Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
  • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

• the invention relates to glass fiber reinforced polyamides and the use of these for thermoforming.
• thermoforming of thermoplastic semi-finished products has become increasingly important in recent years. Last but not least, the ability to quickly develop prototypes offers advantages over more complex competitive processes, such as the injection molding process. Constantly improved thermoplastics allow modern machines and tools to increase the volume output while increasing the precision of the molded parts (Plastics Manual 3/4 "Polyamide", Hanser Verlag Kunststoff, Vienna).
• thermoforming in practice p. 45 ff, Hanser Verlag, Kunststoff, Vienna
• the very narrow processing window of this material class which allowed forming only shortly below the crystallite melting point and the inadequate melt stability of these polymer materials due to the low melt viscosities, allowed the forming to be made from them
• thermoforming of foils also often referred to as deep drawing
• polyamide foils single-layer, multi-layer, co-extruded or laminated
• the expert speaks of films for deep-drawing applications with a film thickness of less than 1500 ⁇ m (thermoforming, Hanser Verlag, Kunststoff, Vienna, 1999).
• the object was therefore to provide a reinforced polyamide from which thermoplastic semi-finished products with a material thickness of greater than 1.5 mm can be produced, from which molded parts with a high degree of deformation and good definition can then be produced using the thermoforming process.
• polymeric materials from the material class of structurally viscous reinforced polyamides such as those e.g. are described in EP-A 0 685 528, can be used very well for thermoforming with the viscosity behavior according to the invention. Forming degrees were achieved that were far from being achieved with previously known materials. The materials show a wide range of forming temperatures.
• molding compounds are characterized by their clear pseudoplastic behavior compared to standard polyamides. This means that these molding compounds have a significantly higher viscosity at low shear rates compared to standard polyamides and comparable high viscosities at high shear rates. This structural viscosity is achieved through an increased degree of branching of these polyamides. This can take place on the one hand in the primary condensation in the so-called VK pipe or in a subsequent compounding.
• polyamides are reinforced by incorporating e.g. Glass fibers or mineral fillers in the polyamide melt e.g. in an extruder.
• the invention therefore relates to reinforced polyamide molding compositions whose viscosity is greater than 1,000 Pas at a shear rate of 10 s -1 and at one
• Shear rate of 1000 s _1 is less than 300 Pas, at a processing temperature of 40 to 80 ° C above the melting point, of the molding compound in question.
• Reinforced polyamide molding compositions are preferred whose viscosity at a shear rate of 10 s " 1 is greater than 1500 Pas and at a shear rate speed of 1000 s _1 less than 280 Pas, at a processing temperature of 40 to 80 ° C above the melting point of the molding compound in question.
• Another object is the use of these molding compositions according to the invention for thermoforming.
• thermoplastic semi-crystalline polyamide A) 98 to 41 parts by weight of thermoplastic semi-crystalline polyamide
• molding compositions are particularly preferred.
• thermoplastic semi-crystalline polyamide A) 67 to 85 parts by weight of thermoplastic semi-crystalline polyamide
• thermoforming for thermoforming.
• the application also relates to thermoformed moldings obtainable from the molding compositions used.
• PA Semi-crystalline polyamides
• thermoplastic polyamide A preference is given to PA 6, PA 66, PA 46, PA 610 PA 6 / 6T or semi-crystalline copolyamides or mixtures based on these components.
• Preferred polyamides for the molding compositions according to the invention are partially crystalline polyamides which can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
• the starting products are preferably aliphatic dicarboxylic acids such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, aliphatic diamines such as hexamethylene diamine, 2,2,4- and 2,4,4- Trimethylhexamethylene diamine, the isomeric diamino-dicyclohexylmethane, diamino-dicyclohexylpropane, Bis-aminomethyl-cyclohexane, aminocarboxylic acids such as aminocaproic acid, or the corresponding lactams. Copolyamides from several of the monomers mentioned are included.
• Caprolactams are particularly preferably used, very particularly preferably ⁇ -caprolactam.
• Polyamide 6 and / or polyamide 6,6 are particularly preferably used. Polyamide 6 is very particularly preferred.
• the polyamides produced according to the invention can also be used in a mixture with other polyamides and / or other polymers.
• Preferred fibrous or particulate fillers and reinforcing materials are glass fibers, glass spheres, glass fabrics, glass mats, aramid fibers, carbon fibers, potassium titanate fibers, natural fibers, amorphous silica, magnesium carbonate, barium sulfate, feldspar, mica, silicates, quartz, kaolin, talc, titanium dioxide, wollaston , among others, which can also be surface-treated.
• Particularly preferred reinforcing materials are commercially available glass fibers.
• the glass fibers which generally have a fiber diameter between 8 and 18 ⁇ m, can be added as continuous fibers or as cut or ground glass fibers, the fibers being coated with a suitable sizing system and an adhesion promoter or adhesion promoter system, e.g. on
• Silane base can be equipped.
• diepoxides based on diglycidyl ether (bisphenol A and epichlorohydrin), based on amine epoxy resins (aniline and epichlorohydrin), based on diglycidyl esters (cycloaliphatic dicarboxylic acids and epichlorohydrin) are used as branching additives C) for the molding compositions according to the invention
• branching additives C are used as branching additives C) for the molding compositions according to the invention
• component D conventional additives, such as agents against heat decomposition,
• Agents against heat crosslinking agents against damage by ultraviolet light, plasticizers, lubricants and mold release agents, nucleating agents, stabilizers and dyes and pigments are used.
• oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
• UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition.
• Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and
• nucleating agents e.g. Sodium phenylphosphinate, aluminum oxide,
• Silicon dioxide and preferably talc are used.
• Lubricants and mold release agents which are usually used in amounts of up to 1% by weight, are preferably ester waxes, penterithrystearate (PETS), long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example Ca or Zn stearate) and amide derivatives (eg ethylene-bis-stearylamide) as well as low molecular weight polyethylene or polypropylene waxes.
• PTS penterithrystearate
• long-chain fatty acids for example stearic acid or behenic acid
• their salts for example Ca or Zn stearate
• amide derivatives eg ethylene-bis-stearylamide
• thermoforming is understood to mean a production process in which a thermoplastic film or plate is heated up to the softening point, deformed in a tool at low pressure, cooled and reworked.
• thermoplastics that can be produced as a film or sheet can also be thermoformed with the restriction that the temperature does not exceed the heat resistance of the material. The inherent strength should be sufficient to prevent excessive sagging or tearing of the film
• the range of thicknesses of freely thermoformable semi-finished products ranges from 0.1 mm thick foils to 10 mm thick plates (plastic handbook 3/4 "Polyamide", Hanser Verlag Kunststoff, Vienna pp. 459, 460.
• thermoforming In thermoforming, the heated semi-finished product only comes into contact with the molding tool on one side. On the contact side of the semi-finished product, the surface contours of the molding tool are precisely depicted. The contour and also the dimensions on the other side of the formed part result from the resulting wall thickness of the thermoformed part.
• positive and negative molding depending on whether the inside or outside of the molded part comes into contact with the molding tool.
• shape accuracy results on the inner contour (positive molding) or the outer contour (negative molding) of the molded part.
• thermoforming are inexpensive thermoforming tools, cheaper thermoforming machines, the possibility of also processing multi-layer materials, foams and pre-printed semi-finished products ("Thermoforming in Practice", Schwarzmann, P., Hanser Verlag, Kunststoff, Vienna, 1997). Examples and comparative examples
• thermoformed articles The quality of the thermoformed articles was assessed on the following features:
• the degree of deformation is the ratio between the maximum drawing depth H and the width B or the diameter D of the mold surface (clear width of the clamping frame surface).
• the degree of stretching is the ratio between the surface of the molded part before trimming (without a clamping edge) and the molded surface.
• Thermoformability The molding behavior is assessed.
• the plate-shaped semi-finished product should have sufficient strength with little sag in the stenter during the heating phase and should be easily deformable by the tool without forming melt overhangs and folds.
• the wall thickness of the individual steps of the thermoformed parts produced with the step tool is measured and the uniformity is assessed.
• the definition sharpness means the accuracy of the contours of the thermoforming tool on the molded part.
• the main criteria are Small radii and surface structures on the contact side to the tool were observed.
• Thermoformed parts are produced from the material and comparative material used according to the invention and are compared.
• PA 6 Durethan® B 31 from Bayer AG (relative solution viscosity: 3, measured in 1% metacresol solution at 25 ° C)
• the components listed below were compounded at 265 ° C. in a twin-screw extruder from Werner & Pfleiderer (100 min -1 ; 10 kg / h), extruded into a water bath and granulated.
• the diepoxide was metered into the feed area of the extruder using a liquid metering pump.
• the granules obtained were each dried at about 70 ° C. in a vacuum drying cabinet for 4 hours.
• the required semi-finished sheet products were produced using the granules produced in accordance with the example on an extrusion system.
• the polymer granules were extruded through an extruder through a slot die and through a Subtracted and calibrated. In this way, plates with a thickness of 3 mm and a width of 800 mm were produced, which were cut to a length of approximately 1100 mm.
• thermoforming tool TW
• the step tool used enables different drawing depths to be set by varying the number of steps (3 steps / 5 steps, 7 steps).
• the individual step height is 30 mm.
• thermoformability the wall thicknesses and the sharpness of the shape were compared for the degrees of stretching set out in the table below.
• thermoformed parts produced from the extruded sheets according to the example is shown in the table below:

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Reinforced Plastic Materials (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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• 1999
  • 1999-10-08 DE DE19948850A patent/DE19948850A1/de not_active Withdrawn
• 2000
  • 2000-09-26 EP EP00967783A patent/EP1222232A1/de not_active Withdrawn
  • 2000-09-26 WO PCT/EP2000/009372 patent/WO2001027202A1/de not_active Application Discontinuation
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  • 2000-09-26 AU AU77827/00A patent/AU7782700A/en not_active Abandoned
  • 2000-09-26 US US10/089,709 patent/US6833429B1/en not_active Expired - Lifetime
  • 2000-09-26 CZ CZ20021183A patent/CZ20021183A3/cs unknown
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• 2002
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