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EP0115661B1 - Electrically conducting material and method of preparing same - Google Patents

Electrically conducting material and method of preparing same Download PDF

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Publication number
EP0115661B1
EP0115661B1 EP83300487A EP83300487A EP0115661B1 EP 0115661 B1 EP0115661 B1 EP 0115661B1 EP 83300487 A EP83300487 A EP 83300487A EP 83300487 A EP83300487 A EP 83300487A EP 0115661 B1 EP0115661 B1 EP 0115661B1
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EP
European Patent Office
Prior art keywords
metal
electrically conducting
polymeric material
sulphide
conducting material
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
EP83300487A
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German (de)
French (fr)
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EP0115661A1 (en
Inventor
Shinji Tomibe
Reizo Gomibuchi
Kiyofumi Takahashi
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.)
Nihon Sanmo Dyeing Co Ltd
Original Assignee
Nihon Sanmo Dyeing Co Ltd
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Priority to DE8383300487T priority Critical patent/DE3377176D1/en
Priority to EP83300487A priority patent/EP0115661B1/en
Publication of EP0115661A1 publication Critical patent/EP0115661A1/en
Application granted granted Critical
Publication of EP0115661B1 publication Critical patent/EP0115661B1/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/53—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with hydrogen sulfide or its salts; with polysulfides
    • 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
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/38—Polyurethanes

Definitions

  • This invention relates to electrically conducting materials and a method of preparing such electrically conducting materials.
  • FR ⁇ A ⁇ 644429 discloses a process for the metallization of fibrous materials in which the fibrous material is treated successively in a cupro-ammoniacal bath containing silver nitrate, a coagulation bath, to the reducing action of hydrogen sulphide and then, finally, in an electrolytic bath containing a metal such as copper or nickel.
  • a metal such as copper or nickel.
  • an electrically conducting material comprising a substantially cyano group-free synthetic polymeric material having adsorbed thereby a sulphide of at least one first metal selected from silver, gold, ruthenium, rhodium, palladium, osmium, indium and platinum, wherein said synthetic polymeric material is selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35 ⁇ 65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols.
  • a method of improving the stability of an electrically conducting, first metal sulphide-carrying, substantially cyano group-free synthetic polymeric material wherein said synthetic polymeric material is selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols and wherein said first metal is selected from copper, cobalt, tin, mercury and lead, comprising treating said polymeric material with a source of ions containing a second metal selected from silver, ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the present invention provides a method of preparing an electrically conducting material, comprising treating a substantially cyano group-free synthetic polymeric material having adsorbed thereby hydrogen sulphide with (a) a source of ions containing a first metal selected from copper, lead, tin, mercury and cobalt and (b) a source of ions containing a second metal selected from silver, gold, ruthenium, rhodium, palladium, osmium, iridium and platinum, said synthetic polymeric material being selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols.
  • the synthetic polymeric materials to which an electrical conductivity may be imparted in accordance with this invention are synthetic polymers capable of adsorbing hydrogen sulphide.
  • cyano group-containing polymers such as polyacrylonitrile, which have no affinity for hydrogen sulphide are not suitable for the purpose of the present invention.
  • the useful synthetic polymers and copolymers are polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols. Mixtures of these polymers with other polymers such as polyolefins may also be used.
  • the synthetic polymers to be imparted with electrical conductivity may be in the form of powder or in the form of a shaped body such a film, plate, fibre, fabric, paper, sheet, block, pellet, thread, string, rod or pipe and can contain customarily employed additives such as an ultraviolet ray-absorber and a molding aid.
  • the electrically conducting material of this invention is comprised of sulphides of a first metal selected from copper, cobalt, tin, mercury and lead and a second metal selected from silver, gold and elements of the platinum group, i.e. ruthenium, rhodium, palladium, osmium, iridium and platinum, supported by the above-mentioned polymeric material.
  • the amount of the first metal sulphide adsorbed by the polymeric material varies depending on the kind of the starting polymeric material and the intended electrical conductivity but is generally in the range of about 0.5 to 30%, preferably 1 to 15%, in terms of elemental metal based on the weight of the starting polymeric material.
  • the amount of the sulphide of the second metal in the electrically conducting material of this invention can be sufficiently low and is, in general, such that the atomic ratio M 2 /M 1 , where M 1 stands for the first metal and M 2 stands forthe second metal, is 0.0001 to 0.5, preferably 0.001-0.3, more preferably 0.01-0.2. Too small an amount of the second metal component is insufficient to attain an improvement in washability, whereas an amount of the second metal component in excess of 0.5 of the M 2 /M 1 atomic ratio tends to lower the electrical conductivity and is also disadvantageous from the economic point of view since the second metal is very expensive.
  • the electrically conducting material of the present invention may be prepared with the use of, as the starting material, the above-mentioned synthetic polymeric material having deposited thereon the first metal sulphide or the above-mentioned synthetic polymeric material having adsorbed thereby hydrogen sulphide.
  • the first metal sulphide-deposited, electrically conducting synthetic polymeric material may be preferably prepared in accordance with the method described in United States Patent No. 3,940,533. Briefly, the method includes treating the above-mentioned synthetic polymeric material with hydrogen sulphide under pressure, and treating the resulting material having adsorbed thereby hydrogen sulphide with first metal-containing ions to form the sulphide of the first metal adsorbed on or within the polymeric material.
  • the resulting product may be further treated with a reducing agent as suggested in British Patent Publication No. 2,078,545A. Further, the treatment with the copper-containing ions may be performed in the presence of a polyphenol such as diphenol as a swelling agent.
  • the electrically conducting, copper sulphide-carrying synthetic polymeric material is also commercially available under a trade mark of "Rhodiastat", which can be suitably employed as the starting material for the preparation of the electrically conducting material of this invention.
  • the synthetic polymeric material having adsorbed thereby first metal sulphide is treated, as such or after being washed with water, in a bath containing ions containing a source of the second metal.
  • ions containing a source of the second metal a salt or complex of the second metal, such as a sulphate, nitrate, chloride, acetate, benzoate, a thiocyanate complex or a thiosulphate complex, may be suitably employed.
  • concentration of the second metal-containing ions in the bath is generally in the range of 0.005-10 g/I, preferably 0.01-6 g/I in terms of the elemental metal.
  • the treatment is performed at a temperature from room temperature to 100°C, preferably 30-80°C, for a period of 0.5-20 hours, preferably 1-10 hours with a ratio by weight of the bath to the material to be treated being in the range of 5:1 to 50:1, preferably 10:1 to 30:1.
  • the treatment with the second metal-containing ions be performed in the presence of a sulphur-containing compound or be followed by a treatment with the sulphur-containing compound to further improve both the stability and the electrical conductivity of the resulting electrically conducting material.
  • the sulphur-containing compound is of a type which is capable of providing sulphur atoms and/or sulphur ions for reaction with the second metal to accelerate the formation of sulphides of the second metal.
  • Illustrative of the sulphur-containing materials are sodium sulphide, sulphur dioxide, sodium hydrogen sulphite, sodium pyrosulphite, sulphurous acid, dithionous acid, sodium dithionite, sodium thiosulphate, thiourea dioxide, hydrogen sulphide, sodium formaldehyde sulphoxylate (rongalite C), zinc formaldehyde sulphoxylate (rongalite Z) and mixtures thereof.
  • the sulphur-containing compound is generally used in an amount of 0.2-5 mols, preferably 0.4-3 mols per mol of the source of second metal-containing ions.
  • the modification with the second metal component is preceded by the formation of first metal sulphide.
  • the sulphides of first and second metals are adsorbed simultaneously on the synthetic polymeric material.
  • a synthetic polymeric material having adsorbed thereon hydrogen sulphide is used as the starting material.
  • the hydrogen sulphide-adsorbed polymeric material may be obtained by contacting the synthetic polymeric material with hydrogen sulphide, preferably under pressure, for 0.5 to 2 hours.
  • the hydrogen sulphide-adsorbed synthetic polymeric material is treated in a bath containing both first metal-containing ions and second metal-containing ions.
  • a water-soluble salt or complex such as a chloride, a sulphate and a nitrate of the first metal is generally used as the source of first metal-containing ions.
  • the concentration of the first metal ions in the bath is generally in the range of 10-100 g/I, preferably 20-40 g/I, in terms of elemental metal.
  • any of the salts or complexes as exemplified previously may be used as the source of ions containing the second metal.
  • the concentration of the second metal-containing ions in this embodiment is the same as in the previously described embodiment.
  • the treatment with the first and second metal ions is generally performed at a temperature in the range from 10 to 100°C, preferably from room temperature to 60°C. Similar to the previously described embodiment, it is preferred that the above treatment be carried out in the presence of or be followed by the treatment with a sulphur-containing compound of the above-mentioned type. The amount of the sulphur-containing compound used is also the same as described previously.
  • the electrically conducting material in which sulphides of the first and second metals are adsorbed by the synthetic polymeric material to form a continuous, electrically conducting layer or deposit at least on the surface thereof.
  • the X-ray diffraction pattern of the electrically conducting material of this invention in which copper and silver are used as the first and second metals, respectively, has been found not to be the same as that deduced from the X-ray diffraction patterns of copper sulphide and silver sulphide.
  • the analysis of the electrically conducting material by an X-ray microanalyzer indicates that the silver exists at the same locations as the copper and sulphur.
  • the electrically conducting layer of this invention shows a property which is not execpted from the properties of a synthetic polymeric material having either the sulphide of the first metal or the sulphide of the second metal
  • the electrically conducting layer is not considered to be formed of a mere mixture of the first metal sulphide and the second metal sulphide. Rather, it is believed that at least some of the first metal sulphide and the second metal sulphide should be present in a mixed crystal-like form in which the second metal is associated with the sulphur atoms or atoms of the first metal sulphide.
  • auxiliary metal component may be incorporated into the electrically conducting material in the same manner as the second metal component.
  • a source of ions containing the auxiliary metal such as a salt or complex thereof is added to the bath which is used for treating the synthetic polymeric material with first metal-containing ions, the source of ions containing the second metal and/or the sulphur-containing compound.
  • the incorporation of the auxiliary metal component can be done independently of the above treatments by treating the synthetic polymeric material in the manner and conditions as in the case of the treatment with the source of ions containing the second metal.
  • the amount of auxiliary metal-containing ions used in either case of treatment is generally 0.01 to 0.5 mol per mol of the first metal-containing ions.
  • the electrically conducting material of this invention when in the form of fibres, may be advantageously utilized in the manufacture of clothes, carpets, interior decorative sheets, gloves or like by themselves or in combination with other fibres because of their freeness of static charging and easiness to be dyed.
  • the electrical conductivity and transparency of the materials of this invention allow the use thereof as a cover or enclosure for electric parts such as integrated circuits and large-scale integrated circuits which are required to be shielded from electrostatic charges during storage or transportation.
  • the powdery, electrically conductive material of this invention may be incorporated into a coating composition to form electrically conductive coatings.
  • the powdery or granular, electrically conductive material of this invention formed from synthetic polymers, such as polyamide, can be subjected to thermal molding conditions to produce electrically conducting molded articles.
  • the electrically conducting materials of this invention lend themselves to numerous applications in many fields.
  • the washability was determined according to the method speculated in Japanese Industrial Standard (JIS) L 1045. That is, a sample was added in a washing liquid containing 3 g/I of a commercially available detergent ("All Temperature Cheer" of Proctor & Gamble Inc.) with a ratio by weight of the sample to the washing liquid of 1:50. The liquid was charged in a dye-fastness testing device together with ten stainless balls and agitated at 50°C for 30 min followed by washing with water and drying. Such a procedure was repeated a number of times for the examination of the fastness to washing. The moisture resistance test was conducted by suspending the sample from the top of a closed glass vessel containing water, the vessel being placed in a thermostat oven to maintain the sample at 60°C and 100% humidity for a given period of time for the examination of the change in its electrical resistivity.
  • JIS Japanese Industrial Standard
  • Example 1 was repeated in the same manner as that described therein except that the treatment bath further contained 5 g/I of sodium thiosulphate and that the treatment time was reduced to 2 hours.
  • the resultant fibre had an electrical resistivity of 1.18x10 -1 and no change in electrical conductivity was observed after 50 times washing operations.
  • a polyamide knit (Toyobo Nylon, 70 denier, 24 filaments) weighing 5 g was suspended within an autoclave to which hydrogen sulphide was charged until the inside pressure reached 5 kg/cm 2 .
  • the treatment of the knit with hydrogen sulphide was carried out at 20°C for 1 hour.
  • the resulting knit having adsorbed thereby hydrogen sulphide was then immersed in 100 ml of an aqueous solution containing 30 g/I of cupric sulphate and 1 g/I silver nitrate, and treated therein at 20°C for 30 min and then at 50°C for 1 hour.
  • the thus treated knit was olive-gray in color and had an electrical resistivity of 1.46x 10 -1 Q-cm.
  • the electrical conductivity remained unchanged through 100 days-moisture-resistance test.
  • Example 3 was repeated in the same manner as that described therein except that the treatment bath contained 15 g/I of sodium thiosulphate in addition to the cupric sulphate and silver nitrate, thereby to give a brown-gray, electrically conducting knit having an electrical resistivity of 1.18x10-' Q-cm. During the course of the treatment, there was observed a small amount of precipitates. No appreciable change was observed after 100 days-moisture-resistance test. The washability test gave the results shown in Table 2.
  • Example 4 was repeated in the same manner as that described therein except that silver sulphate, palladium chloride, gold chloride and platinum chloride were used each in place of silver nitrate, obtaining an improvement in moisture-resistance. Further, Example 4 was repeated using sodium dithionite in place of sodium thiosulphate, with the results similar to the case of sodium thiosulphate.
  • a polyamide knit (Toyobo Nylon, 70 deniers, 24 filaments) weighing 5 g was suspended within an autoclave to which was charged hydrogen sulphide until the inside pressure reached 5 kg/cm2, and treated therein. at 20°C for 1 hour. The resulting knit with hydrogen sulphide being adsorbed thereby was then treated in an aqueous bath containing 30 g/I of cupric sulphate at 20°C for 30 min.
  • Example 5 was repeated in the same manner as that described therein except that palladium chloride was replaced with various amounts of silver nitrate, whereby obtaining electrically conducting knit materials having various Ag/Cu atomic ratios as shown in Table 3.
  • the washability test results are also shown in Table 3.
  • Example 3 was repeated using a polyethylene terephthalate yarn (Trade Mark: Tetoron, 150deniers,30 filaments, manufactured by Toray Co., Ltd. Japan), an aromatic polyamide fibre (Trade Mark: Conex, manufactured by Teijn Co., Ltd., Japan), a polychlal fibre (Trade Mark: Codelan, manufactured by Kojin Co., Ltd., Japan, a copolymer of vinyl alcohol and vinyl chloride), a polyurethane film (Trade Mark: Opelon, manufactured by Toray Co., Ltd., Japan), a polyester powder and a polyamide film, respectively, in place of the polyamide knit, thereby giving electrically conducting materials which withstood 100 days-moisture-resistance test.
  • a polyethylene terephthalate yarn Trade Mark: Tetoron, 150deniers,30 filaments, manufactured by Toray Co., Ltd. Japan
  • an aromatic polyamide fibre Trade Mark: Conex, manufactured by Teijn Co., Ltd., Japan
  • a polyamide knit (Toyobo Nylon, 70 denier, 24 filaments) weighing 5 g was suspended within an autoclave to which hydrogen sulphide was charged until the inside pressure reached 5 kg/cm 2 .
  • the treatment of the knit with hydrogen sulphide was carried out at 20°C for 1 hour.
  • the resulting knit having adsorbed thereby hydrogen sulphide was then immersed in 100 ml of an aqueous solution containing 30 g/I of cobalt acetate, and treated therein at 20°C for 30 min.
  • 0.2 g of silver nitrate and 2 g of sodium thiosulphate were added to the reaction mixture for reaction therewith at 50°C for 2 hours.
  • the thus treated knit was dark brown in color and had an electrical resistivity of 3.6x10-' Q-cm. The electrical conductivity remained unchanged through 100 days-moisture-resistance test.
  • Example 8 was repeated in the same manner as that described therein except that cobalt acetate was replaced with lead acetate, thereby to give a dark gray, electrically conducting knit having an electrical resistivity of 1.2x10 4 Q-cm. No appreciable change was observed after 100 days-moisture-resistance test.
  • the washability test gave the results shown in Table 4.
  • the above procedure was repeated in the same manner as described above, except that no silver nitrate was used.
  • the resultant knit had an electrical resistivity of 1.4x 1 0 4 Q-cm. However, the electrical conductivity was lost after 15 days from the initiation of the moisture-resistance test.
  • the results of the washability test are also shown in Table 4.

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Description

  • This invention relates to electrically conducting materials and a method of preparing such electrically conducting materials.
  • Numerous methods for imparting electrical conductivity to synthetic polymeric materials in the form of a shaped body are known in the art. For example, in United States Patent No. 3,940,533, there is proposed a method for imparting electrical conductivity to polymeric shaped materials such as polyamide fibres, in which the fibres are first contacted with hydrogen sulphide and the resulting fibres having the hydrogen sulphide impregnated therewithin are then immersed in a metal salt solution such as an aqueous copper sulphate solution, to form a deposit of metal sulphide, such as copper sulphide, on the fibres. However, the copper sulphide deposited fibres obtained according to this process is poor in stability, especially in washability, so that the electrical conductivity is lost during storage or use. In British Patent Publication No. 2,078,545 A (published Jan. 13, 1982), there is proposed a method in which an electrically conducting, copper sulphide-deposited fibre, obtained by such a method as disclosed in the above-mentioned U.S. Patent No. 3,940,533, is treated with a reducing agent such as ascorbic acid or hydrazine to increase the atomic ratio Cu/S of the copper sulphide to between 1.5 and 2.0. Although the thus treated electrically conducting fibre can exhibit superior washability in comparison with the non-treated starting fibre, the washability is still desired to be improved in practice.
  • FR―A―644429 discloses a process for the metallization of fibrous materials in which the fibrous material is treated successively in a cupro-ammoniacal bath containing silver nitrate, a coagulation bath, to the reducing action of hydrogen sulphide and then, finally, in an electrolytic bath containing a metal such as copper or nickel. As a result of the reducing reaction with hydrogen sulphide, metallic copper and metallic silver are deposited on the fibrous material and in this state serve to facilitate thefinal electrolytic deposition of metal.
  • In accordance with the present invention there is provided an electrically conducting material comprising a substantially cyano group-free synthetic polymeric material having adsorbed thereby a sulphide of at least one first metal selected from silver, gold, ruthenium, rhodium, palladium, osmium, indium and platinum, wherein said synthetic polymeric material is selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35―65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols.
  • In another aspect of the present invention, there is provided a method of improving the stability of an electrically conducting, first metal sulphide-carrying, substantially cyano group-free synthetic polymeric material, wherein said synthetic polymeric material is selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols and wherein said first metal is selected from copper, cobalt, tin, mercury and lead, comprising treating said polymeric material with a source of ions containing a second metal selected from silver, ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • In a still further aspect, the present invention provides a method of preparing an electrically conducting material, comprising treating a substantially cyano group-free synthetic polymeric material having adsorbed thereby hydrogen sulphide with (a) a source of ions containing a first metal selected from copper, lead, tin, mercury and cobalt and (b) a source of ions containing a second metal selected from silver, gold, ruthenium, rhodium, palladium, osmium, iridium and platinum, said synthetic polymeric material being selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols.
  • The synthetic polymeric materials to which an electrical conductivity may be imparted in accordance with this invention are synthetic polymers capable of adsorbing hydrogen sulphide. Thus, cyano group-containing polymers, such as polyacrylonitrile, which have no affinity for hydrogen sulphide are not suitable for the purpose of the present invention. More specifically, the useful synthetic polymers and copolymers are polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols. Mixtures of these polymers with other polymers such as polyolefins may also be used. The synthetic polymers to be imparted with electrical conductivity may be in the form of powder or in the form of a shaped body such a a film, plate, fibre, fabric, paper, sheet, block, pellet, thread, string, rod or pipe and can contain customarily employed additives such as an ultraviolet ray-absorber and a molding aid.
  • The electrically conducting material of this invention is comprised of sulphides of a first metal selected from copper, cobalt, tin, mercury and lead and a second metal selected from silver, gold and elements of the platinum group, i.e. ruthenium, rhodium, palladium, osmium, iridium and platinum, supported by the above-mentioned polymeric material.
  • The amount of the first metal sulphide adsorbed by the polymeric material varies depending on the kind of the starting polymeric material and the intended electrical conductivity but is generally in the range of about 0.5 to 30%, preferably 1 to 15%, in terms of elemental metal based on the weight of the starting polymeric material.
  • The amount of the sulphide of the second metal in the electrically conducting material of this invention can be sufficiently low and is, in general, such that the atomic ratio M2/M1, where M1 stands for the first metal and M2 stands forthe second metal, is 0.0001 to 0.5, preferably 0.001-0.3, more preferably 0.01-0.2. Too small an amount of the second metal component is insufficient to attain an improvement in washability, whereas an amount of the second metal component in excess of 0.5 of the M2/M1 atomic ratio tends to lower the electrical conductivity and is also disadvantageous from the economic point of view since the second metal is very expensive.
  • The electrically conducting material of the present invention may be prepared with the use of, as the starting material, the above-mentioned synthetic polymeric material having deposited thereon the first metal sulphide or the above-mentioned synthetic polymeric material having adsorbed thereby hydrogen sulphide.
  • The first metal sulphide-deposited, electrically conducting synthetic polymeric material may be preferably prepared in accordance with the method described in United States Patent No. 3,940,533. Briefly, the method includes treating the above-mentioned synthetic polymeric material with hydrogen sulphide under pressure, and treating the resulting material having adsorbed thereby hydrogen sulphide with first metal-containing ions to form the sulphide of the first metal adsorbed on or within the polymeric material. When copper is used as the first metal, the resulting product may be further treated with a reducing agent as suggested in British Patent Publication No. 2,078,545A. Further, the treatment with the copper-containing ions may be performed in the presence of a polyphenol such as diphenol as a swelling agent. The electrically conducting, copper sulphide-carrying synthetic polymeric material is also commercially available under a trade mark of "Rhodiastat", which can be suitably employed as the starting material for the preparation of the electrically conducting material of this invention. Although there is no disclosure in U.S. Patent No. 3,940,533 with respect to the use of cobalt to form the electrically conducting layer, it has been found that the treatment with cobalt ions can also give an electrically conducting material likewise copper and lead.
  • The synthetic polymeric material having adsorbed thereby first metal sulphide is treated, as such or after being washed with water, in a bath containing ions containing a source of the second metal. As the source of ions containing the second metal, a salt or complex of the second metal, such as a sulphate, nitrate, chloride, acetate, benzoate, a thiocyanate complex or a thiosulphate complex, may be suitably employed. The concentration of the second metal-containing ions in the bath is generally in the range of 0.005-10 g/I, preferably 0.01-6 g/I in terms of the elemental metal. The treatment is performed at a temperature from room temperature to 100°C, preferably 30-80°C, for a period of 0.5-20 hours, preferably 1-10 hours with a ratio by weight of the bath to the material to be treated being in the range of 5:1 to 50:1, preferably 10:1 to 30:1.
  • It is preferred that the treatment with the second metal-containing ions be performed in the presence of a sulphur-containing compound or be followed by a treatment with the sulphur-containing compound to further improve both the stability and the electrical conductivity of the resulting electrically conducting material.
  • The sulphur-containing compound is of a type which is capable of providing sulphur atoms and/or sulphur ions for reaction with the second metal to accelerate the formation of sulphides of the second metal. Illustrative of the sulphur-containing materials are sodium sulphide, sulphur dioxide, sodium hydrogen sulphite, sodium pyrosulphite, sulphurous acid, dithionous acid, sodium dithionite, sodium thiosulphate, thiourea dioxide, hydrogen sulphide, sodium formaldehyde sulphoxylate (rongalite C), zinc formaldehyde sulphoxylate (rongalite Z) and mixtures thereof. The sulphur-containing compound is generally used in an amount of 0.2-5 mols, preferably 0.4-3 mols per mol of the source of second metal-containing ions.
  • In the above embodiment, the modification with the second metal component is preceded by the formation of first metal sulphide. In an alternative embodiment, the sulphides of first and second metals are adsorbed simultaneously on the synthetic polymeric material. In this case, a synthetic polymeric material having adsorbed thereon hydrogen sulphide is used as the starting material. The hydrogen sulphide-adsorbed polymeric material may be obtained by contacting the synthetic polymeric material with hydrogen sulphide, preferably under pressure, for 0.5 to 2 hours.
  • The hydrogen sulphide-adsorbed synthetic polymeric material is treated in a bath containing both first metal-containing ions and second metal-containing ions. A water-soluble salt or complex such as a chloride, a sulphate and a nitrate of the first metal is generally used as the source of first metal-containing ions. The concentration of the first metal ions in the bath is generally in the range of 10-100 g/I, preferably 20-40 g/I, in terms of elemental metal. As the source of ions containing the second metal, any of the salts or complexes as exemplified previously may be used. The concentration of the second metal-containing ions in this embodiment is the same as in the previously described embodiment.
  • The treatment with the first and second metal ions is generally performed at a temperature in the range from 10 to 100°C, preferably from room temperature to 60°C. Similar to the previously described embodiment, it is preferred that the above treatment be carried out in the presence of or be followed by the treatment with a sulphur-containing compound of the above-mentioned type. The amount of the sulphur-containing compound used is also the same as described previously.
  • As a result of the foregoing treatments, there is obtained the electrically conducting material in which sulphides of the first and second metals are adsorbed by the synthetic polymeric material to form a continuous, electrically conducting layer or deposit at least on the surface thereof. The X-ray diffraction pattern of the electrically conducting material of this invention in which copper and silver are used as the first and second metals, respectively, has been found not to be the same as that deduced from the X-ray diffraction patterns of copper sulphide and silver sulphide. The analysis of the electrically conducting material by an X-ray microanalyzer indicates that the silver exists at the same locations as the copper and sulphur. Further, in view of the fact that the electrically conducting material of this invention shows a property which is not execpted from the properties of a synthetic polymeric material having either the sulphide of the first metal or the sulphide of the second metal, the electrically conducting layer is not considered to be formed of a mere mixture of the first metal sulphide and the second metal sulphide. Rather, it is believed that at least some of the first metal sulphide and the second metal sulphide should be present in a mixed crystal-like form in which the second metal is associated with the sulphur atoms or atoms of the first metal sulphide.
  • In addition to the above-described second metal, iron or nickel has been found to be effective in improving the quality of the electrically conducting material, especially in lightening the color thereof. Such as auxiliary metal component may be incorporated into the electrically conducting material in the same manner as the second metal component. Thus, a source of ions containing the auxiliary metal, such as a salt or complex thereof is added to the bath which is used for treating the synthetic polymeric material with first metal-containing ions, the source of ions containing the second metal and/or the sulphur-containing compound. If desired, the incorporation of the auxiliary metal component can be done independently of the above treatments by treating the synthetic polymeric material in the manner and conditions as in the case of the treatment with the source of ions containing the second metal. The amount of auxiliary metal-containing ions used in either case of treatment is generally 0.01 to 0.5 mol per mol of the first metal-containing ions.
  • The electrically conducting material of this invention, when in the form of fibres, may be advantageously utilized in the manufacture of clothes, carpets, interior decorative sheets, gloves or like by themselves or in combination with other fibres because of their freeness of static charging and easiness to be dyed. When in the form of a film or plate, the electrical conductivity and transparency of the materials of this invention allow the use thereof as a cover or enclosure for electric parts such as integrated circuits and large-scale integrated circuits which are required to be shielded from electrostatic charges during storage or transportation. The powdery, electrically conductive material of this invention may be incorporated into a coating composition to form electrically conductive coatings. Because of the excellent thermal stability of the sulphides, the powdery or granular, electrically conductive material of this invention formed from synthetic polymers, such as polyamide, can be subjected to thermal molding conditions to produce electrically conducting molded articles. Thus, the electrically conducting materials of this invention lend themselves to numerous applications in many fields.
  • The following examples will further illustrate the present invention. In the examples, the washability was determined according to the method speculated in Japanese Industrial Standard (JIS) L 1045. That is, a sample was added in a washing liquid containing 3 g/I of a commercially available detergent ("All Temperature Cheer" of Proctor & Gamble Inc.) with a ratio by weight of the sample to the washing liquid of 1:50. The liquid was charged in a dye-fastness testing device together with ten stainless balls and agitated at 50°C for 30 min followed by washing with water and drying. Such a procedure was repeated a number of times for the examination of the fastness to washing. The moisture resistance test was conducted by suspending the sample from the top of a closed glass vessel containing water, the vessel being placed in a thermostat oven to maintain the sample at 60°C and 100% humidity for a given period of time for the examination of the change in its electrical resistivity.
    • Example 1
  • 5 g of a commercially available, electrically conducting polyamide staple fibre having a deposit of copper sulphide (trade mark: "Rhodiastat", 7 denier, manufactured by Rhone Poulenc-Textile, France) were immersed in an aqueous solution containing 2 g/I of silver nitrate and heat-treated therein at 45°C for 3 hours. The resultant fibre was washed with water and dried to obtain an electrically conducting fibre of this invention. The results of the washability test are shown in Table 1 together with that of the non-treated, starting fibre.
  • Figure imgb0001
    • Example 2
  • Example 1 was repeated in the same manner as that described therein except that the treatment bath further contained 5 g/I of sodium thiosulphate and that the treatment time was reduced to 2 hours. The resultant fibre had an electrical resistivity of 1.18x10-1 and no change in electrical conductivity was observed after 50 times washing operations.
    • Example 3
  • A polyamide knit (Toyobo Nylon, 70 denier, 24 filaments) weighing 5 g was suspended within an autoclave to which hydrogen sulphide was charged until the inside pressure reached 5 kg/cm2. The treatment of the knit with hydrogen sulphide was carried out at 20°C for 1 hour. The resulting knit having adsorbed thereby hydrogen sulphide was then immersed in 100 ml of an aqueous solution containing 30 g/I of cupric sulphate and 1 g/I silver nitrate, and treated therein at 20°C for 30 min and then at 50°C for 1 hour. The thus treated knit was olive-gray in color and had an electrical resistivity of 1.46x 10-1 Q-cm. The electrical conductivity remained unchanged through 100 days-moisture-resistance test.
  • For the purpose of comparison, the above procedure was repeated in the same manner as described above except that no silver nitrate was used. The resulting knit had an electrical resistivity of 1.38x10-1 Q-cm. However, the electrical conductivity was lost after 15 days from the initiation of the moisture-resistance test. The results of the washability test were as shown in Table 2.
    • Example 4
  • Example 3 was repeated in the same manner as that described therein except that the treatment bath contained 15 g/I of sodium thiosulphate in addition to the cupric sulphate and silver nitrate, thereby to give a brown-gray, electrically conducting knit having an electrical resistivity of 1.18x10-' Q-cm. During the course of the treatment, there was observed a small amount of precipitates. No appreciable change was observed after 100 days-moisture-resistance test. The washability test gave the results shown in Table 2.
    Figure imgb0002
    • Example 5
  • Example 4 was repeated in the same manner as that described therein except that silver sulphate, palladium chloride, gold chloride and platinum chloride were used each in place of silver nitrate, obtaining an improvement in moisture-resistance. Further, Example 4 was repeated using sodium dithionite in place of sodium thiosulphate, with the results similar to the case of sodium thiosulphate.
    • Example 6
  • A polyamide knit (Toyobo Nylon, 70 deniers, 24 filaments) weighing 5 g was suspended within an autoclave to which was charged hydrogen sulphide until the inside pressure reached 5 kg/cm2, and treated therein. at 20°C for 1 hour. The resulting knit with hydrogen sulphide being adsorbed thereby was then treated in an aqueous bath containing 30 g/I of cupric sulphate at 20°C for 30 min. Subsequently, 0.2 g of palladium chloride and 2 g of sodium thiosulphate were added to the bath and the resulting mixture was heated at 50°C and maintained at that temperature for 2 hours, whereby to obtain an electrically conducting knit product having an electrical resistivity of 3.1 x10-1 Q-cm. The product withstood 30 times washing.
    • Example 6
  • Example 5 was repeated in the same manner as that described therein except that palladium chloride was replaced with various amounts of silver nitrate, whereby obtaining electrically conducting knit materials having various Ag/Cu atomic ratios as shown in Table 3. The washability test results are also shown in Table 3.
    Figure imgb0003
    • Example 7
  • Example 3 was repeated using a polyethylene terephthalate yarn (Trade Mark: Tetoron, 150deniers,30 filaments, manufactured by Toray Co., Ltd. Japan), an aromatic polyamide fibre (Trade Mark: Conex, manufactured by Teijn Co., Ltd., Japan), a polychlal fibre (Trade Mark: Codelan, manufactured by Kojin Co., Ltd., Japan, a copolymer of vinyl alcohol and vinyl chloride), a polyurethane film (Trade Mark: Opelon, manufactured by Toray Co., Ltd., Japan), a polyester powder and a polyamide film, respectively, in place of the polyamide knit, thereby giving electrically conducting materials which withstood 100 days-moisture-resistance test.
    • Example 8
  • A polyamide knit (Toyobo Nylon, 70 denier, 24 filaments) weighing 5 g was suspended within an autoclave to which hydrogen sulphide was charged until the inside pressure reached 5 kg/cm2. The treatment of the knit with hydrogen sulphide was carried out at 20°C for 1 hour. The resulting knit having adsorbed thereby hydrogen sulphide was then immersed in 100 ml of an aqueous solution containing 30 g/I of cobalt acetate, and treated therein at 20°C for 30 min. Subsequently, 0.2 g of silver nitrate and 2 g of sodium thiosulphate were added to the reaction mixture for reaction therewith at 50°C for 2 hours. The thus treated knit was dark brown in color and had an electrical resistivity of 3.6x10-' Q-cm. The electrical conductivity remained unchanged through 100 days-moisture-resistance test.
  • For the purpose of comparison, the above procedure was repeated in the same manner as described above except that no silver nitrate was used. The resulting knit had an electrical resistivity of 3.2x10-1 Q-cm. However, the electrical conductivity was lost after 15 days from the initiation of the moisture-resistance test. The results of the washability test were as shown in Table 4.
    • Example 9
  • Example 8 was repeated in the same manner as that described therein except that cobalt acetate was replaced with lead acetate, thereby to give a dark gray, electrically conducting knit having an electrical resistivity of 1.2x104 Q-cm. No appreciable change was observed after 100 days-moisture-resistance test. The washability test gave the results shown in Table 4. For the purpose of comparison, the above procedure was repeated in the same manner as described above, except that no silver nitrate was used. The resultant knit had an electrical resistivity of 1.4x 1 04 Q-cm. However, the electrical conductivity was lost after 15 days from the initiation of the moisture-resistance test. The results of the washability test are also shown in Table 4.
    Figure imgb0004

Claims (15)

1. An electrically conducting material comprising a substantially cyano group-free synthetic polymeric material having adsorbed thereby a'sulphide of at least one first metal selected from copper, cobalt, tin, mercury, and lead, wherein said synthetic polymeric material is selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35―65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols; characterized in that said synthetic polymeric material also has adsorbed thereby a sulphide of at least one second metal selected from silver, gold, ruthenium, rhodium, palladium, osmium, iridium and platinum.
2. An electrically conducting material as claimed in Claim 1, wherein the amount of the sulphide of the first metal is about 0.5 to 30% in terms of elemental metal based on the weight of the polymeric material.
3. An electrically conducting material as claimed in Claim 1 or Claim 2, wherein the amount of the sulphide of the second metal is such that the atomic ratio M2/Ml, where M1 and M2 stand for the first and second metals, respectively, is in the range of about 0.0001 to 0.5.
4. An electrically conducting material as claimed in Claim 3, wherein the atomic ratio M2/M, is in the range of about 0.001 to 0.3.
5. An electrically conducting material as claimed in any preceding claim, wherein the second metal is silver.
6. An electrically conducting material as claimed in any preceding claim, further comprising the sulphide of iron or nickel adsorbed on the polymeric material.
7. An electrically conducting material as claimed in any preceding claim, wherein said polymeric material is in the form of powder or a shaped body.
8. A method of preparing an electrically conducting material as claimed in Claim 1, which comprises the steps of (1) providing an electrically conducting, first metal sulphide-carrying, substantially cyano group-free synthetic polymeric material, wherein said synthetic polymeric material is selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols and wherein said first metal is selected from copper, cobalt, tin, mercury and lead, and (2) treating said polymeric material with a source of ions containing a second metal selected from silver, ruthenium, rhodium, palladium, osmium, iridium and platinum.
9. A method as claimed in Claim 8, wherein said treatment is conducted in the presence of a sulphur-containing compound.
10. A method as claimed in Claim 8 or 9, further comprising treating the product, obtained by treating said polymeric material with said source of ions containing the second metal, with a sulphur-containing compound.
11. A method of preparing an electrically conducting material as claimed in Claim 1, comprising treating a substantially cyano group-free synthetic polymeric material having adsorbed thereby hydrogen sulphide with (a) a source of ions containing a first metal selected from copper, lead, tin, mercury and cobalt and (b) a source of ions containing a second metal selected from silver, gold, ruthenium, rhodium, palladium, osmium, iridium and platinum, said synthetic polymeric material being selected from polyamides, polyesters, polycarbonates, polyamide-imides, aromatic polyamides, polyurethanes, polyvinylalcohols, copolymers of vinyl chloride and vinyl alcohol containing 35-65% by weight of vinyl chloride units, polyethers, polyethylene oxides and polyphenols.
12. A method as claimed in Claim 11, wherein the treatment with components (a) and (b) is within the same treating bath.
13. A method as claimed in Claim 12, wherein the treatment with component (b) is separate from and subsequent to the treatment with component (a).
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FR644429A (en) * 1927-11-22 1928-10-08 New process for the electrolytic metallization of threads, lace, ribbons, etc.
US3940533A (en) * 1972-04-24 1976-02-24 Rhone-Poulenc-Textile Method of attaching metal compounds to polymer articles

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DE3165320D1 (en) * 1980-03-05 1984-09-13 Nihon Sanmo Dyeing Co Electrically conducting fibres and method of making same
FR2485577A1 (en) * 1980-06-26 1981-12-31 Rhone Poulenc Textile TEXTILES WITH IMPROVED CONDUCTIVE PROPERTIES AND PROCESSES FOR THEIR MANUFACTURE

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR644429A (en) * 1927-11-22 1928-10-08 New process for the electrolytic metallization of threads, lace, ribbons, etc.
US3940533A (en) * 1972-04-24 1976-02-24 Rhone-Poulenc-Textile Method of attaching metal compounds to polymer articles

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