EP0868487A1 - Thermoplastische formmassen auf basis von polyethylenterephthalat zum spritzgiessen von formteilen - Google Patents

Thermoplastische formmassen auf basis von polyethylenterephthalat zum spritzgiessen von formteilen

Info

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Withdrawn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)
English (en)
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Emtec Magnetics GmbH filed Critical Emtec Magnetics GmbH
Publication of EP0868487A1 publication Critical patent/EP0868487A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001Injection 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; 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.

Landscapes

  • 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)
EP96944577A 1995-12-22 1996-12-16 Thermoplastische formmassen auf basis von polyethylenterephthalat zum spritzgiessen von formteilen Withdrawn EP0868487A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19548319 1995-12-22
DE19548319A DE19548319A1 (de) 1995-12-22 1995-12-22 Thermoplastische Formmassen zum Spritzgießen von Formteilen und Spritzguß-Formteil daraus
PCT/EP1996/005636 WO1997023566A1 (de) 1995-12-22 1996-12-16 Thermoplastische formmassen auf basis von polyethylenterephthalat zum spritzgiessen von formteilen

Publications (1)

Publication Number Publication Date
EP0868487A1 true EP0868487A1 (de) 1998-10-07

Family

ID=7781142

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96944577A Withdrawn EP0868487A1 (de) 1995-12-22 1996-12-16 Thermoplastische formmassen auf basis von polyethylenterephthalat zum spritzgiessen von formteilen

Country Status (9)

Country Link
US (1) US6046264A (ja)
EP (1) EP0868487A1 (ja)
JP (1) JP2000505122A (ja)
KR (1) KR19990076642A (ja)
CN (1) CN1085704C (ja)
AU (1) AU1301597A (ja)
DE (2) DE19548319A1 (ja)
RU (1) RU2201946C2 (ja)
WO (1) WO1997023566A1 (ja)

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DE10051472B4 (de) * 2000-10-17 2009-06-04 Conti Temic Microelectronic Gmbh Elektronische Baugruppe und Verfahren zur Herstellung einer elektronischen Baugruppe
US20020135102A1 (en) * 2001-02-12 2002-09-26 Forbes Alan H. Injection-molded, mineral-filled articles and processes for making the same
US6893694B2 (en) 2001-05-08 2005-05-17 Pactiv Corporation Containers and sheets made of filled polymer compositions
RU2271929C2 (ru) 2002-04-19 2006-03-20 Сэнт-Гобэн Керамикс Энд Пластикс, Инк. Модифицированный полимерный материал (варианты) и способ формирования экструдированного продукта
US7307125B2 (en) * 2004-12-15 2007-12-11 Ferro Corporation Thermoplastic olefin compositions and injection molded articles made thereof
US7479324B2 (en) 2005-11-08 2009-01-20 Saint-Gobain Ceramics & Plastics, Inc. Pigments comprising alumina hydrate and a dye, and polymer composites formed thereof
SI2043802T1 (sl) * 2006-07-13 2012-11-30 Basf Se Termoplastične mase ki vsebujejo vezalna sredstva za proizvodnjo kovinskih kalupov
EP2209842A1 (en) 2007-10-19 2010-07-28 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate as barrier property enhancer in polymers
US11505638B2 (en) 2017-04-28 2022-11-22 Derrick Corporation Thermoplastic compositions, methods, apparatus, and uses
CN114161656B (zh) * 2021-11-20 2024-08-30 佛山市顺德区容声塑胶有限公司 具有电磁屏蔽功能的夹芯注塑制品制造方法、产品、应用

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Also Published As

Publication number Publication date
JP2000505122A (ja) 2000-04-25
DE19548319A1 (de) 1997-06-26
CN1085704C (zh) 2002-05-29
US6046264A (en) 2000-04-04
DE29621057U1 (de) 1997-03-13
AU1301597A (en) 1997-07-17
CN1205729A (zh) 1999-01-20
KR19990076642A (ko) 1999-10-15
RU2201946C2 (ru) 2003-04-10
WO1997023566A1 (de) 1997-07-03

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