EP0131544B1 - Matière de remplissage conducteur d'électricité - Google Patents

Matière de remplissage conducteur d'électricité Download PDF

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Publication number
EP0131544B1
EP0131544B1 EP84810326A EP84810326A EP0131544B1 EP 0131544 B1 EP0131544 B1 EP 0131544B1 EP 84810326 A EP84810326 A EP 84810326A EP 84810326 A EP84810326 A EP 84810326A EP 0131544 B1 EP0131544 B1 EP 0131544B1
Authority
EP
European Patent Office
Prior art keywords
process according
parts
filler
phthalocyanine
electrically conductive
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.)
Expired
Application number
EP84810326A
Other languages
German (de)
English (en)
Other versions
EP0131544A1 (fr
Inventor
Fridolin Dr. Bäbler
Kurt Dr. Munk
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
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 Ciba Geigy AG filed Critical Ciba Geigy AG
Priority to AT84810326T priority Critical patent/ATE31993T1/de
Publication of EP0131544A1 publication Critical patent/EP0131544A1/fr
Application granted granted Critical
Publication of EP0131544B1 publication Critical patent/EP0131544B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon

Definitions

  • the invention thus relates to a method for producing an electrically conductive filler, characterized in that a mixture of at least one metal phthalocyanine and at least one inorganic filler is pyrolyzed.
  • Suitable metal phthalocyanines are e.g. B. copper, iron, nickel, aluminum, cobalt, manganese, tin, silicon, germanium, lead, titanium, chromium, uranium, magnesium, vanadium, molybdenum or Zinc phthalocyanines, mixtures of two or more different metal phthalocyanines also being possible.
  • the metal phthalocyanines can also be mixed with metal-free phthalocyanines. It is also possible, for example, to use metal phthalocyanines substituted with sulfonic acid, sulfonamide, sulfoester, alkyl, aryl, aryl ether or thioether residues.
  • the metal phthalocyanines can be used in fine or coarse form.
  • the metal phthalocyanine used is preferably copper, nickel, cobalt or iron phthalocyanine, but very preferably copper phthalocyanine, in particular crude ⁇ -copper phthalocyanine for economic reasons.
  • Suitable organic fillers are, in particular, glass, quartz, clay minerals, feldspar, silicates, carbonates, rock flour, clay, oxides or sulfates, which can be synthetic or natural materials, such as.
  • the fillers mentioned can be used individually or
  • Aluminum oxide, wollastonite, titanium dioxide, mica, iron oxide or quartz, in particular finely divided quartz, are preferably used as fillers.
  • electrically conductive fillers produced according to the invention, in which the inorganic filler is crystalline or amorphous quartz with a particle size of 0.01 to 1000 ⁇ m, preferably 2 to 200 ⁇ m.
  • the electrically conductive fillers that can be used in accordance with the invention can be produced by intimately mixing the pigment to be pyrolyzed and the inorganic filler dry or in an aqueous suspension, optionally with grinding, and then, if working in an aqueous suspension, filtering and drying . If necessary, the inorganic filler can be added during the synthesis of the metal phthalocyanine.
  • the pigment to be pyrolyzed are preferably used per 100 parts by weight of dry starting mixture.
  • the mixture of inorganic filler and metal phthalocyanine thus obtained is then pyrolyzed, the inorganic filler being coated with pyrolyzed pigment.
  • the pyrolysis can be carried out at 0.5 to 20 bar, preferably at normal pressure, in air, in inert gas, in air with an increased oxygen content or in hydrogen gas. Pressure, gas and temperature increase as a function of time are generally chosen so that the pigment pyrolyzes in the highest possible yield of carbon and metal. Air or nitrogen are particularly suitable as the gas.
  • the pyrolysis is expediently carried out at temperatures from 650 to 2500 ° C., preferably at temperatures from 800 to 1200 ° C.
  • the process according to the invention preferably takes place at temperatures of 650 to 2500 ° C., at a pressure of 0.5 to 20 bar and in air, inert gas, in air with increased oxygen content or in hydrogen gas, but very preferably at 800 to 1200 ° C. and at normal pressure in air instead.
  • heating a 1: 1 mixture of quartz powder / Cu phthalocyanine in air to 1050 ° C (at normal pressure) gives a product consisting of approximately 61% by weight of silicon dioxide, 30% by weight of carbon, 6.4 % By weight copper and 2.6% by weight nitrogen.
  • the electrical conductivity at room temperature is approximately 10 Q-1 cm- 1 .
  • the pyrolysis product is obtained in continuous or loose, dark gray to black solid mass and is usually broken and pulverized.
  • the electrically conductive fillers produced according to the invention are particularly suitable for incorporation into high-molecular organic or inorganic material.
  • a high molecular organic Material are suitable for.
  • the high-molecular compounds mentioned can exist as plastic masses, melts or solutions.
  • the conductive fillers produced according to the invention can be added to the high-molecular organic material by the methods customary in the art, before or during shaping, or also as a dispersion or in the form of preparations. Depending on the purpose, you can add other substances, such as. B. light stabilizers, heat stabilizers, plasticizers, binders, pigments and / or dyes, carbon black, flame retardants or other fillers.
  • the electrically conductive filler according to the invention is preferably used in an amount of 0.5 to 70, preferably 15 to 60 percent by weight (per total mixture).
  • the additives can also be added before or during the polymerization.
  • Epoxy resins which are hardened with dicarboxylic acid anhydrides are preferably used as resin / hardener components.
  • the electrically conductive fillers produced according to the invention can be incorporated, for. B. cement, concrete, glasses, ceramic materials, inorganic polymers such as polysilicic acid or polyphosphoric acid derivatives, alone or in a mixture with organic polymers, such as asphalt, mentioned.
  • the electrically conductive fillers produced according to the invention are preferably used in an amount of 5 to 70, preferably 15 to 60 percent by weight (per total mixture).
  • plastic systems with excellent mechanical and electrical properties can be produced economically. They have a reinforcing effect on the carrier material and are characterized by good electrical conductivity. Certain plastics, for example epoxy resins, containing the fillers according to the invention also have a constant electrical conductivity over a wide temperature range.
  • Casting resin compositions for example epoxy casting resins, containing the fillers produced according to the invention also have good processing properties even with high conductivity (for example no or only low thixotropy) and lead to molded parts without a reduction in the mechanical properties.
  • high conductivity for example no or only low thixotropy
  • the fillers obtained according to the invention can be incorporated into plastics in a mixture with metals, for example in the form of powders, chips or fibers.
  • the metal to be used here and its concentration depend on the area of application and should not impair the mechanical properties and the resistance, for example, to the decomposition of the plastic products produced with it. These are, for example, steel fibers and / or aluminum flakes. Instead of metals, carbon fibers can also be used.
  • the electrical conductivity can be specifically adjusted by dilution with the fillers mentioned at the beginning or by adding graded amounts of the fillers produced according to the invention in such plastics or in inorganic materials, for example in such a way that electrically partially conductive compositions are formed. This is particularly important for controlling electrical fields and / or for reducing surface or space charges.
  • the electrically conductive fillers produced according to the invention are not only suitable for the production of antistatic and electrically conductive polymer compositions, plastic articles and coatings. They can also be used to manufacture batteries and other objects in microelectronics, in or as sensors, as catalysts for certain chemical reactions, for the production of solar collectors, for shielding sensitive electronic components and high-frequency fields [EMI shielding], for equipotential bonding and glow protection higher load capacity of electrical systems and machines, for controlling electrical fields and charges in electrical devices or as surface heating conductors.
  • EMI shielding shielding sensitive electronic components and high-frequency fields
  • Example 1 90 parts of quartz powder Wllb from SIHELCO AG (SH-Birsfelden) are mixed well with 90 parts of crude ⁇ -copper phthalocyanine for 30 minutes on a Turbula machine from WA Bachofen (CH-Basel). The mixture is heated in a quartz glass vessel, the lid of which has a small opening, in an oven to 1050 ° C. within 6 hours. After 0.5 hours at this temperature, the mixture is cooled and 157 parts are obtained, a gray-black, solid mass which is pulverized in a laboratory mixer. The powder has a composition of 61.5% by weight SiO 2 , 30% by weight C, 6.5% by weight Cu and 2% by weight N The electrical conductivity, measured on the compressed powder, is Room temperature 10 Scm- 1 (2 electrodes measurement on micropressling).
  • Cu-Pc copper phthalocyanine "according to F. Beck,” Bunsen Society Reports, Physical Chemistry “68 (1964), pages 558-567.
  • Example 5 50 parts Wl ® from SIHELCO AG (Birsfelden CH-) are thoroughly mixed together with 50 parts of nickel phthalocyanine for 30 minutes on a Turbula machine from WA Bachofen (CH-Basel). The mixture is heated in a quartz glass vessel, the lid of which has a small opening, to 1000 ° C. in an oven within 6 hours. The mixture is kept at 1000 ° C. for 1 hour and then allowed to cool to room temperature. This gives 86.2 parts of a gray-black solid mass which is powdered. The electrical conductivity of the powder thus obtained is 12 Scm- 1 at room temperature .
  • Example 12 270 parts of an analogous manner to Example 1 produced the filler from 135 parts of quartz powder W12 ® from SIHELCO AG and 135 parts of the obtained in Example 1 electrically conductive powder are added to 100 parts of Araldite CY 225 ® (modified bisphenol A epoxy resin having an Molecular weight of 380) and 80 parts of the hardener HY 925® (modified dicarboxylic anhydride). The mixture is heated to 80 ° C., homogenized with a paddle stirrer and vented for 3 minutes. The mixture is then poured into molds preheated to 80 ° C and cured for 4 hours at 80 ° C and for 8 hours at 140 ° C (DIN No. 16945). The following data are measured on the martensets and plates produced in this way:
  • Example 13 For the coloring of PVC, a mixture of 65 parts of stabilized PVC, 35 parts of dioctyl phthalate and 25 parts of the product obtained according to Example 1 is used
  • the soft PVC film obtained in this way has a specific surface resistance R o , measured according to DIN 53482 (electrode arrangement A), of 5.5. 10 10 2 cm.
  • EXAMPLE 14 25 parts of the product obtained according to Example 1, 37.5 parts of polyethylene wax AC-617 0 from Allied Chemicals and 125 parts of sodium chloride are kneaded at 80-110 ° C. for 6 hours in a 300-part laboratory kneader. Then 62.5 parts of MOPLEN MOB-120 ® from Montecatini are incorporated into the plasticine. The kneading compound is cooled to 30 ° C in the running kneader, a gray-black powdery mass is formed, which is finely pulverized with approx. 3 liters of water on a FRYMA Z 050 toothed colloid mill.
  • the suspension obtained is filtered off and the presscake is washed free of chloride with water.
  • the product obtained is dried in a vacuum drying cabinet at 50-60 ° C. This gives 120 parts of a fine, loose, gray-black polyolefin preparation which, after extrusion on a laboratory extruder (Temp.Zone 1: 160 ° C; Zone 2: 190 ° C; Zone 3: 220 ° C; Zone 4: 170 ° C), is a thermoplastic Mass results. This mass has an electrical volume resistance of approx. 4 - 10 5 ⁇ cm, and is excellently suited for the production of injection molded articles or fibers.
  • Example 15 In a 300 parts by volume of comprehensive laboratory kneader, 32 parts of the product obtained according to Example 1, 48 parts DYNAPOL ® 206 of the company Dynamit Nobel, 160 parts of sodium chloride and 25-32 parts by volume of diacetone alcohol for about 5 hours at Kneaded at 80 ° C. Water is then added dropwise in the running kneader and at the same time cooled until the kneading mass is converted into granules. The granules are ground on a FRYMA dental colloid mill Z 050 with plenty of water, filtered off, the press cake obtained is washed salt-free with water and then dried in a vacuum drying cabinet at 65-70 ° C. A gray-black powdery mass is obtained, which is extruded into a cord on a laboratory extruder and then granulated on a chopping machine. The 40% polyester preparation thus obtained has an electrical volume resistance of 10 4 to 10 5 Qcm.
  • EXAMPLE 16 If the procedure is analogous to that of Example 1, but using 5 parts of quartz powder W1® instead of 90 parts and 95 parts of ⁇ -copper phthalocyanine instead of 90 parts, a product containing about 12% by weight of copper is obtained. It is an excellent catalyst for the reaction described in Example 17 for the preparation of an anthraquinoid wool dye.
  • Example 17 Reaction scheme 20.2 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid sodium are stirred with 300 parts of water and, after the addition of 13.8 parts of sodium carbonate, 11.25 parts of I-aminobenzene-4-sulfonic acid are gradually added. 7 portions of 1 part each of the product obtained according to Example 16, finely powdered, are added to the mixture heated to 85 ° C. as a catalyst at intervals of 45 minutes. After the last addition, the mixture is stirred for a further hour at 85-90 ° C., then 7.5 parts of sodium carbonate, 11.25 parts of 1-aminobenzene-4-sulfonic acid and 1 part of the product obtained according to Example 16 are added.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (11)

1. Procédé de préparation d'un produit de charge électroconducteur, procédé caractérisé en ce que l'on soumet à une pyrolyse un mélange d'une ou de plusieurs phtalocyanines métallifères et d'une ou de plusieurs charges minérales.
2. Procédé selon la revendication 1 dans lequel on emploie comme phtalocyanine métallifère une phtalocyanine de cuivre, de nickel, de cobalt ou de fer.
3. Procédé selon la revendication 1 dans lequel on emploie une phtalocyanine de cuivre.
4. Procédé selon la revendication 1 dans lequel on emploie de la ß-phtalocyanine de cuivre.
5. Procédé selon la revendication 1 dans lequel on emploie comme charge minérale de l'oxyde d'aluminium, de la wollastonite, de l'oxyde de fer, du dioxyde de titane, du mica ou du quartz.
6. Procédé selon la revendication 1 dans lequel on emploie comme charge minérale du quartz cristallisé ou amorphe en particules de 0,01 à 1000 µm.
7. Procédé selon la revendication 1 dans lequel on effectue la pyrolyse à des températures de 650 à 2500° C sous une pression de 0,5 à 20 bars dans de l'air, dans un gaz inerte, dans de l'air à teneur accrue en oxygène ou dans de l'hydrogène.
6. Procédé selon la revendication 1 dans lequel on effectue la pyrolyse à l'air à des températures de 800 à 1200° C, à la pression normale.
9. L'application du procédé selon l'une quelconque des revendications précédentes pour preparer des produits de charge destinés à être incorporés dans des matières organiques macromoléculaires.
10. L'application du procédé selon l'une quelconque des revendications précédentes pour préparer des produits de charge destinés à être incorporés dans des matières minérales.
11. L'application du procede selon l'une quelconque des revendications précédentes pour preparer des produits de charge destinés à être incorporés dans des résines époxydes.
EP84810326A 1983-07-08 1984-07-02 Matière de remplissage conducteur d'électricité Expired EP0131544B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84810326T ATE31993T1 (de) 1983-07-08 1984-07-02 Elektrisch leitende fuellmittel.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CH376683 1983-07-08
CH3766/83 1983-07-08
CH5153/83 1983-09-22
CH515383 1983-09-22
CH617/84 1984-02-09
CH61784 1984-02-09

Publications (2)

Publication Number Publication Date
EP0131544A1 EP0131544A1 (fr) 1985-01-16
EP0131544B1 true EP0131544B1 (fr) 1988-01-13

Family

ID=27172246

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84810326A Expired EP0131544B1 (fr) 1983-07-08 1984-07-02 Matière de remplissage conducteur d'électricité

Country Status (7)

Country Link
US (1) US4554094A (fr)
EP (1) EP0131544B1 (fr)
AU (1) AU561786B2 (fr)
CA (1) CA1217043A (fr)
DE (1) DE3468769D1 (fr)
FI (1) FI76102C (fr)
NO (1) NO161224C (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4720418A (en) * 1985-07-01 1988-01-19 Cts Corporation Pre-reacted resistor paint, and resistors made therefrom
GB8622752D0 (en) * 1986-09-22 1986-10-29 Shell Int Research Conductive polymer compositions
US4711708A (en) * 1986-10-09 1987-12-08 Gas Research Institute Chemically modified electrodes for the catalytic reduction of CO2
US4756807A (en) * 1986-10-09 1988-07-12 Gas Research Institute Chemically modified electrodes for the catalytic reduction of CO2
DE3804381C2 (de) * 1988-02-12 1993-10-28 Sachsenwerk Ag Ohmscher Spannungsteiler für eine Hochspannungsanlage
DE4015929A1 (de) * 1990-05-17 1991-11-21 Asea Brown Boveri Isolator
US5366664A (en) * 1992-05-04 1994-11-22 The Penn State Research Foundation Electromagnetic shielding materials
DE9316606U1 (de) * 1993-10-29 1994-11-24 Siemens AG, 80333 München Schleifring- bzw. Kommutatormotor
CN1039506C (zh) * 1994-09-12 1998-08-12 宝山钢铁(集团)公司 室内空间静电防治和泄漏方法
DE9415851U1 (de) * 1994-09-30 1995-08-03 Siemens AG, 80333 München Schleifring- bzw. Kommutatormotor
DE19500849A1 (de) * 1995-01-13 1996-07-18 Abb Research Ltd Elektrisches Bauteil
US20010014399A1 (en) * 1997-02-26 2001-08-16 Stanley J. Jasne Conductive uv-curable epoxy formulations
JP3032491B2 (ja) * 1997-08-27 2000-04-17 大塚化学株式会社 印刷用シート
US20060108567A1 (en) * 2002-07-23 2006-05-25 Charati Sanjay G Conductive poly (arylene ether) compositions and methods of making the same
US8999200B2 (en) * 2002-07-23 2015-04-07 Sabic Global Technologies B.V. Conductive thermoplastic composites and methods of making

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3538021A (en) * 1968-05-07 1970-11-03 Gen Motors Corp Resistor composition
US4252565A (en) * 1976-04-08 1981-02-24 Ciba-Geigy Corporation Stabilized phthalocyanines
GB1535434A (en) * 1976-12-01 1978-12-13 Ciba Geigy Ag Flocculation inhibitors
JPS5940172B2 (ja) * 1977-10-28 1984-09-28 東洋インキ製造株式会社 フタロシアニン顔料組成物
US4347173A (en) * 1980-06-06 1982-08-31 Westinghouse Electric Corp. Opaque black dye for color coding of wire enamels, varnishes and synthetic resins
US4304719A (en) * 1981-01-23 1981-12-08 The United States Of America As Represented By The Secretary Of The Navy Conducting iodine-doped fluorometallophthalocyanines
US4477608A (en) * 1982-08-20 1984-10-16 Ciba-Geigy Corporation Compositions containing graphite

Also Published As

Publication number Publication date
CA1217043A (fr) 1987-01-27
FI76102B (fi) 1988-05-31
AU561786B2 (en) 1987-05-14
FI842682A (fi) 1985-01-09
AU3039084A (en) 1985-01-10
NO161224C (no) 1989-07-19
DE3468769D1 (en) 1988-02-18
NO842777L (no) 1985-01-09
US4554094A (en) 1985-11-19
EP0131544A1 (fr) 1985-01-16
FI842682A0 (fi) 1984-07-04
NO161224B (no) 1989-04-10
FI76102C (fi) 1988-09-09

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