of the plate and is intended to increase the tackiness of the mass _e 0 (z, B _o a butadiene nitrile latex)

The following example shows the manufacture of a thin plate described, which are further processed in the vacuum deep-drawing process should ». ■: '- ■■;

Example 2:

40 parts of a copolymer of vinyl chloride and vinylidene chloride are dissolved in 150 parts of toluene. 8 parts are then added to the solution a stabilizer mixture and 26 parts of talc. In a nail mill this first mixture is then made with .80 parts asbestos fibers Class 5 and 120 parts of a copolymer of vinyl chloride and vinyl acetate mixed. The copolymer swells in the Mixture, but does not dissolve »Finally you add to the pas tosen ■ mass add 20 parts of Yfasser. *

This pasty © Masee is used to make the main layer, d «lr. to form the so-called body, a plate überr a Gründschicht that "from a mass which was beschrieberien in Example 1 and produced there for the same purpose type used. The plate wuir & EClick ^a! laminate calender prepared in the manner already described above, wherein the individual layers were each 0.0015 cm "thick and the finished panel was 0.15 cm thick,

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Claims (1)

Ί569468 - 12 PATENT CLAIMS 1, Rigid plate made of a predominantly polyvinyl chloride polymer material, which is rigid at room temperature in the unreinforced state and in which a reinforcing fiber material is evenly distributed so that all the fibers lie in or essentially in the plane of the plate _e 2 "Rigid plate according to claim 1, characterized in that the polymer material consists primarily of a vinyl chloride homopolymer «, 3 «Rigid plate according to claim 1 or 2, characterized in that the Polymer material also contains a copolymer of vinyl chloride and vinylidene chloride. 4t rigid plate according to claim 1 to 3, characterized in that the Polymer material also a copolymer of vinyl chloride and vinyl acetate contain 5. Rigid plate according to one of the preceding claims, characterized in that that the polymer material is 40 to 70 percent by weight of the plate matters. 6 «Rigid plate according to one of the preceding claims, characterized in that that the fiber material consists entirely or predominantly of inorganic fibers. 7. Rigid plate according to claim 6, characterized in that it is 20 to 100 percent by weight the inorganic fibers consist of asbestos fibers. 8. Rigid plate according to claim 7> characterized in that the inorganic Fibers consist of a mixture of glass fibers and asbestos fibers. 109883/1312 9 ″, method for producing the rigid plate according to claims 1 to 8, characterized in that the predominantly polyvinyl ■! Existing chloride, at room temperature in an unreinforced state rigid polymer material in liquid form and the fibers a.homo- ' . gene pasty mass produces by applying the same to a hot calender roller continuously produces superimposed layers, the laminate thus formed is cut into panels and the Removes the plates from the roller and lets them cool down 10 «Method according to claim 9», characterized in that the polymer material also contains a copolymer of vinyl chloride and another monomer, which in solution in a volatile organic Solvent is present " 11 «The method according to claim 10, characterized in that the copolymer consists of a vinyl chloride-vinylidene chloride copolymer ^. stands, which was present dissolved in toluene 12o method according to claim 10 or 11, characterized in that the Main amount of the polymer material made from a vinyl chloride homopolymer exists, which is present as a dispersion or emulsion in a liquid ,: is, while the remaining amount of the polymer material consists of a Vinyl chloride copolymer, which is in solution in a volatile organic solvent, 15 · The method according to claim 12, characterized in that the vinyl chloride. Homopolymer is emulsified with water, 14. The method according to claim 12, characterized in that the solution of the Vinyl chloride copolymer in the volatile organic solution, medium forms the liquid in which at least part of the vinyl chloride homopolymer is dispersed, 15 «The method according to claim 11, characterized in that the polymer material from a mixture of a copolymer of vinyl chloride with Vinylidene chloride, which is dissolved in toluene, and a copolymer consists of vinyl chloride with vinyl acetate, which is in the liquid is dispersed, BATH ORiGiNAL 109883/1312 ~ " "' I6o method according to one of claims 10 to 14 »ds, characterized in that that the initial layers on the hot calender roll from one pasty mass formed γ / earth, which has a relatively high proportion of Yinyl chloride-llischpolymerisat, while the remaining layers be formed from a mass which contains a relatively small proportion of yinyl chloride copolymer » 17 · For further processing according to claim 9 suitable pasty leaves, consisting of a fiber material and a polymer material in liquid Form, which is partly made of a vinyl chloride Honopolyiaerisat, which is dispersed in Y / water, and partly from a vinyl chloride / inylidene chloride copolymer which is dissolved in toluene » BATH 109883M312 *