EP0868487A1 - Thermoplastic moulding materials based on polyethylene terephthalate for use in injection moulding of parts - Google Patents

Thermoplastic moulding materials based on polyethylene terephthalate for use in injection moulding of parts

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Publication number
EP0868487A1
EP0868487A1 EP96944577A EP96944577A EP0868487A1 EP 0868487 A1 EP0868487 A1 EP 0868487A1 EP 96944577 A EP96944577 A EP 96944577A EP 96944577 A EP96944577 A EP 96944577A EP 0868487 A1 EP0868487 A1 EP 0868487A1
Authority
EP
European Patent Office
Prior art keywords
weight
molding compositions
compositions according
thermoplastic
molding
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96944577A
Other languages
German (de)
French (fr)
Inventor
Norbert Müller
Jochen Eicher
Karl-Heinz Sartor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Emtec Magnetics GmbH
Original Assignee
Emtec Magnetics GmbH
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Filing date
Publication date
Application filed by Emtec Magnetics GmbH filed Critical Emtec Magnetics GmbH
Publication of EP0868487A1 publication Critical patent/EP0868487A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • the invention relates to thermoplastic molding compositions and injection molded parts produced therefrom.
  • Plastic mixtures consisting predominantly of polyalkylene terephthalate are already known. PET and PBT mixtures with approximately 30% glass fiber additive for increasing the strength, the stability and the modulus of elasticity are known. PBT blends are preferred for injection molding because they are easier to process
  • Ultradur® B4300G2 is a glass fiber-reinforced PBT molding compound from BASF Aktiengesellschaft. (This molding compound is
  • the technical molded parts made from it are stiff, tough and dimensionally stable, e.g. for program switches, knobs, buttons, thermostatic parts, handles of heating devices (see BASF plastics, Ultradur® polybutylene terephthalate (PBT)
  • thermoplastic molding composition which, as essential components, A) 37 to 96% by weight of a thermoplastic polyethylene terephthalate, B) 1 to 20% by weight of 35 polymer composition and C) 4 to 30% by weight of one contain pigment-shaped reinforcing agents.
  • the moldings produced therefrom being sprayable at a temperature 40 of above 245 to 300 ° C.
  • thermoplastic molding compositions for injection molding molded parts containing predominantly a thermoplastic polyethylene terephthalate and a polymeric composition are given by a weight ratio of 50 to 60% by weight of polyethylene terephthalate
  • moldings are sprayable with a melt temperature between about 245 to 300 ° C.
  • the molding compositions predominantly contain polyurethane as the polymer composition, so that they are easy to injection mold and process. It is also advantageous if the moisture content of the molding compositions is at most 0.1% by weight, in particular 0.05% by weight.
  • the pigment reinforcing agent suitably consists of metal and / or metal oxide pigments.
  • the pigments can have an average average particle size of less than / equal to 400 ⁇ m. This enables a uniform pigment distribution to be achieved.
  • the pigments have a length to thickness ratio of about 5: 1 to about 15: 1.
  • the properties of the injection molded parts can be improved if about 0.2 to about 0.8, in particular about 0.5% by weight of talc is contained in the molding composition. As a result, both the flowability, the demoldability and the surface smoothness of the molded parts are improved, while lowering the necessary hydraulic pressure in the system.
  • the molding compositions according to the invention can also be used favorably because of their very low isotropic shrinkage of about 0.2% lengthways and crossways.
  • the molding compositions can be processed particularly advantageously in injection molding devices with a closure nozzle and hot runner system, in order to produce optimal molded parts with relatively good cycle times.
  • Cold runner devices can also be used advantageously. It is also practically favorable if the screw conveyors of the injection molding devices have a diameter of 20 to 80 mm, in particular 25 to 60 mm.
  • the molding compositions are also expediently processable in multi-layer injection molding or in sandwich injection molding.
  • the molding compositions have a density of greater than or equal to 1.4 g / cm 3 , in particular of 1.48 g / cm 3 .
  • the molding compositions can expediently contain chromium dioxide pigments as pigments, which are finely divided and can be readily distributed in the molding composition.
  • the molding compositions are also characterized by a volume flow index (MVI) at 275 ° C / 2.16 kg of at least about 10 25 ml / 10 min.
  • MVI volume flow index
  • injection molded parts from the molding compositions according to the invention advantageously have a relatively large density of greater than or equal to 1.4 g / cm 3 , which is very advantageous for some applications.
  • a further advantageous property of the injection molded part is obtained by using chromium dioxide pigment, since an essentially uniform anthracite color with high gloss could be achieved.
  • a very small shrinkage of the molded part lengthwise and transversely of about 0.2% can be achieved.
  • dimensionally stable molded articles can advantageously be produced. 5
  • a relatively high modulus of elasticity of>. 3,200 MPa / mm 2 in particular from approx. 3,500 to approx. 3,700 MPa / mm 2 , makes the molding compound interesting for many types of high-quality molded parts.
  • the molding compositions should have a relatively low chlorine content of less than or equal to 0.5% by weight, in particular no chlorine content to avoid corrosion of the injection molding devices.
  • the thermoplastic molding composition predominantly contains polyethylene terephthalate (PET) in the% by weight range from 37 to 96% by weight, preferably 60 to 77% by weight, or else 50 to 60% by weight or else 69 to 77 wt .-% or 41 to 50 wt .-%.
  • PET polyethylene terephthalate
  • Polyethylene terephthalate contains an aromatic ring in the main chain, which is substituted by ethyl groups.
  • Polyethylene terephthalate is a polyester made of terephthalic acid and a C 2 diol component.
  • the component to be used as the polymer composition is used in an amount of about 1 to 20% by weight, preferably 4 to 12% by weight or 10 to 20% by weight or 12 to 20% by weight or 4 to 6% by weight .-% related. 5
  • This polymer mass preferably contains a polyurethane or polyurethane copolymers or condensates.
  • polyacrylates polymethacrylates, polyacrylamide, vinyl polymers such as polystyrene, polyvinyl propionate and polyacrylonitrile, 10 cellulose-containing binders such as cellulose esters, in particular cellulose nitrates, cellulose acetates, cellulose acetopropionate and cellulose acetobutyrate, phenoxy resins and epoxy resins.
  • the amount used as pigment reinforcing agent should be 4 to 15 30% by weight, expediently 4 to 21% by weight or also 20 to 30% by weight or also 18 to 30% by weight or also 15 to 21% by weight. -%.
  • Oxide pigments such as ⁇ -Fe 2 0 3 , ⁇ -Fe 3 0 4 and Cr0 2 and metallic pigments such as Fe, Co 0 and Ni are suitable as pigment-like reinforcing agents. These pigments can contain further chemical elements and / or compounds.
  • the pigments should have an average particle size of 400 nm or less. If chromium dioxide (Cr0 2 ) is preferably used, the particle size is approximately 250 to 300 nm.
  • the metal 5 and / or metal oxide pigments or particles can expediently have a length-to-thickness ratio of 5: 1 to 15: 1. In the case of Cr0 2 pigments, this ratio is approximately 15: 1.
  • Inorganic or organic pigments can be used as further pigment additives or fillers, e.g. Aluminum oxide, silicon oxide, zirconium oxide, titanium oxide, carbon black, polyethylene, polypropylene and also thixotropic substances, e.g. amorphous silica.
  • the thermoplastic molding composition can in principle contain up to about 1% by weight of carboxylic acids having 10 to 20 carbon atoms, such as stearic acid, palmitic acid or derivatives, such as salts, esters or amides thereof, and also esters of pentaerythritol with long-chain fatty acids, contain. 0
  • the molding compositions if about 0.2% by weight to about 0.8% by weight, in particular about 0.5% by weight, of talc has been added. This improves the injection molding ability and the ability to be removed from the mold, and also improves the flame protection of the moldings, which is already achieved by the above-mentioned metal and / or metal oxide pigment fraction, these pigments acting as synergists with for polyester - Known flame retardant additives, such as ethylene to tetrabromophthalimide and oligomeric tetrabromobisphenol A carbonates, are used.
  • Polyurethane elastomers combined with relatively brittle polymers such as phenoxy resins, polycarbonate, polyester resins are used as the polymer composition for the purpose of the present invention.
  • Such polyurethanes were produced by reacting hydroxyl-containing polyethers or polyesters with isocyanates, it being possible for the polymer mixtures to also be crosslinked with polyisocyanates, e.g. if the brittle polymers used have OH groups.
  • a dispersion can be prepared from the polymer mass and the pigment and possibly also with the addition of the polyethylene terephthalate in a known manner, e.g. in an agitator mill with the addition of known dispersants, the components are mixed or dispersed with one another.
  • the addition of talc and / or other fillers mentioned above is also advantageous.
  • the finished dispersion can then be extruded, shaped as an extrudate, cooled and e.g. be crushed as granules.
  • the polymer mass and the pigment are premixed and then the PET and the talc and / or other fillers are added individually or likewise premixed.
  • the mixing temperatures like the later injection molding temperatures, are between approximately 245 ° C. and 300 ° C., in particular approximately 260 ° C. to approximately 290 ° C.
  • thermoplastic molding compositions according to the invention are notable for good injection molding properties in cold runner, bar sprue, sandwich and hot runner injection molding techniques with a closure needle system.
  • the molded articles produced in this way have relatively good mechanical and electrical properties (for shielding electromagnetic waves) and particularly low distortion of the parts (dimensional stability).
  • the molding compositions are therefore suitable for the economical production of small parts, coils and coil cores for strip-shaped materials, housing parts, containers, in particular for the entertainment and data device industry (device housing, including accessories therefor, such as housings for recording media such as photo films, etc.) .). Assembly parts for window construction, shells for tool cases etc. example
  • a polyethylene terephthalate with an average molecular weight M n number average of about 30,000 and a viscosity number of 73 ml / g (measured on a 0.5% by weight solution in phenol / o-dichlorobenzene (weight ratio 1 : 1) (Netralen® SP 3700 $ from BASF Aktiengesellschaft, 67056 Ludwigshafen).
  • a polymer mass consisting of an isocyanate resin Desmodur® from Bayer AG, Leverkusen, crosslinked with a partially branched polyester made of diacids e.g. Desmolphes of the 2000 series from Bayer AG as reactants and in particular diols or triols as crosslinkers to regulate the course of the reaction.
  • Desmodur® Desmodur® from Bayer AG
  • Leverkusen crosslinked with a partially branched polyester made of diacids e.g. Desmolphes of the 2000 series from Bayer AG as reactants and in particular diols or triols as crosslinkers to regulate the course of the reaction.
  • Thickness ratio of about 15: 1.
  • the components were in a weight ratio of approximately
  • Component ratio A 70% by weight
  • Component ratio B 10% by weight
  • Component ratio C 20% by weight
  • Test specimens were produced from this granulate and characteristic values measured on the granulate or on the test specimen in comparison to the BASF product Ultradur® B4300G2 mentioned at the beginning. SO ä Ul ae> s
  • the modulus of elasticity is dependent on the PET content in the range from approximately 3250 MPa / mm 2 for more than 90% by weight PET to approximately 3700 MPa / mm 2 for approximately 75% by weight PET. 5
  • thermoplastic molding composition I was also tested in injection molding behavior and met the expectations.
  • the melt temperature was about 270 ° C at a spray pressure PE of between 18 to 50 bar and a holding pressure of 10 52 bar.
  • the cycle time when spraying test specimens was 30 or 40 P / sec.
  • a Windsor SP 80/3, Arburg 270E machine with 800 KN or 500 KN locking force was used as the injection molding device.
  • An injection molding tool with an open hot runner system turned out to be unsuitable, therefore cold runner, bar sprue, screen cut and hot runner tools, the latter with a locking needle system, result as usable injection molding tools.
  • the molding composition according to the invention is also advantageously suitable for
  • the invention relates to a thermoplastic molding composition based on polyethylene terephthalate, preferably contains 37 to 96% by weight of PET, 1 to 20% by weight of a polymer composition, preferably containing polyurethane, and also approximately 4 to 30% by weight of a pigment Reinforcing means made of metal and / or metal oxide.
  • the molded parts 0 can be processed suitably for injection molding and the molding compositions produced therefrom have advantageous properties, in particular with regard to a low shrinkage factor and a higher density compared to a comparable polybutylene terephalate (PBT) filled with glass fibers.
  • PBT polybutylene terephalate
  • the thermoplastic molding composition can advantageously be used for small parts, housing parts, in particular for electronic and data devices.
  • thermoplastic molding composition based on polyethylene terephthalate preferably contains 37 to 96% by weight of PET, 1 to 20% by weight of a polymer composition, preferably containing polyurethane, and also about 4 to 30% by weight of a pigmented tonic made of metal and / or metal oxide .
  • the molding compositions can advantageously be processed in injection molding and the molded parts produced therefrom have advantageous properties, in particular with regard to a higher density and very low isotropic shrinkage with a comparable high modulus of elasticity, compared with a comparable polybutylene terephthalate (PBT) filled with glass fibers .
  • PBT polybutylene terephthalate
  • thermoplastic molding composition can be used advantageously for small parts, housing parts of all types, in particular for electronics and data devices.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

A thermoplastic moulding material based on polyethylene terephthalate contains preferably 37-96 wt % PET, 1-20 wt % polymer material containing preferably polyurethane, and approximately 4-30 wt % pigment-type stiffening agent of, in particular, metal and/or metal oxide CrO2. The moulding materials can be advantageously processed in injection moulding and the resulting mouldings have advantageous properties, in particular higher density, compared to a comparable glass fibre-filled polybutylene terephthalate (PBT). The proposed thermoplastic moulding material can be advantageously used for small parts and housing parts, especially for electronic and data-processing devices.

Description

THERMOPLASTISCHE FORMMASSEN AUF BASIS VON POLYETHYLENTEREPHTHALAT ZUM SPRITZGIESSEN VON FORMTEILEN THERMOPLASTIC MOLDING MATERIALS BASED ON POLYETHYLENE TEREPHTHALATE FOR INJECTION MOLDING OF MOLDED PARTS
5 Beschreibung5 Description
Die Erfindung betrifft thermoplastische Formmassen und daraus hergestellte Spritzguß-Formteile.The invention relates to thermoplastic molding compositions and injection molded parts produced therefrom.
10 Es sind vorwiegend aus Polyalkylenterephthalat bestehende Kunst¬ stoff-Mischungen bereits bekannt. Bekannt sind PET- und PBT- Mischungen mit ca. 30 % Glasfaser-Zusatz zur Erhöhung der Festig¬ keit, der Standfestigkeit und des E-Moduls. PBT-Mischungen werden für den Spritzguß bevorzugt, da sie sich leichter verarbeiten10 Plastic mixtures consisting predominantly of polyalkylene terephthalate are already known. PET and PBT mixtures with approximately 30% glass fiber additive for increasing the strength, the stability and the modulus of elasticity are known. PBT blends are preferred for injection molding because they are easier to process
15 lassen als PET-Mischungen, aber sie haben eine geringere Festig¬ keit.15 leave as PET mixtures, but they have a lower strength.
Mit Ultradur® B4300G2 ist von der BASF Aktiengesellschaft eine glasfaserverstärkte PBT-Formmasse bekannt. (Diese Formmasse istUltradur® B4300G2 is a glass fiber-reinforced PBT molding compound from BASF Aktiengesellschaft. (This molding compound is
20 leicht fließend für den Spritzguß geeignet und enthält 10 Gew.-% Glasfasern. Die daraus hergestellten technischen Formteile sind steif, zäh und dimensionsstabil, z.B. für Programmschalter, Kne¬ bel, Knöpfe, Thermostatteile, Griffe von Heizapparaturen, (vgl. BASF Kunststoffe, Ultradur® Polybuthylenterephthalat (PBT) Sorti-20 easy flowing for injection molding and contains 10% by weight of glass fibers. The technical molded parts made from it are stiff, tough and dimensionally stable, e.g. for program switches, knobs, buttons, thermostatic parts, handles of heating devices (see BASF plastics, Ultradur® polybutylene terephthalate (PBT)
25 mentsübersicht, Produktmerkmale Verwendung Richtwerte, April 1994)25 overview, product characteristics, use of guideline values, April 1994)
Es ist Aufgabe der Erfindung eine PET-Mischung bereitzustellen, die wirtschaftlicher herzustellen ist und die z.T. günstigere Pa- 30 rameter als bekannte PBT-Mischungen aufweisen.It is an object of the invention to provide a PET mixture which is more economical to produce and which in some cases. have more favorable parameters than known PBT mixtures.
Die Aufgabe wird mit einer thermoplastischen Formmasse gelöst, die als wesentliche Komponenten A) 37 bis 96 Gew.-% eines thermoplastischen Polyethylenterephathalats, B) 1 bis 20 Gew.-% 35 Polymer-Masse und C) 4 bis 30 Gew.-% eines pigmentförmigen Ver- stärkungsmittels enthalten.The object is achieved with a thermoplastic molding composition which, as essential components, A) 37 to 96% by weight of a thermoplastic polyethylene terephthalate, B) 1 to 20% by weight of 35 polymer composition and C) 4 to 30% by weight of one contain pigment-shaped reinforcing agents.
Es ist auch vorteilhaft, wenn die thermoplastische FormmasseIt is also advantageous if the thermoplastic molding compound
40 als wesentliche Komponente A40 as essential component A
69 bis 77 Gew. -% oder69 to 77% by weight or
60 bis 77 Gew. -% oder eines Polyethylenterephthalats 45 50 bis 60 Gew.-% oder60 to 77% by weight or a polyethylene terephthalate 45 50 to 60% by weight or
41 bis 50 Gew. -%41 to 50% by weight
undand
als wesentliche Komponente B 12 bis 20 Gew. -% oderas essential component B 12 to 20% by weight or
10 bis 20 Gew. -% 10 oder einer Polymer-Masse10 to 20 wt.% 10 or a polymer mass
4 bis 12 Gew. -% oder4 to 12% by weight or
4 bis 6 Gew. -%4 to 6% by weight
15 und15 and
als wesentliche Komponente Cas an essential component C
20 bis 30 Gew. -% oder 20 18 bis 30 Gew. -% oder eines pigmentförmigen20 to 30% by weight or 20 18 to 30% by weight or a pigment
15 bis 21 Gew. -% Verstärkungsmitteis enthält. oderContains 15 to 21% by weight of reinforcing agent. or
4 bis 21 Gew. -% 254 to 21% by weight 25
Damit wird eine sehr günstige und problemlos spritzbare Formmasse erhalten, die sich wesentlich von bekannten Formmassen unter¬ scheiden.This gives a very inexpensive molding compound which can be sprayed without problems and which differs significantly from known molding compounds.
30 Ebenfalls vorteilhafte thermoplastischen Formmassen zum Spritz¬ gießen von Formteilen enthalten überwiegend ein thermoplastisches Polyethylenterephthalat {PET), Pigmente und eine Polymermasse in einem Gewichtsverhältnis von30 Also advantageous thermoplastic molding compositions for injection molding of molded parts predominantly contain a thermoplastic polyethylene terephthalate (PET), pigments and a polymer composition in a weight ratio of
35 60 bis 77 Gew. -% Polyethylenterephthalat 4 bis 12 Gew. -% Polymer-Masse 4 bis 21 Gew. -% eines Pigment-Verstärkungsmitteis,35 60 to 77% by weight of polyethylene terephthalate 4 to 12% by weight of polymer composition 4 to 21% by weight of a pigment reinforcing agent,
wobei die daraus hergestellten Formteile mit einer Temperatur 40 von oberhalb 245 bis 300°C spritzbar sind.the moldings produced therefrom being sprayable at a temperature 40 of above 245 to 300 ° C.
Ebenfalls vorteilhafte thermoplastische Formmassen zum Spritz¬ gießen von Formteilen, enthaltend überwiegend ein thermoplasti¬ sches Polyethylenterephthalat und eine polymere Masse sind gege- 5 ben durch ein Gewichtsverhältnis von 50 bis 60 Gew.-% PolyethylenterephthalatLikewise advantageous thermoplastic molding compositions for injection molding molded parts, containing predominantly a thermoplastic polyethylene terephthalate and a polymeric composition are given by a weight ratio of 50 to 60% by weight of polyethylene terephthalate
10 bis 20 Gew.-% Polymer-Masse10 to 20 wt .-% polymer mass
20 bis 30 Gew.-% eines pigmentförmigen Verstärkungsmitteis,20 to 30% by weight of a pigment-shaped reinforcing agent,
wobei die Formteile mit einer Massetemperatur zwischen etwa 245 bis 300°C spritzbar sind.wherein the moldings are sprayable with a melt temperature between about 245 to 300 ° C.
Es ist günstig, wenn die Formmassen als Polymer-Masse überwiegend Polyurethan enthalten, damit sie gut spritzgießbar und gut verarbeitbar sind. Vorteilhaft ist auch, wenn der Feuchtigkeits¬ gehalt der Formmassen höchstens 0,1 Gew.-%, insbesondere 0,05 Gew.-%, beträgt.It is advantageous if the molding compositions predominantly contain polyurethane as the polymer composition, so that they are easy to injection mold and process. It is also advantageous if the moisture content of the molding compositions is at most 0.1% by weight, in particular 0.05% by weight.
Das Pigment-Verstärkungsmittel besteht zweckmäßig aus Metall- und/oder Metalloxid-Pigmenten.The pigment reinforcing agent suitably consists of metal and / or metal oxide pigments.
In zweckmäßiger Ausbildung können die Pigmente eine mittlere durchschnittliche Teilchengröße von kleiner/gleich 400 μm besit¬ zen.Damit läßt sich eine gleichmäßige Pigmentverteilung errei- chen.In an expedient embodiment, the pigments can have an average average particle size of less than / equal to 400 μm. This enables a uniform pigment distribution to be achieved.
Es ist auch vorteilhaft, wenn die Pigmente ein Längen-zu-Dicken- Verhältnis von etwa 5:1 bis etwa 15:1 aufweisen.It is also advantageous if the pigments have a length to thickness ratio of about 5: 1 to about 15: 1.
Die Eigenschaften der Spritzguß-Formteile lassen sich verbessern, wenn etwa 0,2 bis etwa 0,8, insbesondere etwa 0,5 Gew.-% Talkum in der Formmasse enthalten sind. Dadurch werden sowohl die Fließ- fähigkeit, die Entformbarkeit und die Oberflächenglätte der Form¬ teile verbessert, bei Senkung des notwendigen hydraulischen Drucks im System.The properties of the injection molded parts can be improved if about 0.2 to about 0.8, in particular about 0.5% by weight of talc is contained in the molding composition. As a result, both the flowability, the demoldability and the surface smoothness of the molded parts are improved, while lowering the necessary hydraulic pressure in the system.
Die erfindungsgemäßen Formmassen sind auch günstig wegen ihrer sehr geringen isotropen Schwindung von längs und quer je etwa 0,2 % verwendbar.The molding compositions according to the invention can also be used favorably because of their very low isotropic shrinkage of about 0.2% lengthways and crossways.
Die Formmassen sind besonders vorteilhaft in Spritzguß-Vorrich¬ tungen mit Verschlußdüse und Heißkanal-System verarbeitbar, um optimale Formteile bei relativ guten Zykluszeiten herzustellen.The molding compositions can be processed particularly advantageously in injection molding devices with a closure nozzle and hot runner system, in order to produce optimal molded parts with relatively good cycle times.
Kaltkanalvorrichtungen sind ebenfalls vorteilhaft verwendbar. Es ist pratisch auch günstig, wenn die Förderschnecken der Spritz- gußvorrichtungen einen Durchmesser von 20 bis 80 mm, insbesondere von 25 bis 60 mm, besitzen.Cold runner devices can also be used advantageously. It is also practically favorable if the screw conveyors of the injection molding devices have a diameter of 20 to 80 mm, in particular 25 to 60 mm.
Die Formmassen sind zweckmäßig auch im Mehrschichtspritzguß oder im Sandwichspritzguß verarbeitbar. Die Formmassen besitzen eine Dichte von größer/gleich 1,4 g/cm3, insbesondere von 1,48 g/cm3.The molding compositions are also expediently processable in multi-layer injection molding or in sandwich injection molding. The molding compositions have a density of greater than or equal to 1.4 g / cm 3 , in particular of 1.48 g / cm 3 .
Die Formmassen können zweckmäßig Chromdioxid-Pigmente als Pig- 5 mente enthalten, die feinteilig sind und sich gut in der Form¬ masse verteilen lassen.The molding compositions can expediently contain chromium dioxide pigments as pigments, which are finely divided and can be readily distributed in the molding composition.
Die Formmassen sind außerdem gekennzeichnet durch einen Volumen- Fließ-Index (MVI) bei 275°C/2,16 kg von wenigstens etwa 10 25 ml/10 min.The molding compositions are also characterized by a volume flow index (MVI) at 275 ° C / 2.16 kg of at least about 10 25 ml / 10 min.
Dadurch werden die Spritzgußeigenschaften, besonders gegenüber Polybuthylenterephthalat-Formmassen, noch verbessert.As a result, the injection molding properties, especially compared to polybutylene terephthalate molding compositions, are further improved.
15 Spritzguß-Formteile aus den erfindungsgemäßen Formmassen weisen zweckmäßig eine relativ große Dichte von größer/gleich 1,4 g/cm3 auf, was für einige Anwendungsen sehr vorteilhaft ist. Eine wei¬ tere vorteilhafte Eigenschaft des Spritzguß-Formteils wird durch Verwendung von Chromdioxid-Pigment erhalten, da eine im wesent- 0 liehen gleichmäßige Anthrazit-Farbe bei hohem Glanz erzielbar wurde. Als weiterer Vorteil des Spritzguß-Formteils wird eine sehr geringe Schwindung des Formteils von längs und quer etwa 0,2 % erreichbar. Dadurch lassen sich vorteilhaft dimensions¬ stabile Formkörper herstellen. 515 injection molded parts from the molding compositions according to the invention advantageously have a relatively large density of greater than or equal to 1.4 g / cm 3 , which is very advantageous for some applications. A further advantageous property of the injection molded part is obtained by using chromium dioxide pigment, since an essentially uniform anthracite color with high gloss could be achieved. As a further advantage of the injection molded part, a very small shrinkage of the molded part lengthwise and transversely of about 0.2% can be achieved. As a result, dimensionally stable molded articles can advantageously be produced. 5
Ein relativ hoher E-Modul von >.3.200 MPa/rnm2, insbesondere von ca. 3.500 bis ca. 3.700 MPa/mm2, macht die Formmasse interessant für viele Arten von hochwertigen Formteilen. Die Formmassen soll¬ ten hinsichtlich der Spritzguß-Anwendung einen relativ niedrigen 0 Chloranteil von kleiner/gleich 0,5 Gew. -%, insbesondere keinen Chloranteil aufweisen zur Vermeidung der Korrosion der Spritzguß- Vorrichtungen.A relatively high modulus of elasticity of>. 3,200 MPa / mm 2 , in particular from approx. 3,500 to approx. 3,700 MPa / mm 2 , makes the molding compound interesting for many types of high-quality molded parts. With regard to the use of injection molding, the molding compositions should have a relatively low chlorine content of less than or equal to 0.5% by weight, in particular no chlorine content to avoid corrosion of the injection molding devices.
Die thermoplastische Formmasse enthält überwiegend Polyethylen- 5 terephthalat (PET) im Gew.-%-Bereich von 37 bis 96 Gew.-%, bevor¬ zugt 60 bis 77 Gew.-%, oder auch 50 bis 60 Gew.-% oder auch 69 bis 77 Gew.-% oder auch 41 bis 50 Gew.-%.The thermoplastic molding composition predominantly contains polyethylene terephthalate (PET) in the% by weight range from 37 to 96% by weight, preferably 60 to 77% by weight, or else 50 to 60% by weight or else 69 to 77 wt .-% or 41 to 50 wt .-%.
Polyethylenterephthalat enthält in der Hauptkette einen aroma- 0 tischen Ring, der durch Ethylgruppen substituiert ist. Poly¬ ethylenterephthalat ist ein Polyester aus Terephthalsäure und einer C2-Diol-Komponente.Polyethylene terephthalate contains an aromatic ring in the main chain, which is substituted by ethyl groups. Polyethylene terephthalate is a polyester made of terephthalic acid and a C 2 diol component.
5 55 5
Die als Polymer-Masse einzusetzende Komponente wird in einer Menge von etwa 1 bis 20 Gew.-%, vorzugsweise 4 bis 12 Gew.-% oder 10 bis 20 Gew.-% oder 12 bis 20 Gew.-% oder 4 bis 6 Gew.-% ver¬ wandt. 5The component to be used as the polymer composition is used in an amount of about 1 to 20% by weight, preferably 4 to 12% by weight or 10 to 20% by weight or 12 to 20% by weight or 4 to 6% by weight .-% related. 5
Diese Polymer-Masse enthält vorzugsweise ein Polyurethan oder Polyurethan-Copolymerisate oder -Kondensate. Als Polymer-Masse kommen auch Polyacrylate, Polymethacrylate, Polyacrylamid, Vinyl- polymere wie Polystyrol, Polyvinyl-Propionat und Polyacrylnitril, 10 cellulosehaltige Bindemittel wie Celluloseester, insbesondere Cellulosenitrate, Cellusloseacetate, Celluloseacetopropionat und Celluloseacetobutyrat, Phenoxyharze und Epoxyharze, in Betracht.This polymer mass preferably contains a polyurethane or polyurethane copolymers or condensates. Also suitable as polymer mass are polyacrylates, polymethacrylates, polyacrylamide, vinyl polymers such as polystyrene, polyvinyl propionate and polyacrylonitrile, 10 cellulose-containing binders such as cellulose esters, in particular cellulose nitrates, cellulose acetates, cellulose acetopropionate and cellulose acetobutyrate, phenoxy resins and epoxy resins.
Die als Pigment-Verstärkungsmittel eingesetzte Menge sollte 4 bis 15 30 Gew. -%, zweckmäßig 4 bis 21 Gew. -% oder auch 20 bis 30 Gew. -% oder auch 18 bis 30 Gew. -% oder auch 15 bis 21 Gew. -% betragen.The amount used as pigment reinforcing agent should be 4 to 15 30% by weight, expediently 4 to 21% by weight or also 20 to 30% by weight or also 18 to 30% by weight or also 15 to 21% by weight. -%.
Als pigmentförmige Verstärkungsmittel kommen oxidische Pigmente wie γ-Fe203, γ-Fe304 und Cr02 sowie metallische Pigmente wie Fe, Co 0 und Ni in Betracht. Diese Pigmente können weitere chemische Elemente und/oder Verbindungen enthalten. Die Pigmente sollen eine mittlere durchschnittliche Teilchengröße von kleiner/gleich 400 nm besitzen. Bei vorzugsweiser Verwendung von Chromdioxid (Cr02) beträgt die Teilchengröße etwa 250 bis 300 nm. Die Metall- 5 und/oder Metalloxid-Pigmente oder Partikel können zweckmäßig ein Längen-zu-Dicken-Verhältnis von 5:1 bis 15:1 aufweisen. Bei Cr02-Pigmenten beträgt dieses Verhältnis etwa 15:1.Oxide pigments such as γ-Fe 2 0 3 , γ-Fe 3 0 4 and Cr0 2 and metallic pigments such as Fe, Co 0 and Ni are suitable as pigment-like reinforcing agents. These pigments can contain further chemical elements and / or compounds. The pigments should have an average particle size of 400 nm or less. If chromium dioxide (Cr0 2 ) is preferably used, the particle size is approximately 250 to 300 nm. The metal 5 and / or metal oxide pigments or particles can expediently have a length-to-thickness ratio of 5: 1 to 15: 1. In the case of Cr0 2 pigments, this ratio is approximately 15: 1.
Als weitere pigmentförmige Zusatzstoffe oder Füllstoffe können 0 anorganische oder organische Pigmente verwendet werden, wie z.B. Aluminiumoxid, Siliziumoxid, Zirkoniumoxid, Titaniumoxid, Ruß, Polyethylen, Polypropylen und auch thixotrope Substanzen, z.B. amorphe Kieselsäure.Inorganic or organic pigments can be used as further pigment additives or fillers, e.g. Aluminum oxide, silicon oxide, zirconium oxide, titanium oxide, carbon black, polyethylene, polypropylene and also thixotropic substances, e.g. amorphous silica.
5 Als Gleit- und Entformungsmittel kann die thermoplastische Form¬ masse grundsätzlich bis etwa zu 1 Gew.-% Carbonsäuren mit 10 bis 20 Kohlenstoffatomen wie Stearinsäure, Palmitinsäure oder Derivate, wie Salze, Ester oder Amide davon, sowie Ester des Pentaerythrits mit langkettigen Fettsäuren, enthalten. 05 As a lubricant and mold release agent, the thermoplastic molding composition can in principle contain up to about 1% by weight of carboxylic acids having 10 to 20 carbon atoms, such as stearic acid, palmitic acid or derivatives, such as salts, esters or amides thereof, and also esters of pentaerythritol with long-chain fatty acids, contain. 0
Es hat sich für die Formmassen als zweckmäßig herausgestellt, wenn etwa 0,2 Gew.-% bis etwa 0,8 Gew.-%, insbesondere etwa 0,5 Gew.-% Talkum zugemischt sind. Dadurch wird die Spritzgu߬ fähigkeit und die Entformbarkeit verbessert, als auch der Flamm- 5 schütz der Formkörper noch verbessert, der schon durch den oben¬ erwähnten Metall- und/oder Metalloxid-Pigmentanteil erreicht wird, wobei diese Pigmente als Synergisten mit für Polyester be- kannten Flammschutzzusätzen, wie z.B. Ethylen- bis -tetrabrom- phthalimid und oligomere Tetrabrombisphenol A-Carbonate, einge¬ setzt werden.It has proven to be expedient for the molding compositions if about 0.2% by weight to about 0.8% by weight, in particular about 0.5% by weight, of talc has been added. This improves the injection molding ability and the ability to be removed from the mold, and also improves the flame protection of the moldings, which is already achieved by the above-mentioned metal and / or metal oxide pigment fraction, these pigments acting as synergists with for polyester - Known flame retardant additives, such as ethylene to tetrabromophthalimide and oligomeric tetrabromobisphenol A carbonates, are used.
Als Polymer-Masse zum Zwecke der vorliegenden Erfindung werden Polyurethan-Elastomere mit relativ spröden Polymeren wie Phenoxi- harze, Polycarbonat, Polyesterharzen kombiniert, eingesetzt. Solche Polyurethane wurden durch Umsetzung von hydroxylgruppen¬ haltigen Polyethern oder Polyestern mit Isocyanaten hergestellt, wobei die Polymermischungen auch mit Polyisocyanaten vernetzt sein können, z.B. wenn die mitverwendeten spröden Polymere OH- Gruppen aufweisen.Polyurethane elastomers combined with relatively brittle polymers such as phenoxy resins, polycarbonate, polyester resins are used as the polymer composition for the purpose of the present invention. Such polyurethanes were produced by reacting hydroxyl-containing polyethers or polyesters with isocyanates, it being possible for the polymer mixtures to also be crosslinked with polyisocyanates, e.g. if the brittle polymers used have OH groups.
Die Herstellung einer Dispersion aus der Polymer-Masse und dem Pigment sowie eventuell auch unter Zugabe des Polyethylen- terephthalats kann in bekannter Weise so erfolgen, z.B. in einer Rührwerksmühle unter Zusatz von bekannten Dispergiermitteln, die Komponenten miteinander vermischt bzw. dispergiert werden. Dabei ist auch die Zugabe von Talkum und/oder anderen oben erwähnten Füllstoffen vorteilhaft. Anschließend kann die fertige Dispersion in Extrudiereinrichtungen, als Extrudat geformt, abgekühlt und z.B. als Granulat zerkleinert werden.A dispersion can be prepared from the polymer mass and the pigment and possibly also with the addition of the polyethylene terephthalate in a known manner, e.g. in an agitator mill with the addition of known dispersants, the components are mixed or dispersed with one another. The addition of talc and / or other fillers mentioned above is also advantageous. The finished dispersion can then be extruded, shaped as an extrudate, cooled and e.g. be crushed as granules.
Es können auch z.B. die Polymer-Masse und das Pigment vorgemischt werden und dann das PET und das Talkum und/oder andere Füllstoffe einzeln oder ebenfalls vorgemischt hinzugegeben werden. Die Mischtemperaturen liegen, wie auch die späteren Spritzgußtempe¬ raturen zwischen etwa 245°C und 300°C, insbesondere bei etwa 260°C bis etwa 290°C.For example, the polymer mass and the pigment are premixed and then the PET and the talc and / or other fillers are added individually or likewise premixed. The mixing temperatures, like the later injection molding temperatures, are between approximately 245 ° C. and 300 ° C., in particular approximately 260 ° C. to approximately 290 ° C.
Die erfindungsgemäßen thermoplastischen Formmassen zeichnen sich durch gute Spritzgußeigenschaften in Kaltkanal-, Stangenanguß-, Sandwich- und Heißkanal-Anspritztechniken mit Verschlußnadel-Sy¬ stem auf. Die damit hergestellten Formkörper besitzen relativ gute mechanische und elektrischen Eigenschaften (zur Abschirmung elektromagnetischer Wellen) und einen besonders geringen Verzug der Teile (Formstabilität) . Die Formmassen sind daher geeignet zur wirtschaftlichen Herstellung von Kleinteilen, Spulen und Spu¬ lenkernen für streifenförmige Materialien, Gehäuseteilen,Behäl- tem, insbesondere für die Unterhaitungs- und Datengeräteindu- strie (Gerätegehäuse, einschließlich Zubehör dafür, wie Gehäuse für Aufzeichnungsträger wie Fotofilme, etc.). Montageteile für den Fensterbau, Schalen für Werkzeugkoffer usw.. BeispielThe thermoplastic molding compositions according to the invention are notable for good injection molding properties in cold runner, bar sprue, sandwich and hot runner injection molding techniques with a closure needle system. The molded articles produced in this way have relatively good mechanical and electrical properties (for shielding electromagnetic waves) and particularly low distortion of the parts (dimensional stability). The molding compositions are therefore suitable for the economical production of small parts, coils and coil cores for strip-shaped materials, housing parts, containers, in particular for the entertainment and data device industry (device housing, including accessories therefor, such as housings for recording media such as photo films, etc.) .). Assembly parts for window construction, shells for tool cases etc. example
Es wurden folgende Komponenten eingesetzt:The following components were used:
A) Ein Polyethylenterephthalat mit einem mittleren Molekular¬ gewicht Mn (Zahlenmittelwert von etwa 30000 und einer Viskositätszahl von 73 ml/g (gemessen an einer 0,5 gew. -%igen Lösung in Phenol/o-Dichlorbenzol (Gew. -Verhältnis 1:1) (Netralen® SP 3700$ der BASF Aktiengesellschaft, 67056 Ludwigshafen) .A) A polyethylene terephthalate with an average molecular weight M n (number average of about 30,000 and a viscosity number of 73 ml / g (measured on a 0.5% by weight solution in phenol / o-dichlorobenzene (weight ratio 1 : 1) (Netralen® SP 3700 $ from BASF Aktiengesellschaft, 67056 Ludwigshafen).
B) Eine Polymer-Masse bestehend aus einem Isocyanatharz Desmodur® der Bayer AG, Leverkusen, vernetzt mit einem teil¬ weise verzweigten Polyester aus Disauren z.B. Desmolphen der 2000er Reihe der Bayer AG als Reaktionsmittel sowie ins¬ besondere Di- oder Triole als Vernetzer zur Regelung des Reaktionsverlaufs.B) A polymer mass consisting of an isocyanate resin Desmodur® from Bayer AG, Leverkusen, crosslinked with a partially branched polyester made of diacids e.g. Desmolphes of the 2000 series from Bayer AG as reactants and in particular diols or triols as crosslinkers to regulate the course of the reaction.
C) Ein feinteiliges Cr02-Pigment mit einer Teilchengröße von etwa 250 bis etwa 300 nm von Nadelform mit einem Längen-zu-C) A finely divided Cr0 2 pigment with a particle size of about 250 to about 300 nm of needle shape with a length to
Dicken-Verhältnis von etwa 15:1.Thickness ratio of about 15: 1.
Die Komponenten wurden in einem Gewichtsverhältnis von etwaThe components were in a weight ratio of approximately
Komponentenverhältnis A 70 Gew. -%Component ratio A 70% by weight
Komponentenverhältnis B 10 Gew. -%Component ratio B 10% by weight
Komponentenverhältnis C 20 Gew. -%Component ratio C 20% by weight
wie oben angegeben, dispergiert und unter Zugabe von 0,5 Gew.-% Talkum miteinander vermischt und extrudiert in Granulatform. Es ist auch möglich, erst ein Agglomerat herzu¬ stellen, dann mit Talkum zu vermischen und ein Granulat her- zustellen.as stated above, dispersed and mixed with one another with the addition of 0.5% by weight of talc and extruded in the form of granules. It is also possible to first produce an agglomerate, then mix it with talc and produce a granulate.
Aus diesem Granulat wurden Probekörper hergestellt und charakteristische Werte am Granulat bzw. am Probekörper im Vergleich zu dem eingangs genannten BASF-Produkt Ultradur® B4300G2 gemessen. SO ä Ul ae>sTest specimens were produced from this granulate and characteristic values measured on the granulate or on the test specimen in comparison to the BASF product Ultradur® B4300G2 mentioned at the beginning. SO ä Ul ae> s
0000
I erfindungsgemäße thermoplastische Formmasse πI thermoplastic molding composition π
II Ultradur® B4300 G2 (BASF AG) H βs II Ultradur® B4300 G2 (BASF AG) H βs
Der E-Modul ist abhängig vom PET-Anteil im Bereich von etwa 3250 MPa/mm2 bei über 90 Gew. -% PET bis etwa 3700 MPa/mm2 bei etwa 75 Gew. -% PET. 5The modulus of elasticity is dependent on the PET content in the range from approximately 3250 MPa / mm 2 for more than 90% by weight PET to approximately 3700 MPa / mm 2 for approximately 75% by weight PET. 5
Die erfindungsgemäße thermoplastische Formmasse I wurde auch im Spritzgußverhalten getestet und erfüllte die gestellten Erwar¬ tungen. Die Massetemperatur lag dabei etwa bei 270°C bei einem Spritzdruck PE von zwischen 18 bis 50 bar und einem Nachdruck von 10 52 bar. Die Zykluszeit beim Spritzen von Probekörpern ergab sich zu 30 oder 40 P/sec. Als Spritzgußvorrichtung wurde eine Maschine vom Typ Windsor SP 80/3, Arburg 270E verwendet, mit 800 KN bzw. 500 KN Zuhaltekraft.The thermoplastic molding composition I according to the invention was also tested in injection molding behavior and met the expectations. The melt temperature was about 270 ° C at a spray pressure PE of between 18 to 50 bar and a holding pressure of 10 52 bar. The cycle time when spraying test specimens was 30 or 40 P / sec. A Windsor SP 80/3, Arburg 270E machine with 800 KN or 500 KN locking force was used as the injection molding device.
15 Ein Spritzgußwerkzeug mit offenem Heißkanal-System erwies sich als ungeeignet, daher ergeben sich Kaltkanal-, Stangenanguß-, Schirmanschnitt und Heißkanal-Werkzeuge, letztere mit Verschlu߬ nadel-System, als zweckmäßig verwendbare Spritzgußwerkzeuge. Auch eignet sich die erfindungsgemäße Formmasse vorteilhaft für die15 An injection molding tool with an open hot runner system turned out to be unsuitable, therefore cold runner, bar sprue, screen cut and hot runner tools, the latter with a locking needle system, result as usable injection molding tools. The molding composition according to the invention is also advantageously suitable for
20 Verarbeitung im Mehrschichtspritzguß, z.B. mit Koinjektionstech- nik oder im Sandwichspritzguß, insbesondere wegen der Form¬ stabilität der Formmassen.20 Processing in multi-layer injection molding, e.g. with co-injection technology or in sandwich injection molding, in particular because of the dimensional stability of the molding compositions.
Es wurden weitere erfindungsgemäße Formmassen zu Testkörpern mit 5 unterschiedlichen Formen und Gewichten verspritzt mit dem Ergeb¬ nis, daß eine gleichmäßige Plastifizierung bei guter Entformbar- keit mit glatter und glänzender Oberfläche, ohne Werkzeugbelag und ohne Verbrennungen an den Testkörpern erreicht wurde. Der Schneckendurchmesser lag dabei bei 50 mm, die Massetemperatur 0 wurde von 250°C bis 280°C in 10 Grad-Schritten variiert sowie die Werkzeugtemperaturen von 50°C, 60°C, 75°C und 90°C eingestellt. Die Testkörper wurden sowohl im Schirmanschnitt- als auch im Punktanschnitt-Verfahren hergestellt.Further molding compositions according to the invention were injection molded into test specimens with 5 different shapes and weights, with the result that uniform plasticization with good demouldability was achieved with a smooth and glossy surface, without tooling and without burns on the test specimens. The screw diameter was 50 mm, the melt temperature 0 was varied from 250 ° C to 280 ° C in 10 degree steps and the tool temperatures of 50 ° C, 60 ° C, 75 ° C and 90 ° C. The test specimens were produced using both the screen cut and the spot cut method.
5 Die Erfindung betrifft eine thermoplastische Formmasse auf Poly- ethylenterephthalatbasis, enthält vorzugsweise 37 bis 96 Gew.-% PET, 1 bis 20 Gew. -% einer Polymer-Masse, enthaltend vorzugsweise Polyurethan, sowie etwa 4 bis 30 Gew. -% eines pigmentförmigen Verstärkungsmitteis aus Metall und/oder Metalloxid. Die Formteile 0 sind für den Spritzguß geeignet verarbeitbar und die daraus her¬ gestellten Formmassen haben vorteilhafte Eigenschaften, ins¬ besondere hinsichtlich eines geringen Schwindungsfaktors und einer höheren Dichte verglichen mit einem vergleichbaren Polybu- thylenterephalat (PBT) mit Glasfasern gefüllt. Vorteilhaft ver- 5 wendbar ist die thermoplastische Formmasse für Kleinteile, Gehäuseteile, insbesondere für Elektronik- und Datengeräte. Eine thermoplastische Formmasse auf Polyethylenterephthalatbasis enthält vorzugsweise 37 bis 96 Gew. -% PET, 1 bis 20 Gew. -% einer Polymer-Masse, enthaltend vorzugsweise Polyurethan, sowie etwa 4 bis 30 Gew. -% eines pigmentförmigen Stärkungsmittels aus Metall und/oder Metalloxid. Die Formmassen sind im Spritzguß vorteilhaft verarbeitbar und die daraus hergestellten Formteile haben vor¬ teilhafte Eigenschaften, insbesondere hinsichtlich einer höheren Dichte sowie sehr geringer isotroper Schwindung bei vergleichba¬ rem hohen E-Modul, verglichen mit einem vergleichbaren Polybuthy- lenterephthalat (PBT) mit Glasfasern gefüllt.5 The invention relates to a thermoplastic molding composition based on polyethylene terephthalate, preferably contains 37 to 96% by weight of PET, 1 to 20% by weight of a polymer composition, preferably containing polyurethane, and also approximately 4 to 30% by weight of a pigment Reinforcing means made of metal and / or metal oxide. The molded parts 0 can be processed suitably for injection molding and the molding compositions produced therefrom have advantageous properties, in particular with regard to a low shrinkage factor and a higher density compared to a comparable polybutylene terephalate (PBT) filled with glass fibers. The thermoplastic molding composition can advantageously be used for small parts, housing parts, in particular for electronic and data devices. A thermoplastic molding composition based on polyethylene terephthalate preferably contains 37 to 96% by weight of PET, 1 to 20% by weight of a polymer composition, preferably containing polyurethane, and also about 4 to 30% by weight of a pigmented tonic made of metal and / or metal oxide . The molding compositions can advantageously be processed in injection molding and the molded parts produced therefrom have advantageous properties, in particular with regard to a higher density and very low isotropic shrinkage with a comparable high modulus of elasticity, compared with a comparable polybutylene terephthalate (PBT) filled with glass fibers .
Vorteilhaft verwendbar ist die thermoplastische Formmasse für Kleinteile, Gehäuseteile jeder Art, insbesondere für Elektronik- und Datengeräte. The thermoplastic molding composition can be used advantageously for small parts, housing parts of all types, in particular for electronics and data devices.

Claims

Patentansprüche claims
1. Thermoplastische Formmassen, enthaltend als wesentliche Kom- ponenten1. Thermoplastic molding compositions containing as essential components
A) 37 bis 96 Gew.-% eines thermoplastischen Polyethylen- terephthalatsA) 37 to 96 wt .-% of a thermoplastic polyethylene terephthalate
B) 1 bis 20 Gew.-% einer Polymer-MasseB) 1 to 20 wt .-% of a polymer mass
undand
C) 4 bis 30 Gew.-% eines pigmentförmigen Verstärkungsmit- tels.C) 4 to 30% by weight of a pigment-shaped reinforcing agent.
2. Thermoplastische Formmassen nach Anspruch 1, enthaltend als wesentliche Komponenten2. Thermoplastic molding compositions according to claim 1, containing as essential components
A) 60 bis 77 Gew.-% eines thermoplastischen Polyethylen- terephthalatsA) 60 to 77 wt .-% of a thermoplastic polyethylene terephthalate
B) 4 bis 12 Gew.-% einer Polymer-MasseB) 4 to 12 wt .-% of a polymer mass
undand
C) 4 bis 21 Gew.-% eines pigmentförmigen Verstärkungsmit- tels.C) 4 to 21% by weight of a pigment-shaped reinforcing agent.
3. Thermoplastische Formmassen nach Anspruch 1, enthaltend als wesentliche Komponenten3. Thermoplastic molding compositions according to claim 1, containing as essential components
A) 50 bis 60 Gew.-% eines thermoplastischen Polyethylen- terephthalatsA) 50 to 60 wt .-% of a thermoplastic polyethylene terephthalate
B) 10 bis 20 Gew.-% einer Polymer-MasseB) 10 to 20 wt .-% of a polymer mass
undand
C) 20 bis 30 Gew.-% eines pigmentförmigen Verstärkungsmit- tels.C) 20 to 30% by weight of a pigment-shaped reinforcing agent.
4. Thermoplastische Formmassen nach Anspruch 3, enthaltend als wesentliche Komponenten A) 41 bis 50 Gew.-% eines thermoplastischen Polyethylen- terephthalats4. Thermoplastic molding compositions according to claim 3, containing as essential components A) 41 to 50 wt .-% of a thermoplastic polyethylene terephthalate
B) 12 bis 20 Gew.-% einer Polymer-MasseB) 12 to 20 wt .-% of a polymer mass
undand
C) 18 bis 30 Gew.-% eines pigmentförmigen Verstärkungsmit- tels.C) 18 to 30% by weight of a pigment-shaped reinforcing agent.
5. Thermoplastische Formmassen nach Anspruch 2, enthaltend als wesentliche Komponenten5. Thermoplastic molding compositions according to claim 2, containing as essential components
A) 69 bis 77 Gew.-% eines thermoplastischen Polyethylen- terephthalateA) 69 to 77 wt .-% of a thermoplastic polyethylene terephthalate
B) 4 bis 6 Gew.-% einer Polymer-MasseB) 4 to 6% by weight of a polymer mass
undand
C) 15 bis 21 Gew.-% eines pigmentförmigen Verstärkungsmit- tels.C) 15 to 21% by weight of a pigment-shaped reinforcing agent.
6. Thermoplastische Formmassen zum Spritzgießen von Formteilen, enthaltend überwiegend ein thermoplastisches Polyethylen¬ terephthalat und eine polymere Masse nach einem der Ansprüche 1, 2 oder 5, gekennzeichnet durch ein Gewichtsverhältnis von6. Thermoplastic molding compositions for injection molding of molded parts containing predominantly a thermoplastic polyethylene terephthalate and a polymeric composition according to one of claims 1, 2 or 5, characterized by a weight ratio of
60 bis 77 Gew.-% Polyethylenterephthalat 4 bis 12 Gew.-% Polymer-Masse60 to 77 wt .-% polyethylene terephthalate 4 to 12 wt .-% polymer mass
4 bis 21 Gew.-% eines pigmentförmigen Verstärkungsmitteis,4 to 21% by weight of a pigment-shaped reinforcing agent,
wobei die Formteile mit einer Massetemperatur zwischen etwa 245 bis 300°C spritzbar sind.wherein the moldings are sprayable with a melt temperature between about 245 to 300 ° C.
7. Thermoplastische Formmassen zum Spritzgießen von Formteilen, enthaltend überwiegend ein thermoplastisches Polyethylen¬ terephthalat und eine polymere Masse nach einem der Ansprü¬ che 1, 3 oder 4,gekennzeichnet durch ein Gewichtsverhältnis von7. Thermoplastic molding compositions for injection molding of molded parts, containing predominantly a thermoplastic polyethylene terephthalate and a polymeric composition according to one of claims 1, 3 or 4, characterized by a weight ratio of
50 bis 60 Gew.-% Polyethylenterephthalat50 to 60% by weight of polyethylene terephthalate
10 bis 20 Gew.-% Polymer-Masse10 to 20 wt .-% polymer mass
20 bis 30 Gew.-% eines pigmentförmigen Verstärkungsmitteis, wobei die Formteile mit einer Massetemperatur zwischen etwa 245 bis 300°C spritzbar sind.20 to 30% by weight of a pigment-shaped reinforcing agent, wherein the moldings are sprayable with a melt temperature between about 245 to 300 ° C.
8. Formmassen nach den Ansprüchen 1 bis 7, dadurch gekennzeich- 5 net, daß die Polymer-Masse überwiegend Polyurethan enthält.8. Molding compositions according to claims 1 to 7, characterized in that the polymer composition contains predominantly polyurethane.
9. Formmassen nach einem der Ansprüche 1 bis 8, dadurch gekenn¬ zeichnet, daß der Feuchtigkeitsgehalt höchstens 0,1 Gew.-%, insbesondere 0,05 Gew. -% beträgt.9. Molding compositions according to one of claims 1 to 8, characterized in that the moisture content is at most 0.1% by weight, in particular 0.05% by weight.
1010
10. Formmassen nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Pigmente aus Metall und/oder Metalloxid bestehen.10. Molding compositions according to one or more of claims 1 to 9, characterized in that the pigments consist of metal and / or metal oxide.
15 11. Formmassen nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Pigmente eine mittlere durch¬ schnittliche Teilchengröße von kleiner gleich 400 nm besit¬ zen.15 11. Molding compositions according to one or more of claims 1 to 10, characterized in that the pigments have a mean average particle size of less than or equal to 400 nm.
20 12. Formmassen nach Anspruch 10 oder 11, dadurch gekennzeichnet, daß die Metall- und/oder Metalloxid-Pigmente ein Längen-zu- Dicken-Verhältnis von 5:1 bis 15:1 aufweisen.20 12. Molding compositions according to claim 10 or 11, characterized in that the metal and / or metal oxide pigments have a length-to-thickness ratio of 5: 1 to 15: 1.
13. Formmassen nach einem der Ansprüche 1 bis 12, dadurch gekenn- 25 zeichnet, daß sie 0,2 bis 0,8, insbesonders 0,5 Gew.-% Talkum enthalten.13. Molding compositions according to one of claims 1 to 12, characterized marked 25 that they contain 0.2 to 0.8, in particular 0.5 wt .-% talc.
14. Formmassen nach einem der Ansprüche 1 bis 13, dadurch gekenn¬ zeichnet, daß sie in Spritzguß-Vorrichtungen mit Verschluß-14. Molding compositions according to one of claims 1 to 13, characterized gekenn¬ characterized in that they are in injection molding devices with closure
30 düse und Heißkanal-System verarbeitbar sind.30 nozzle and hot runner system can be processed.
15. Formmassen nach einem der Ansprüche 1 bis 14, dadurch gekenn¬ zeichnet, daß sie in Spritzguß-Vorrichtungen mit Kaltkanal- System verarbeitbar sind.15. Molding compositions according to one of claims 1 to 14, characterized gekenn¬ characterized in that they can be processed in injection molding devices with a cold runner system.
3535
16. Formmassen nach einem der Ansprüche 1 bis 15, dadurch gekenn¬ zeichnet, daß sie im Mehrschichtspritzguß, insbesondere mit Koinjektionstechnik, oder im Sandwichspritzguß verarbeitbar sind. 016. Molding compositions according to one of claims 1 to 15, characterized gekenn¬ characterized in that they can be processed in multi-layer injection molding, in particular with co-injection technology, or in sandwich injection molding. 0
17. Spritzguß-Formteil aus einer Kunststoff-Mischung nach Anspruch 1 bis 5 und einem oder mehreren Ansprüchen 6 bis 13 und 19, gekennzeichnet durch eine Dichte von > 1,4 g/cm3, insbesondere von 1,48 g/cm3. 5 17. injection molding from a plastic mixture according to claim 1 to 5 and one or more claims 6 to 13 and 19, characterized by a density of> 1.4 g / cm 3 , in particular of 1.48 g / cm 3 . 5
18. Formmassen nach Anspruch 1 und einem oder mehreren der An¬ sprüche 1 bis 17, dadurch gekennzeichnet, daß der Volumen- Fließ-Index (MVI) bei 275°C/2,16 kg wenigstens etwa18. Molding compositions according to claim 1 and one or more of claims 1 to 17, characterized in that the volume flow index (MVI) at 275 ° C / 2.16 kg at least approximately
25 ml/10 min beträgt. 5Is 25 ml / 10 min. 5
19. Formmassen nach Anspruch 1 bis 18, dadurch gekennzeichnet, daß die Pigmente aus Cr02-Pigmenten bestehen.19. Molding compositions according to claim 1 to 18, characterized in that the pigments consist of Cr0 2 pigments.
20. Formteil aus den thermoplastischen Formmassen gemäß einem der 10 Ansprüche 1 bis 7 als wesentliche Komponente.20. Molding from the thermoplastic molding compositions according to one of 10 claims 1 to 7 as an essential component.
21. Formteil, im Spritzguß hergestellt, nach Anspruch 19 und 20, gekennzeichnet durch einen E-Modul von > 3200 MPa/mm2, ins¬ besondere von ca. 3500 MPa/mm2 bis ca. 3700 MPa/mm2.21. Molded part, produced by injection molding, according to claims 19 and 20, characterized by an elastic modulus of> 3200 MPa / mm 2 , in particular from approximately 3500 MPa / mm 2 to approximately 3700 MPa / mm 2 .
1515
22. Spritzguß-Formteil nach Anspruch 20, hergestellt aus einer Formmasse nach Anspruch 15, gekennzeichnet durch eine im wesentlichen gleichmäßige Anthrazit-Farbe und einen hohen Glanz.22. Injection molded part according to claim 20, produced from a molding composition according to claim 15, characterized by a substantially uniform anthracite color and a high gloss.
2020th
23. Spritzguß-Formteil nach Anspruch 18, gekennzeichnet durch eine geringe Schwindung des spritzgegossenen Teils von längs und quer, von etwa je 0,2 %.23. Injection molded part according to claim 18, characterized by a slight shrinkage of the injection-molded part lengthways and crossways, of about 0.2% each.
25 24. Formmassen nach Anspruch 14 oder 15, dadurch gekennzeichnet, daß die Förderschnecke der Spritzguß-Vorrichtung einen Durch¬ messer von 20 bis 80 mm, insbesondere von 25 bis 60 mm, auf¬ weist.25 24. Molding compositions according to claim 14 or 15, characterized in that the screw conveyor of the injection molding device has a diameter of 20 to 80 mm, in particular 25 to 60 mm.
30 25. Formmassen nach Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß ein Chloranteil nicht größer ist als 0,5 Gew. -% des Ge¬ wichts der Masse, insbesondere nicht vorhanden ist.30 25. Molding compositions according to claims 1 to 7, characterized in that a chlorine content is not greater than 0.5% by weight of the weight of the composition, in particular is not present.
3535
00
5 5
EP96944577A 1995-12-22 1996-12-16 Thermoplastic moulding materials based on polyethylene terephthalate for use in injection moulding of parts Withdrawn EP0868487A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19548319 1995-12-22
DE19548319A DE19548319A1 (en) 1995-12-22 1995-12-22 Thermoplastic molding compounds for the injection molding of molded parts and injection molded molded part therefrom
PCT/EP1996/005636 WO1997023566A1 (en) 1995-12-22 1996-12-16 Thermoplastic moulding materials based on polyethylene terephthalate for use in injection moulding of parts

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EP0868487A1 true EP0868487A1 (en) 1998-10-07

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KR (1) KR19990076642A (en)
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AU (1) AU1301597A (en)
DE (2) DE19548319A1 (en)
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DE19548319A1 (en) 1997-06-26
CN1085704C (en) 2002-05-29
US6046264A (en) 2000-04-04
DE29621057U1 (en) 1997-03-13
AU1301597A (en) 1997-07-17
CN1205729A (en) 1999-01-20
KR19990076642A (en) 1999-10-15
RU2201946C2 (en) 2003-04-10
WO1997023566A1 (en) 1997-07-03

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