COLD SHAPING OF PVC, PP AND ABS OR MABS HALTIGEN POLYMERS

The available patent application refers to a procedure for the transfer of PVC, PP and ABS or MABS haltigen polymers into a condition of duktiler ductility by application of force as well as a procedure, with which following the transfer into the condition of duktiler ductility the polymers are transformed in a further step.

Styrolhaltige of polymers are used in a multiplicity of applications e.g. in the furniture industry or in the automobile industry. In particular styrolhaltige foils can serve for the protection and for the refinement of surfaces, for example can furniture, doors or Bilderrahmen, instead of a lacquer finish too be received, with a plastic foil cover (for example PermaSkin® procedures of the Anmelderin). Plastic foils are used also for the production of body parts (PFM® = paintless film molding the Anmelderin). A further example from the furniture making is the lining of furniture edges with Kantenumleimern, whereby for the Kantenumleimer frequently ABS or MABS haltige polymers and/or PVC are used.

In past procedures the foils are processed thereby below the glass transition temperature (TG) of the appropriate polymers. The foils are deformed in such a way with the fact that they adapt to the form of the underground. Depending upon mechanical load and/or application of force, i.e. bending angle and/or bending radius, so-called white break can occur with the deformation. Ranges with small hair-cracks (“crazes”) form, in which the polymer deformed insufficiently duktil. This Crazes is a reference to material failure beginning. Such zones can resist a further load or the attack of a shatter crack-releasing medium generally less.

In the context of the available invention by ductility and/or duktiler ductility of the polymers the plastic ductility of the polymers without the occurrence is understood about white break. Duktile ductility and/or ductility means that a material under application of force without the occurrence of disturbances or break can be deformed vividly.

With actually transparent polymers white breaking behavior shows up in the occurrence of gloomy ranges, with dyed foils visibly becomes white marks. These defects are for aesthetic reasons unwanted, in particular in an Design-oriented branch like the furniture making, particularly since they indicate material failure beginning. Usually the defects are eliminated by warming up, this can happen by means of irradiation within the infrared range. Lacking the moreover one the gloss can be impaired by ductility by polymers with strong surface gloss with shaping processes. Also here it concerns an unwanted and disturbing optical fault.

The deformation behavior of polystyrene below TG became of Meijer et al. examined (polymer 42 (2001) 1271; Polymere 44 (2003) 1171). They could show that polystyrene can be deformed after previous mechanical load for short time duktil. It concerns a temporary effect. Mechanical load existed in rollers of the sample test specimens, which led to a thickness reduction around 32%. With itself following compression tests the Schererweichung, which is called as a cause for the occurrence of defects with deformation, had nearly completely disappeared with the pre-treated samples contrary to the untreated and/or aged samples. With course stretch attempts the pre-treated samples could be stretched homogeneous around approx. 20%, until tearing entered, untreated or again aged samples tore with approximately 2% stretch, before the yield point was reached. Duktiles flowing it concerns, if the samples can be deformed around at least 6%.

Staffs from amorphous Homopolystyrol (“standard polystyrene”) let themselves be transformed generally only satisfying, after during the pretreatment the rollers on certain temperatures, frequently for instance 40°C was lowered, pre-heatedly and the rolling deer number on 0,5 s-1. Immediately after rolling the shoulder staffs in principle a large deformation is possible, for example by spiral-like repeated rotating. The sample test specimens are generally cloudy after the shaping however optically and show numerous a splice places. The gloomy ranges represent white break and point out beside a splice places that the sample test specimens were deformed not sufficiently duktil. It can be said that this procedure is not suitable thus for the shaping of standard polystyrene at temperatures below its glass transition temperature.

Task of the available invention is the supply of a procedure for the transfer PVC, PP and ABS or MABS haltigen polymers into a condition of duktiler ductility, so that white-break-free deforming of the polymers is possible. If the polymers are processed after transfer into duktil the ductile condition, they are not to show defects after the subsequent treatment. Preferably the procedure is to be feasible at low temperatures, in particular below the respective glass transition temperature.

This task solved by a procedure for the transfer characterized by PVC, PP and ABS or MABS haltigen polymers into a condition of duktiler ductility, by the effect Kraft on the polymers below their respective glass transition temperature, until white-break-free deforming is possible.

It was found surprising that by the application of force according to invention used the polymers become ductile duktil, which is called them can white break-free is deformed. This has the consequence that - after previous application of force - transparent polymers can be transformed while maintaining their full transparency, thus without occurrence of optically disturbing, cloudy defects. Colored polymers can be brightened without causing or be transformed white marks and polymers with high surface gloss without loss of their gloss.

The white break can be determined by optical procedures and (electrons) microscopic procedures. Generally the polymer will be examined however visually, since the human eye is sensitive enough. With transparent products so-called Haze appears, finally stops itself a white turbidity. With colored products the appropriate place becomes brighter by the increase of the scattered light portion. White products lose at gloss.

Although quantification is possible only over optical and/or (electrons) microscopic procedures, the visual examination is sufficient. In the context of the available invention the term designates “white break-free” from there the condition in which the polymer received in the procedure does not exhibit a white break, which can be determined by the specialist by visual examination or which for planned application as disturbing one does not classify.

The condition of duktiler ductility caused by the application of force is not of duration and the duktile ductility diminishes with progressive time. The exact period of the duktilen ductility depends on the used polymer or polymer mixture as well as the intensity of the application of force.

In an execution form PVC or PP is transferred of the invention by influencing Kraft a ductility duktiler below their glass transition temperature into a condition.

With PP in the available invention polypropylene is marked and with PVC polyvinyl chloride. With according to invention used PVC it concerns PVC, which does not contain or only in small quantities commercial or the specialist well-known softeners, this PVC also hard PVC or PVC hard calls itself.

In a further execution form ABS and MABS haltige polymers are transferred of the available invention by influencing Kraft a ductility duktiler below their glass transition temperature into a condition.

By ABS haltigen polymers in the available invention styrene, butadiene and acrylonitrile containing copolymers and polymer mixtures are understood at least. The styrene, butadiene and the acrylonitrile of containing copolymers and polymer mixtures can contain further, that specialist well-known monomer places than monomer components.

By MABS haltigen polymers in the available invention copolymers and polymer mixtures are understood, which contain Methylmethacrylat, acrylonitrile, butadiene and styrene as monomer components. The MABS haltigen polymers can contain further, that specialist well-known monomer places than monomer components.

Copolymers can be statistic copolymers, block copolymers from two, three and more blocks, star copolymers, grafting copolymers or nuclear bowl copolymers with two, three and more layers.

Polymer mixtures mixtures from Homopolymeren, copolymers as well as from CO and Homopolymeren are called. The polymer mixtures can contain two, three, four and more polymer components. The polymer mixtures can be present homogeneous or heterogeneously mixed.

According to invention used the polymers can contain further usual, the specialist well-known additives such as Verarbeitungshilfsmittel, fillers, Farbpigmente and coloring materials, Antioxidantien, thermal stabilizers, Antistatika, flame protection means and the like.

Styrene in the available invention styrene as such as well as those the specialist admitted styrene derivatives called, as with 1 to 8 C-atoms containing alkyl residues substituted styrene, like Vinyltoluole, among them α-Methylstyrol, α-Chlorstyrol as well as mixtures of it.

As the further monomer component usual, the specialist know admitted monomers to be used, for example aliphatic, aromatic and araliphatic esters of the acrylic acid and Methacrylsäure, Methacrylnitril, Maleininsäureanhydrid, mark A IMIDe, serve like Isopren and olefinische monomers as well as mixtures of it.

The ABS used in the available invention preferably contains between 5 and 45 Gew. - % acrylonitrile, between 1 and 50 Gew. - % butadiene and between 5 and 94 Gew. - % styrene as well as if necessary or several that far mentioned above monomer components. It can do that after the specialist admitted procedures for example in the Bulk or in solution, suspension or emulsion to be polymerized. The ABS can be manufactured also by mixing the individual polymers or copolymers.

The MABS used in the available invention preferably contains between 1 and 60 Gew. - % Methylmethacrylat, between 1 and 35 Gew. - % acrylonitrile, between 1 and 50 Gew. - % butadiene as well as between 5 and 90 Gew. - % styrene as well as if necessary or several that far mentioned above monomer components. It knows procedures after the usual, the specialist admitted to be manufactured.

Preferred the copolymers and polymer mixtures ABS and MABS without further monomer component are used. Also in this case the quantity specifications standing above are valid for the individual monomer components.

The application of force according to invention on PVC, PP as well as ABS or MABS haltigen polymers is possible, prefer with presses, bending, stretching, kneading, generally influencing shear panels, twisting or rolling the polymers by means of rollers into the condition of duktiler ductility transferred. For the different polymers used in accordance with this invention as well as the different kinds of the application of force according to invention the parameters needed for the procedure are determined such as duration and intensity of the application of force by suitable preliminary tests. This means that depending upon selected polymer and selected kind of the application of force with different attitudes tests are accomplished, until the shaping of the polymer following on it is white break-free possible.

During application of force by rollers the rolling procedures are generally stopped by choice of the gap thickness and the rolling deer number. The exactly needed attitudes can be determined by preliminary tests. Preferred the gap is selected in such a way that rolling leads to a thickness reduction of at least 5%, particularly preferentially of at least 10%, completely particularly preferentially from at least 25%. The flow velocity of the polymer lies between 0.1 and 20 m/min, preferentially between 1 and 15 m/min, particularly preferentially between 5 and 10 m/min. Flow velocity and rolling deer number can be converted with the help of the roller diameter into one another. The rolling deer number will indicate cycles per second in s-1 or the unit equivalent in addition.

Rolling is accomplished preferentially by means of a Kalander, which or its rollers can be keep at a moderate temperaturable.

The transfer into the condition of duktiler ductility by application of force is usually accomplished at ambient temperature. It can be made however also at easily increased temperatures. The temperature is not to exceed thereby the glass transition temperature respective polymers. With polymer mixtures the individual components can exhibit different glass transition temperatures, this are for example with the polymer mixtures the case modified by means of india rubber; the polymers used as Kautschukmodifizierer possess partially glass transition temperature of 0°C and lower. If heterogeneous, thus polymer mixtures available in several phases show two glass transition temperatures, becomes in the available invention on the glass transition temperature of the polymer, copolymer referred or the polymer mixture, which forms the matrix phase.

Preferred the application of force is accomplished completely particularly preferentially at least at least 10°C, particularly preferentially 40°, 70°C below TG

In accordance with a preferential execution form of the available invention PVC can take place into a condition of the duktilen ductility a shaping of the polymers following the transfer by application of force ABS or MABS haltigen polymers, the PP or. In the procedure according to invention the period between application of force and shaping of the polymers is selected in such a way that the polymers can be still deformed duktil. The possible temporal distance between application of force and shaping can be determined by suitable preliminary tests, become preferably the polymers directly following the application of force transformed. The shaping generally less as 30 min after the application of force, prefers less than 5 min thereafter taking place.

The shaping knows for example by means of the specialist admitted procedures such as Kalandrieren, a bending, a coining/shaping and drawing procedure such as deep-drawing to be accomplished.

Of according to invention by means of application of force into the condition duktiler ductility of transferred polymers can be deformed, without with it defects in the polymers arise, and are characterised by white-break-free bending behavior, i.e. with transparent polymers no gloomy places arise and dyed polymers can without developing white marks be deformed with bending. Further the surface gloss of the polymers remains.

The polymers transferred in the procedure according to invention into the duktilen condition can be processed for example in the form of foils in many applications, like the Perma Skin procedure; Furniture, doors, windows or Bilderrahmen can be provided with a polymer coat. Due to the white-break-free subsequent treatment according to invention pre-treated the polymers for the employment within Design-oriented ranges are suitable, within which great importance is attached to the optical impression of the products. In addition e.g. belong the furniture industry, the automobile industry or the packaging industry. The procedure according to invention opens a larger freedom in form choice and Design with the employment of the polymers.

The procedure according to invention for the lining of furniture edges with ABS or MABS haltigen Kantenumleimern is used favourably. The Kantenumleimer applied in the procedure according to invention on the furniture edges shows clearly less white break, also edges with stronger roundnesses leave themselves, i.e. smaller bending radii without disturbing, of white break are due marks or defects than in the conventional procedures with PVC, PP and ABS or MABS haltigen polymers umleimen.

In particular the available procedure for the direct integration in Kantenumleimmaschinen is suitable, as on the Kantenumleimer before applying on the furniture edge by two rollers integrated into the machine a Kraft is expenditure-practiced and these in one duktil ductile condition is in this way transferred and directly afterwards on the furniture edge is applied.

After the procedure according to invention also three-dimensional bodies can be formed out of the polymers, in particular in the form of foils. In addition for example packing counts both more decoratively and protecting nature for different goods such as food, small articles, Kosmetika, Kleingeräte, intermediate packing to protection against transport damages, employments to the keeping of small articles, toy, table-ware from plastic or hollow body such as flower boxes. The forms made of according to invention pre-treated the polymers are not limited in their size. Also large things can be formed out of the duktilen polymers, for example sand boxes.

Also is suitable the procedure for extruded polymers or polymer mixtures, which are subjected to Formgebungsverfahren afterwards to the extruding still another. For example profiles and semi-finished material can be processed such as pipes in the procedure according to invention.

In the following the procedures according to invention are to be described on the basis of examples.

The examples 1 to 3 were accomplished on the basis of 4 mm of thick, sprayingpoured shoulder staffs, used in example 4 foils of different thickness. The roller distance amounted to 2 mm, so far not differently indicated.

Standard polystyrene with a middle molecule mass of 275.000 D, (not according to invention):

1. A) Rollers at ambient temperature with a rolling deer number of 0,2 s-1:
   • Cold-rolling in most cases leads to break and zerspleißenden shoulder staffs.
2. B) Rollers with 40°C and a rolling deer number of 0,2 s-1:
   • Immediately after rolling the shoulder staffs a large deformation was possible, for example by spiral-like repeated rotating. The sample test specimens were however optically cloudy after the shaping and showed numerous a splice places.
3. C) Rollers with 40°C and a rolling deer number of 0.2 s-1, 1 min. rest period:
   • No twisting without break more possible.

Shaping of ABS with a middle molecule mass of 130.000 g/mol, a styrene content of 58%, a butadiene content of 24% and a acrylonitrile content of 17%.

1. A) Deformation without pretreatment by rollers (not according to invention):
   • Rotate the sample test specimen led to break, cracking or strong white breaking behavior.
2. B) Pretreatment of the samples by rollers at ambient temperature and rolling deer numbers of 0,2 s-1 (according to invention):

The sample test specimens let themselves deform very easily duktil, for example by spiral-like repeated rotating. At the partially strongly rotated sample test specimens no white breaking behavior was to be discovered. A splices was not to be observed. After the shaping the sample test specimens showed turbidity-free transparency.

Investigation of the influence of the roller distance on the basis of ABS from example 2, roller distance = 3.5 mm at ambient temperature and a rolling deer number of 0.2 s-1:

The shoulder staffs let themselves deform duktil and white break-free.

Investigation of the white breaking behavior of colored foils from ABS in accordance with example 2 with the temperatures and attitudes of the roller gap indicated in the tables 1-5 with flow velocities of the foils from 5 to 10 m/min. The diameter of the roller amounted to 500 mm. In the column “thickness” is indicated the thickness of the foil before rolling, in the column “thickness after rolling” the foil thickness after rolling. The white breaking behavior was qualitatively judged and divided in three categories: “Bad” means occurrence of white break, “well” marginal note, hardly visible occurrence of white break and “very good” is called, to white break does not arise not.