EP0181587B1 - 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
EP0181587B1
EP0181587B1 EP85114008A EP85114008A EP0181587B1 EP 0181587 B1 EP0181587 B1 EP 0181587B1 EP 85114008 A EP85114008 A EP 85114008A EP 85114008 A EP85114008 A EP 85114008A EP 0181587 B1 EP0181587 B1 EP 0181587B1
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Prior art keywords
polymer
copolymer
polymers
ethylene
styrene
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German (de)
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EP0181587A3 (en
EP0181587A2 (fr
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Bernhard Dr. Wessling
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Zipperling Kessler GmbH and Co
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Zipperling Kessler GmbH and Co
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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 Q to approximately 10 8 to 10 10 Q (cf. DE-PS-3 347 704.3).
  • a further reduction in the specific resistance to approx. 10 1 to 10 7 Qcm semiconductor to antistatic finish
  • 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 a reduction in volume resistance.
  • 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 is extremely dependent on the geometry, in particular the ratio of length to diameter, and the surface of the added particles, on the type of polymer and on the dispersion method used.
  • 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-2 901 758 and 2 901 776 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-3 208 841 and 3 208 842 disclose the two- to three-stage production of conductive black-containing polyvinyl chloride blends with other polymers, in particular ethylene-vinyl acetate copolymers.
  • the thermoplastic composition should contain 15% by weight of carbon black, the polymer components and the process serve to improve the 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.
  • DE-AS-2 808 675 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 Q can be achieved.
  • the additional quantities required to achieve percolation are approximately 10 to 20% by weight of carbon black or approximately 30 to 50% by weight of metal powder, depending on the geometry and surface of the particles, the interfacial tension of the polymer and the temperature (cf. also Miyasaka, loc. cit., 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 solubility parameter between which a difference of about 0.3 to 1.5 (cal / cm 3) 1/2 exists, wherein the polymer a forming the continuous phase substantially contains 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) with polyvinyl pyrrolidone-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 is preferably less than 50% by weight, for example 10 to 49% by weight should.
  • the 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 as used in polyacetylene (PAc), poly-1,3,5, ... n-substituted polyacetylenes, acetylene copolymers, and 1,3-tetramethylene-bridged polymers, e.g. B.
  • polymers and similar derivatives of polyacetylene resulting from the polymerization of 1,6-heptadiin 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
  • PPy polypyrroles
  • PPhc polyphthalocyanines
  • organic conductors are understood to mean conductive non-polymeric organic substances, in particular complex salts or charge transfer complexes, e.g. B. the different modifications of tetracyanoquinodimethane (TCNQ) salts.
  • Carbon black is preferably added to the polymer blends according to the invention in an amount of 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 wt .-%; 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 S2 are achieved.
  • polycaprolactone can be incorporated into almost all polymers, with single-phase microstructures (with styrene / acrylonitrile copolymer, polyvinyl chloride or polycarbonate as polymer B), drop structures (with polyethylene or ethylene-vinyl acetate as polymer B) or the particularly preferred ones in the light microscope Can form conductor tracks (with polyether polyurethane or acrylonitrile / methacrylate / butadiene copolymer as polymer B). Even with an addition of the order of 1 to 3% by weight, a surface resistance of approximately 10 5 to 10 8 2 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. B. a preferably liquid peroxide, and thereby to achieve a crosslinking of the polymers in 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 melt with the polymer B and polymerized when 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.
  • polymer A ethylene-vinyl acetate
  • polymer B polyvinyl chloride
  • 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
  • organic conductive polymer or a non-polymeric organic conductor be present in an amount of more than 10, preferably about 15% by weight.
  • 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.
  • conductive substances such as conductive carbon black and mix this with caprolactam (as polymer B) and a catalyst in a manner known per se.
  • caprolactam as polymer B
  • a catalyst in a manner known per se.
  • a conductive, thermoplastically processable block copolymer is obtained in which the blocks derived from the prepolymer form a continuous conductor track in the matrix.
  • specific conductivity values of around 10 2 to 10 4 Qcm are achieved with a prepolymer content of 10 to 20% by weight and a carbon black content in the prepolymer of approximately 20%, corresponding to a carbon black content in the blend of 2 to 4% by weight.
  • the desired coupling reaction may need to be catalyzed, e.g. B. transesterification or transamidation reactions with p-toluenesulfonic acid.
  • EP-A-168 620 describes the crystallization of N-methylquinoline-TCNQ dissolved in polycaprolactone.
  • TCNQ salt crystallizes out, however, some of the phases separate again, since the mixture must be kept thermoplastic for long periods without shearing and the compatibility is not sufficient to maintain the microscopic network structure under these conditions.
  • the addition of p-toluenesulfonic acid stabilizes the interfaces by catalytic transesterification.
  • 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 can be particularly advantageous for various applications.
  • 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 2 .
  • 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 obtained in this way (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 to a finished product (e.g. a plate). extruded, the melt temperature was about 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 conductivity carbon black is largely in the polystyrene phase, while the SBS radial block copolymer is dispersed in the matrix without interrupting the conductivity bridges.
  • the correct dispersion was checked by mixing three parts of the polyacetylene-polycaprolactone concentrate with 100 parts of polycaprolactone on a roller mill and squeezing them thinly in a laboratory press. A deep blue color appeared and no black dots (polyacetylene agglomerates) were visible.
  • 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 °.
  • 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: ca.1012Q).

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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)

Claims (15)

1. Mélanges de polymères thermoplastiques antistatiques ou semiconducteurs de l'électricité, à base de polymères organiques, de substances conductrices de l'électricité et d'additifs usuels, caractérisés en ce qu'ils contiennent deux polymères thermoplastiques A et B partiellement compatibles, dont le polymère A présente, à une temperarature donnée, une plus faible viscosité à chaud que le polymère B, et entre lesquels existe une différence d'environ 0,3 à 1,5 (cal/cm3)1/2 de paramètre de solubilité, le polymère A, qui constitue la phase continue, contenant essentiellement les substances conductrices de l'électricité.
2. Mélanges de polymères selon la revendication 1, caractérisés en ce qu'ils contiennent, en tant que polymères A et B, l'une des combinaisons copolymère éthylène/acétate de
vinyle-polychlorure de vinyle,
copolymère éthylène/acétate de vinyle-polyéthylène,
polyéthylène chloré-copolymère acrylonitrile/butadiène/styrène,
copolymère séquencé styrène/butadiène/styrène-polyéthylène,
polystyrène-copolymère séquencé styrène/butadiène/styrène,
copolymère polyamide-polyamide, polyamide-polyoxyméthylène,
copolymère éthylène/acétate de vinyle-copolymère acrylonitrile/butadiène/styrène,
poly-a-méthylstyrène-polychlorure de vinyle,
copolymère éthylène/acétate de vinyle/monoxyde de carbone-polychlorure de vinyle,
copolymère éthylène/acétate de vinyle/monoxyde de carbone-polyuréthanne,
polyuréthanne-polyamide, polyuréthanne-polycarbonate,
polycaprolactone-polyéther polyuréthanne,
polyester polyuréthanne-polychlorure de vinyle,
polyuréthanne-copolymère acrylonitrile/butadiène/styrène,
polycaprolactone-copolymère acrylonitrile/méthacrylate/butadiène,
polycaprolactone-polyuréthanne ou polycaprolactone copolymère éthylène/acétate de vinyle.
3. Mélanges de polymères selon la revendication 1 ou 2, caractérisés en ce que les polymères A et/ou B sont chacun des mélanges de polymères thermoplastiques compatibles entre eux.
4. Mélanges de polymères selon l'une des revendications 1 à 3, caractérisés en ce que le rapport pondéral polymère A : polymère B est < 1 : 1.
5. Mélanges de polymères selon l'une des revendications 1 à 4, caractérisé en ce qu'ils contiennent, en tant que substances conductrices, une poudre ou des fibres métalliques, des fibres de carbone, du noir de carbone conducteur ayant une surface BET > 250 m2/g et une absorption de phtalate de dibutyle > 140 CM 2/100 g, des polymères organiques conducteurs de l'électricité ou des conducteurs organiques non polymères, ou des mélanges de ceux-ci.
6. Mélanges de polymères selon l'une des revendications 1 à 5, caractérisés en ce qu'ils contiennent les substances conductrices en une quantité de 0,5 à 10 % en poids, par rapport au mélange de polymères.
7. Mélanges de polymères selon les revendications 1 à 5, caractérisés en ce qu'ils contiennent des agents chimiques de réticulation pour un ou plusieurs des polymères.
8. Procédé pour la préparation des mélanges de polymères selon les revendications 1 à 7, caractérisé en ce que
a) dans une première étape, on disperse les substances conductrices dans une solution ou masse fondue du polymère A ou d'un prépolymère pour le polymère A, éventuellement on élimine le solvant et ensuite, dans une seconde étape, on fait fondre le concentré conférant la conductibilité ainsi préparé, ou, dans le cas d'utilisation d'un prépolymère, on le polymérise, avec le polymère B, ou
b) on disperse les substances conductrices directement dans une masse fondue constituée des polymères A et B, et éventuellement on granule le mélange de polymères ainsi obtenu.
9. Procédé selon la revendication 8, caractérisé en ce que l'on applique le procédé b) à la combinaison de polymères polystyrène (polymère A) et copolymère styrène/butadiène/ styrène (polymère B).
10. Procédé selon l'une des revendications 8 ou 9, caractérisé en ce que, pour la réticulation des polymères, on chauffe le mélange de polymères contenant l'agent chimique de réticulation ou on irradie le mélange de polymères.
11. Procédé selon l'une des revendications 8 à 10, caractérisé en ce que l'on engendre la compatibilité partielle requise des polymères par réaction chimique pendant la préparation thermoplastique du mélange ou pendant le formage thermoplastique de celui-ci.
12. Procédé selon la revendication 11, caractérisé en ce que l'on effectue, sur ou entre des polymères A et B réactifs, des réactions d'addition, d'estérification, de transestérification, de saponification, de transamidation et/ou d'élimination, catalysées ou non catalysées.
13. Procédé selon l'une des revendications 11 ou 12, caractérisé en ce que l'on utilise, en tant que polymères A et B, l'une des combinaisons terpolymère éthylène modifié avec de l'anhydride maléique/propylène/diène- polyamide,
polyéthylène modifié avec de l'anhydride maléique-polyamide,
polyéthylène modifié avec de l'anhydride maléique-polystyrène,
polystyrène modifié avec de l'anhydride maléique-polyéthylène,
polycaprolactone-polyéthylène modifié avec de l'anhydride maléique,
polycaprolactone-terpolymère éthylène modifié avec de l'anhydride maléique/propylène/ diène,
polycaprolactone-polystyrène modifié avec de l'anhydride maléique,
poly(alcool vinylique)-copolymère éthylène/acétate de vinyle,
propionate de cellulose-copolymère éthylène/acétate de vinyle,
propionate de cellulose-polytéréphtalate d'éthylène,
propionate de cellulose-polycarbonate,
copolymère éthylène/acétate de vinyle-polytéréphtalate d'éthylène, ou copolymère éthylène/acétate de - vinyle-polycarbonate.
14. Utilisation des mélanges de polymères selon l'une des revendications 1 à 7, pour la préparation de revêtements, feuilles, pièces moulées ou corps moulés, à volume constant, antistatiques ou semiconducteurs de l'électricité.
15. Utilisation selon la revendication 13, caractérisée en ce que l'on étire les feuilles, pièces moulées ou corps moulés, pour l'obtention d'une direction préférentielle pour le passage du courant.
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

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

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DE (2) DE3440617C1 (fr)

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EP0181587A2 (fr) 1986-05-21
DE3570796D1 (en) 1989-07-06
DE3440617C1 (de) 1986-06-26
US4929388A (en) 1990-05-29
ATE43745T1 (de) 1989-06-15

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