EP0181587A2 - Mélanges polymères thermoplastiques antistatiques ou électriquement semi-conducteurs, procédé pour leur fabrication et leur mise en oeuvre - Google Patents

Mélanges polymères thermoplastiques antistatiques ou électriquement semi-conducteurs, procédé pour leur fabrication et leur mise en oeuvre Download PDF

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Publication number
EP0181587A2
EP0181587A2 EP85114008A EP85114008A EP0181587A2 EP 0181587 A2 EP0181587 A2 EP 0181587A2 EP 85114008 A EP85114008 A EP 85114008A EP 85114008 A EP85114008 A EP 85114008A EP 0181587 A2 EP0181587 A2 EP 0181587A2
Authority
EP
European Patent Office
Prior art keywords
polymer
copolymer
polymers
ethylene
vinyl acetate
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.)
Granted
Application number
EP85114008A
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German (de)
English (en)
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EP0181587A3 (en
EP0181587B1 (fr
Inventor
Bernhard Dr. Wessling
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.)
Zipperling Kessler GmbH and Co
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Zipperling Kessler GmbH and Co
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Priority to AT85114008T priority Critical patent/ATE43745T1/de
Publication of EP0181587A2 publication Critical patent/EP0181587A2/fr
Publication of EP0181587A3 publication Critical patent/EP0181587A3/de
Application granted granted Critical
Publication of EP0181587B1 publication Critical patent/EP0181587B1/fr
Expired legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon

Definitions

  • thermoplastic polymers which are electrical insulators per se.
  • Mainly non-polymeric additives such as in particular antistatic agents, can be used to provide statically easily chargeable polymers with antistatic properties.
  • the surface resistance can be reduced from 10 12 to 10 16 ⁇ down to approx . Reach 10 8 to 1010 2 (see DE-PS 33 47 704.3).
  • a further reduction in the specific resistance to approximately 1 0 1 to 10 ßcm (semiconducting to antistatic finish) can be achieved with the aid of conductive additives such as metal fibers or particles, carbon fibers, conductive carbon black (cf. A. Sternfield, Modern Plastics International, No. 7 , 48ff (1982)).
  • conductive additives such as metal fibers or particles, carbon fibers, conductive carbon black (cf. A. Sternfield, Modern Plastics International, No. 7 , 48ff (1982)).
  • These additives are used in amounts of approximately 10 to 30% by weight. They not only lead to a superficial antistatic finish, but also to
  • the increase in the electrical conductivity from the initial value of the non-conductive polymer to a value characteristic of the conductive substance is not linearly dependent on the concentration of the substance added. Rather, a more or less steep increase in conductivity is observed at the breakthrough point (percolation point), which is due to the fact that the particles of the conductive substance are now sufficiently close or touching, thereby forming continuous current paths or conductor tracks.
  • the breakthrough point depends on the geometry, in particular the ratio of length to diameter, and the surface of the added particles, the type of polymer and on the applied D ispergiermethode very heavily dependent.
  • the percolation point is the turning point of the curve when the logarithm of the conductivity is plotted against the concentration of the conductive additive.
  • DE-OS 29 01 758 and 29 01 776 describe the production of a network of conductive carbon black (through which the current flows) in a molding compound made of polyethylene as a matrix.
  • the molding compound described is only suitable for the discontinuous production of plates in the pressing process, but not for continuous processing by extrusion or other conventional processing methods for thermoplastics, since the network and thus the conductivity are destroyed.
  • DE-OS 32 08 841 and 32 08 842 disclose the two- to three-stage production of conductive black-containing polyvinyl chloride blends with other polymers, especially ethylene-vinyl acetate copolymers.
  • the thermoplastic composition should contain 15% by weight of carbon black, the polymer components and the process serve to improve processability.
  • DE-OS 25 17 358 mentions the addition of rubber to increase the impact strength without reducing the proportion of soot.
  • the carbon black is added to a previously produced homogeneous polymer / rubber mixture.
  • soot-containing polyethylene / polyamide blends that the soot is concentrated in the polyethylene phase and not in the polyamide islands. This can easily be explained by the large difference in the softening or melting ranges and the incompatibility of the two polymers.
  • the polyamide behaves like a non-melting filler, so that there is no compatible blend good application properties is obtained.
  • the soot contents required for sufficient conductivity are very high and even exceed the contents in homogeneous preparations based on one polymer or several fully compatible polymers which are common in industrial practice today.
  • DE-AS 28 08 675 describes a process in which polyethylene with conductive carbon black is added to the polyoxymethylene resin. In this way, however, only surface resistances of more than 10 6 n can be achieved.
  • the object of the invention is, therefore, olymerblends provide antistatic or electrically semiconducting thermoplastically processable P, which contain a significantly lower content of electrically conductive additives than hitherto usual, having can be but thermoplastic (at least substantial) to give the conductivity to process and good mechanical properties .
  • the previously necessary to achieve the percolation added amounts are from about 10 to 20 wt.% R ow and about 30 to 50 wt.% Metal powder, depending on the geometry and surface of the particles, the interfacial tension of the polymer and the temperature (see FIG. Thereto also Miyasaka, aa0., whereby the theoretical values have so far not been achievable).
  • the invention relates to antistatic or electrically semiconducting thermoplastic polymer blends based on organic polymers and electrically conductive substances, which are characterized in that they contain two partially compatible thermoplastic polymers A and B, of which the polymer A at a given temperature compared to the polymer B. has a lower melt viscosity and between which there is a solubility parameter difference of approximately 0.3 to 1.5 (cal / cm 3) 1/3, the polymer A forming the continuous phase essentially containing the electrically conductive substances.
  • polymer A and / or polymer B can be mixtures of thermoplastic polymers which are fully compatible with one another.
  • examples of such mixtures are styrene-acrylonitrile copolymer (SAN) with chlorinated polyethylene (PEC) and polyvinyl butyral (PVB) Polyvinylpyrrolidone-vinyl acetate copolymer (PVP-VA).
  • the conductive additive is essentially in polymer A, which forms the continuous phase of the blend.
  • polymer A is normally in a deficit, i.e. a weight ratio of polymer A: polymer B ⁇ 1: 1 is used.
  • the proportion of polymer A in the mixture of polymers A and B is preferably about 20 to 40% by weight.
  • the amount of polymer A depends on the amount of conductive additives present, since, based on the total blend, the amount of polymer A and conductive additives should preferably be less than 50% by weight, for example 10 to 49% by weight.
  • electrically conductive auxiliary is preferably conductive carbon black with a BET surface area> 250 m 2 / g and with a dibutylphthalate absorption> 140 cm 3/100 g use.
  • carbon fibers, metal powder or fibers, electrically conductive organic polymers or non-polymeric organic conductors are also suitable.
  • Conductive polymers are understood to mean polyconjugated systems such as those found in polyacetylene (PAc), poly-1,3,5, ...
  • n-substituted polyacetylenes, acetylene copolymers, and 1,3-tetramethylene-bridged polymers for example in from Polymerization of 1,6-heptadiin resulting polymers and similar derivatives of polyacetylene are present; these also include the different modifications of polyparaphenylenes (PPP), the different modifications of polypyrroles (PPy), the different modifications of polyphthalocyanines (PPhc) and other polymeric organic conductors.
  • PPP polyparaphenylenes
  • Py polypyrroles
  • PPhc polyphthalocyanines
  • These can be present as such or as polymers (“doped") complexed with oxidizing or reducing substances; the complexation generally leads to an increase in the electrical conductivity by several orders of magnitude down to the area of metallic conductors.
  • Organic conductors are understood to mean conductive non-polymeric organic substances, in particular complex salts or charge transfer complexes, for example the different modifications of te
  • Carbon black is preferably added to the polymer blends according to the invention in an amount of about 0.5 to 10, in particular 4 to 10,% by weight, based on the polymer blend.
  • the required content may be higher and up to 30% by weight; however, it is regularly lower than in the previously known products, in which the conductive additive is present in the polymer in a uniformly dispersed manner.
  • Surface resistance values of 10 to 10 6 ⁇ are achieved.
  • polycaprolactone whereby single-phase microstructures (with styrene / acrylonitrile copolymer, polyvinyl chloride or polycarbonate as the polymer) can be used in the light microscope B), drop structures (with polyethylene or ethylene-vinyl acetate as polymer B) or also the particularly preferred conductor tracks (with polyether polyurethane or acrylonitrile / methacrylate / butadiene copolymer as polymer B). Even with an addition in the order of 1 to 3% by weight, a surface resistance of approximately 10 5 to 108 g is obtained.
  • the polymer blends according to the invention can also contain conventional additives such as stabilizers, pigments, lubricants, etc.
  • conventional additives such as stabilizers, pigments, lubricants, etc.
  • chemical crosslinkers e.g. a preferably liquid peroxide, and thereby to achieve a crosslinking of the polymers during the subsequent processing of the blends with heating, which brings about a mechanical stabilization of the conductor tracks achieved according to the invention.
  • the crosslinking agent is particularly preferably added to polymer A or to the conductivity concentrate consisting of polymer A and the conductive substances, in order to stabilize the conductor tracks in the matrix made of polymer B.
  • the procedure can be followed in a first step by dispersing the conductive substances in a solution or melt of polymer A or a prepolymer for polymer A, if appropriate removing the solvent, and then in a second step prepared conductivity concentrate melted with the polymer B and polymerized using a prepolymer.
  • suitable polymer combinations it is also possible to disperse the conductive substances directly into a melt of polymers A and B.
  • the first-mentioned method of operation is particularly suitable, for example, for the combination of ethylene-vinyl acetate (polymer A) and polyvinyl chloride (polymer B), since the preparation of a conductivity concentrate from this polymer A and carbon black and subsequent melt mixing with the polymer B gives substantially better results, in particular one even lower soot content with the same electrical conductivity, obtained than with the one-step process.
  • the mechanical properties of the polymer blends according to the invention are excellent. In particular, they show very good impact strength values ("without break").
  • Conductivity concentrates which contain polymer A and a conductive substance are used for the production process described above.
  • conductive carbon black in an amount of more than 15% by weight, preferably about 20% by weight, metal powder in an amount of more than 50% by weight, or an organic conductive polymer or a non-polymeric organic conductor in an amount of more than 10, preferably about 15,% by weight.
  • These conductivity concentrates are preferably added directly to polymer B in the production of end products.
  • crosslinking it may be desirable to crosslink the polymers to stabilize the structure. If chemical crosslinking agents are added to the polymer blend, this can be done by heating during the manufacture of the blend or during its processing. On the other hand, it is also possible to achieve crosslinking in a manner known per se by irradiation.
  • a conductive, thermoplastically processable block copolymer is obtained in which the blocks derived from the prepolymer form a continuous conductor track in the matrix.
  • L eitschreibsonne to 10 2 to 10 4 2cm at a content of prepolymer from 10 to 20 wt.%
  • a carbon black content in the prepolymer of about 20% corresponding to a content of carbon black in the blend of 2 to 4 wt.%.
  • the desired coupling reaction may have to be catalyzed, e.g. Transesterification or transamidation reactions with p-toluenesulfonic acid.
  • the polymer blends according to the invention can, if appropriate, first be granulated and supplied as granules to further processors. On the other hand, they can also be processed directly into finished products.
  • the blends are particularly suitable for the production of antistatic, electrically conductive coatings, foils, molded parts or moldings.
  • the films or molded parts produced from the polymer blends are mechanically stretched, this leads to an alignment of the conductor tracks, with the result that the stretched materials show a preferred flow direction, which is particularly advantageous for various applications can.
  • the granulate By extrusion, the granulate could be used to produce thermoformed sheets with a surface resistance of 0.5 to 5.10 4 ⁇ .
  • the plates had an impact strength (DIN 53453) "without break” and a notched impact strength of 14 mJ / mm.
  • Example 1 As described in Example 1, 79% by weight of ethylene-vinyl acetate copolymer (with a vinyl acetate content of 7%), in addition to conventional stabilizers and processing aids, were admixed with 20% by weight of carbon black and mixed with one another at 170.degree.
  • the conductivity concentrate thus obtained (specific resistance according to the four-point method approx. 5 Qcm) was granulated in a second operation with stabilized polyvinyl chloride granules (K value 67 or 70) or immediately extruded to a finished product (for example a plate), the melt temperature was approx. 185 to 190 ° C.
  • the semiconducting polymer blend obtained or the finished plate showed an impact strength "without break" and the electrical properties listed in Table 1 below.
  • the polyacetylene concentrate was extruded on a single-screw extruder with the polymers B listed in the table below to form a polymer blend, with either a granulate or a finished product being produced.
  • the product obtained can, for example, be made more conductive ("doped") by treatment with iodine. The results shown in the following table were obtained.
  • a mixture of 1.2% TCNQ complex in PCL is mixed in an internal mixer with the same amount of EVA (30% VA) at 130-160 0 .
  • the mass obtained is pressed out into a film. This is pressed at 190 ° C. for 30 seconds, the TCNQ complex dissolving.
  • the film is then immediately annealed in hot water at 95 ° C. for 10 minutes and then quenched in water at 15 ° C. Tempering at 95 ° produces tuft-shaped, very long TCNQ complex crystal needles.
  • the film has a surface resistance of 3 x 10 8 ⁇ (without TCNQ: approx. 10 12 ⁇ ).

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Conductive Materials (AREA)
EP85114008A 1984-11-07 1985-11-04 Mélanges polymères thermoplastiques antistatiques ou électriquement semi-conducteurs, procédé pour leur fabrication et leur mise en oeuvre Expired EP0181587B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85114008T ATE43745T1 (de) 1984-11-07 1985-11-04 Antistatische bzw. elektrisch halbleitende thermoplastische polymerblends, verfahren zu deren herstellung und deren verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3440617 1984-11-07
DE3440617A DE3440617C1 (de) 1984-11-07 1984-11-07 Antistatische bzw. elektrisch halbleitende thermoplastische Polymerblends,Verfahren zu deren Herstellung und deren Verwendung

Publications (3)

Publication Number Publication Date
EP0181587A2 true EP0181587A2 (fr) 1986-05-21
EP0181587A3 EP0181587A3 (en) 1986-12-30
EP0181587B1 EP0181587B1 (fr) 1989-05-31

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EP85114008A Expired EP0181587B1 (fr) 1984-11-07 1985-11-04 Mélanges polymères thermoplastiques antistatiques ou électriquement semi-conducteurs, procédé pour leur fabrication et leur mise en oeuvre

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US (1) US4929388A (fr)
EP (1) EP0181587B1 (fr)
AT (1) ATE43745T1 (fr)
DE (2) DE3440617C1 (fr)

Cited By (21)

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EP0231068A3 (en) * 1986-01-14 1987-09-16 Raychem Corporation Conductive polymer composition
WO1989000755A1 (fr) * 1986-01-14 1989-01-26 Raychem Corporation Composition polymere conductrice
US5106540A (en) * 1986-01-14 1992-04-21 Raychem Corporation Conductive polymer composition
EP0231068A2 (fr) * 1986-01-14 1987-08-05 RAYCHEM CORPORATION (a Delaware corporation) Composition polymère conductrice
EP0280173A3 (en) * 1987-02-25 1990-05-23 Showa Denko Kabushiki Kaisha Radical polymerizable composition
EP0280173A2 (fr) * 1987-02-25 1988-08-31 Showa Denko Kabushiki Kaisha Composition polymérisable par réaction radicale
US5137993A (en) * 1987-02-25 1992-08-11 Showa Denko K.K. Radical polymerizable composition
EP0296263A1 (fr) * 1987-06-23 1988-12-28 The Dow Chemical Company Composite de polymère-latex électroconducteur
US5106538A (en) * 1987-07-21 1992-04-21 Raychem Corporation Conductive polymer composition
GB2214511A (en) * 1988-01-29 1989-09-06 Zipperling Kessler & Co A method of preparing compositions with optimized conductivity behaviour
EP0337487A1 (fr) * 1988-04-15 1989-10-18 Showa Denko Kabushiki Kaisha Composition polymère électroconductrice
US5213736A (en) * 1988-04-15 1993-05-25 Showa Denko K.K. Process for making an electroconductive polymer composition
WO1991006592A1 (fr) * 1989-10-24 1991-05-16 Exxon Chemical Patents Inc. Copolymere greffe de polylactone sur un squelette de polymere
US5130371A (en) * 1989-10-24 1992-07-14 Exxon Chemical Patents Inc. Crystalline polyolefin graft copolymers
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EP0658277A4 (fr) * 1992-09-04 1995-12-20 Unisearch Ltd Electrode plastique flexible et conductrice et son procede.
EP0658277A1 (fr) * 1992-09-04 1995-06-21 Unisearch Ltd. Electrode plastique flexible et conductrice et son procede
FR2721324A1 (fr) * 1994-06-16 1995-12-22 Tiag Ind Matériau polymère antistatique.
US6015509A (en) * 1994-12-14 2000-01-18 International Business Machines Corporation Composition containing a polymer and conductive filler and use thereof
EP0717418A2 (fr) * 1994-12-14 1996-06-19 International Business Machines Corporation Composition contenant un polymère et un matériau de remplissage conducteur et utilisation de celle-ci
EP0717418A3 (fr) * 1994-12-14 1997-02-19 Ibm Composition contenant un polymère et un matériau de remplissage conducteur et utilisation de celle-ci
US5916486A (en) * 1994-12-14 1999-06-29 International Business Machines Corporation Method for providing discharge protection or shielding
US5922466A (en) * 1994-12-14 1999-07-13 International Business Machines Corporation Composite comprising a metal substrate and a corrosion protecting layer
US5997773A (en) * 1994-12-14 1999-12-07 International Business Machines Corporation Method for providing discharge protection or shielding
WO1999050351A1 (fr) * 1998-03-31 1999-10-07 Basf Aktiengesellschaft Corps moules en polyoxymethylene
US6284832B1 (en) 1998-10-23 2001-09-04 Pirelli Cables And Systems, Llc Crosslinked conducting polymer composite materials and method of making same
US6417265B1 (en) 1998-10-23 2002-07-09 Pirelli Cables And Systems Llc Crosslinked conducting polymer composite materials and method of making same
US6315956B1 (en) 1999-03-16 2001-11-13 Pirelli Cables And Systems Llc Electrochemical sensors made from conductive polymer composite materials and methods of making same
EP1218176A1 (fr) * 1999-08-17 2002-07-03 Pirelli Cables and Systems LLC Compose de remplissage a conducteur torsade et cables l'utilisant
EP1218176A4 (fr) * 1999-08-17 2003-08-20 Pirelli Cables & Systems Llc Compose de remplissage a conducteur torsade et cables l'utilisant
US7148281B2 (en) 2001-04-04 2006-12-12 Premix Oy Polymer blend and method of preparing same
DE10242955A1 (de) * 2002-09-17 2004-03-25 Schütz GmbH & Co. KGaA Kunststoffaß und Verfahren zur Herstellung des Fasses
DE10242955B4 (de) * 2002-09-17 2005-03-10 Schuetz Gmbh & Co Kgaa Kunststoffaß und Verfahren zur Herstellung des Fasses

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EP0181587A3 (en) 1986-12-30
DE3570796D1 (en) 1989-07-06
ATE43745T1 (de) 1989-06-15
US4929388A (en) 1990-05-29
EP0181587B1 (fr) 1989-05-31
DE3440617C1 (de) 1986-06-26

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