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WO1999050179A1 - Poudre conductrice et composition conductrice transparente - Google Patents

Poudre conductrice et composition conductrice transparente Download PDF

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Publication number
WO1999050179A1
WO1999050179A1 PCT/JP1999/001516 JP9901516W WO9950179A1 WO 1999050179 A1 WO1999050179 A1 WO 1999050179A1 JP 9901516 W JP9901516 W JP 9901516W WO 9950179 A1 WO9950179 A1 WO 9950179A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
conductive powder
fiber
amorphous silica
silica fiber
Prior art date
Application number
PCT/JP1999/001516
Other languages
English (en)
Japanese (ja)
Inventor
Yukiya Hareyama
Hidetoshi Ogawa
Original Assignee
Otsuka Chemical Co., Ltd.
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 Otsuka Chemical Co., Ltd. filed Critical Otsuka Chemical Co., Ltd.
Priority to CA002325582A priority Critical patent/CA2325582A1/fr
Priority to EP99910702A priority patent/EP1069072A1/fr
Publication of WO1999050179A1 publication Critical patent/WO1999050179A1/fr

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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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides

Definitions

  • the present invention relates to a conductive powder having excellent transparency and conductivity, and a transparent conductive composition containing the conductive powder.
  • transparency and conductivity may be required for the purpose of preventing static electricity or for use as electrodes, heating elements, or the like.
  • Several methods have been proposed as methods for imparting such transparency and conductivity. For example, (1) antimony-doped oxidized particles made of fine particles below the wavelength of visible light are kneaded with resin to form a film or paint, and (2) ) — A method of forming a thin film on the surface of a widely used indium oxide / tin oxide compound generally called an ITO film by a sputtering method or the like has been proposed.
  • the particle size of the powder particles is small, the agglomeration force is strong, the aggregates are easily formed as secondary particles, and the dispersibility becomes a problem when a paint is formed. It is necessary to increase the amount of addition in order to form a conductive path.
  • the above method (2) is excellent in both conductivity and transparency, but has a problem that the raw material is expensive and the equipment for forming the thin film becomes dogish.
  • amorphous silicones that are relatively transparent when blended into coatings and films, etc.
  • a method of blending a resin with a conductive powder obtained by coating a conductive metal oxide such as oxidized iron on a force particle or a force particle Japanese Patent Application Laid-Open No. 2-2186876 and a patent (Kaihei 5-116930 Publication No.).
  • An object of the present invention is to provide a conductive powder having excellent transparency and conductivity as compared with conventional conductive powders, and a transparent conductive composition containing the conductive powder.
  • an amorphous silica fiber obtained by acid-treating a calcium silicate fiber comprises one or more selected from tin oxide, antimony oxide, indium oxide, and zinc oxide. It is characterized by being coated with a metal oxide.
  • Such an amorphous silica fiber can be obtained, for example, by subjecting a calcium silicate fiber to an acid treatment, as in the first aspect.
  • the amorphous silica fiber may be an amorphous siliceous fiber obtained by acid-treating a calcium silicate fiber.
  • the amorphous silica fiber may be an amorphous silica fiber. It is preferable that the refractive index of the high strength fiber is 1.4 to 1.8. By setting the refractive index in such a range, more excellent transparency can be obtained when blended in a polymer such as a resin. Obtainable.
  • the coating amount of the metal oxide is preferably 10 to 100 parts by weight based on 100 parts by weight of the amorphous silica fiber. If the coating amount of the metal oxide is too small, sufficient conductivity as a conductive powder may not be obtained in some cases. On the other hand, if the coating amount of the metal oxide is too large, the effect of improving the conductivity corresponding thereto is not recognized, which is economically disadvantageous and tends to decrease transparency.
  • the metal oxide to be coated is selected from tin oxide, antimony oxide, indium oxide, and zinc oxide, and is preferably tin oxide containing antimony oxide, or indium oxide / oxide called ITO. Metal oxide and zinc oxide are used. From the viewpoint of uniformly covering the surface of the amorphous silica fiber and providing high conductivity, tin oxide containing antimony oxide is preferable.
  • the content of antimony oxide is preferably 1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of tin oxide. By doping antimony into tin oxide in this way, the conductivity of tin oxide can be increased.
  • a hydroxide or the like of the target metal oxide is coated on the surface of the amorphous silica fiber in an aqueous solution. Then, after dehydration and drying, a heat treatment is performed to form a conductive metal oxide film on the surface of the amorphous silicon fiber.
  • the hydroxide or the like of the metal oxide can be adjusted by hydrolyzing the metal compound.
  • the metal compound those soluble in water or a water-soluble organic solvent are preferable.
  • acidic or alkaline water-soluble compounds such as halides and oxides, and metal alcohols and metal oxides
  • examples thereof include those soluble in a water-soluble organic solvent such as cetyl acetate toner.
  • C Specific production methods include: By adding a solution of the genus compound and hydrolyzing it, these insolubles are deposited on the surface of the fiber and adhered thereto. Accordingly, the metal compound is hydrolyzed by adding these solutions to the aqueous dispersion of fibers under the condition of hydrolysis, or adding these solutions to the aqueous dispersion.
  • the first method of hydrolysis is to use an organic compound such as an alcoholate or acetyl acetonate as a metal compound, dissolve these in a water-soluble organic solvent, and disperse the amorphous silica fiber in water.
  • an organic compound such as an alcoholate or acetyl acetonate
  • dissolve these in a water-soluble organic solvent dissolve these in a water-soluble organic solvent
  • disperse the amorphous silica fiber in water There is a method in which the metal compound is hydrolyzed by being added to the liquid to deposit the metal compound on the fiber surface.
  • These hydrolysis reactions may be performed under heating or in the presence of an alkaline substance.
  • an alkaline substance hydroxides, carbonates, ammonium compounds and the like of alkali metals can be used.
  • a halide is used as a metal compound, and an alcohol solution of these is added to the aqueous dispersion of the amorphous sily fiber.
  • the hydrolysis reaction may be performed under heating or in the presence of an alkaline substance.
  • the alkaline substance the same substance as in the first method described above can be used.
  • a third method for hydrolysis there is a method of adding an aqueous solution of a metal compound to the aqueous dispersion of amorphous silica fibers. Since this method does not use an organic solvent, it is a preferable method from the viewpoints of working environment, environmental pollution, disaster prevention, and economic efficiency. Also in this method, it is possible to carry out hydrolysis under heating or in the presence of an alkaline substance.
  • an amorphous silica fiber obtained by subjecting a calcium silicate fiber to an acid treatment is used as the amorphous silica fiber.
  • the calcium silicate fiber for example, calcium silicate fiber such as wollastonite or zonolite can be used.
  • the acid treatment of the calcium silicate fiber allows the silicate calcium fiber From which calcium is removed to obtain amorphous silica fibers.
  • the acid treatment is not particularly limited as long as it is an acid treatment capable of forming amorphous silica fibers while keeping the fiber shape of the calcium silicate fiber, but an acid treatment using a weak acid is generally used. preferable.
  • a treatment with carbonic acid is preferable. That is, it is preferable to blow carbon dioxide gas into the aqueous dispersion of calcium silicate fibers.
  • the calcium in the calcium silicate is removed as calcium carbonate, and the fiber can be maintained in an amorphous silicon fiber while maintaining the fiber shape.
  • an acid such as oxalic acid or nitric acid is added to decompose the calcium carbonate. And can be removed.
  • the amorphous siliceous fiber obtained as described above is obtained while maintaining the fiber shape of the raw material calcium silicate fiber. Therefore, it is possible to obtain an amorphous silicon fiber having a fiber length and an aspect ratio substantially equal to those of the raw material calcium silicate fiber. Therefore, the fiber length and the aspect ratio of the amorphous silica fiber can be adjusted by selecting the fiber length and the aspect ratio of the raw material wollastonite fiber.
  • the fiber shape of the amorphous silica fiber a fiber length of 1 to 500 m and an aspect ratio of 5 to 500 are preferable, and a fiber length of 10 to 500 m and more preferably The ratio is 10 to 100.
  • the refractive index of the amorphous silica fiber 1.4 to 1. Is preferably 8, more preferably 1.. 4 to 1.
  • C transparent electrically conductive composition of the present invention is a 6 Is characterized in that the conductive powder of the present invention is contained in a binder.
  • the binder include synthetic polymer compounds such as thermoplastic resins and thermosetting resins, natural resins and their derivatives, and metal-containing materials. Organic compounds, inorganic binders, and inorganic or organic compound emulsions.
  • thermoplastic resin examples include engineering plastics such as polyolefin resin, polyvinyl chloride resin, ABS resin, polystyrene resin, acryl resin, POM resin, PBT resin, and PPS resin.
  • thermosetting resin examples include a phenol resin and an epoxy resin.
  • examples of other synthetic polymer compounds include polyphosphazene.
  • the binder one or more of the above binders can be freely selected and used according to the purpose and use.
  • the transparent conductive composition of the present invention is a conductive resin composition
  • a filler, a reinforcing agent, a pigment, an antioxidant, an antistatic agent, and a lubricant are used as long as necessary transparency is not impaired.
  • a heat stabilizer, a flame retardant, and the like may be appropriately added.
  • the surface of the conductive powder of the present invention may be surface-treated with a coupling agent or the like, and the surface-treated conductive powder may be mixed with a binder.
  • a normal mixing operation for example, a mixing method such as a Banbury mixer method, an internal mixer method, and an extrusion granulation method can be appropriately employed.
  • the transparent conductive composition of the present invention has excellent transparency, it is useful for use in the form of a molded product such as a coating film, a film, and a sheet.
  • the coating film can be formed by using an ordinary coating material such as a solvent-type coating, a water-based coating, or an emulsion coating.
  • a film sheet it can be formed by a usual film forming method and a sheet forming method.
  • the conductive powder 3 contains 1-8 0 weight%, the volume resistivity is not more than 1 0 1 ° ⁇ ⁇ cm, the total light transmittance of 3 0-1 0 0% It is preferable that If the content of the conductive powder is too small, desired conductivity may not be obtained, and if the content of the conductive powder is too large, transparency may be reduced. Further, in applications where conductivity is required for the purpose of preventing static electricity or the like, it is often required that the volume resistivity is less than 101 ⁇ ⁇ cm. Further, the total light transmittance is preferably 30% or more, and more preferably 50% or more.
  • ADVANTAGE OF THE INVENTION According to this invention, it can be set as the electroconductive powder which can be mix
  • a transparent conductive composition having excellent transparency and excellent conductivity can be obtained.
  • the conductive powder of the present invention is useful as an electrostatic coating or as an electrodeposition primer in the field of coating steel plates and the like.
  • the conductive powder of the present invention by adding the conductive powder of the present invention to a base layer of a metallic paint in the field of coating steel plates or the like, a base layer that can be overcoated without a primer can be provided.
  • the composition of the coating used as the base layer include those comprising the conductive powder of the present invention, an aluminum paste, a pigment, and a polyester melamine binder.
  • the conductive powder of the present invention exhibits an excellent matting effect in addition to imparting a desired conductivity when blended into a paint, so that it is particularly useful in applications in the above-mentioned respective coating fields. Things. BEST MODE FOR CARRYING OUT THE INVENTION
  • Calcium silicate fiber (trade name “Vistal”, manufactured by Otsuka Chemical Co., Ltd.
  • the dispersion was bubbled into the dispersion at a flow rate of 00 m 1 / min and treated for 20 hours. After completion of the treatment, the mixture was cooled to 40 ° C., and while stirring, concentrated nitric acid (67.5%) was added dropwise over 24 O ml Z for 10 minutes, and then stirring was continued for 1 hour.
  • the obtained product was an amorphous silica fiber, having an average fiber length of 23 ⁇ , an average fiber diameter of 0.777 m, an average aspect ratio of 30 and a refractive index of 1.5.
  • amorphous silica fiber obtained in the Production Example disperse it in 2.5 liters of deionized water, keep it at 70 ° C, and stir with tin chloride and antimony chloride.
  • the mixed hydrochloric acid solution and aqueous sodium hydroxide solution were simultaneously dropped separately, and the mixture was further stirred for 2 hours while maintaining the pH at about 3. Thereafter, the resultant was filtered, washed with water, dehydrated, dried at 110 ° C. for 10 hours, and further heat-treated at 450 ° C. to obtain a fibrous conductive powder of the present invention.
  • the amount of tin oxide was 25 parts by weight, and the amount of antimony oxide was 5 parts by weight, based on 100 parts by weight of the base material.
  • white Tokabon (trade name “two Ppushiru”, Japan Siri force Industry Co., Ltd., the main component S i 0 2, the average particle diameter of 1 6 m, a refractive index of 1.
  • a conductive powder was prepared in the same manner as in Example 1 except that 4 8) was used.c Comparative Example 2
  • Example 1 except that muscovite (trade name "Z-20", manufactured by Hikawa Mining Co., Ltd., scale-like, average particle size 50 m, refractive index 1.56) is used as the base material.
  • muscovite trade name "Z-20", manufactured by Hikawa Mining Co., Ltd., scale-like, average particle size 50 m, refractive index 1.56
  • a conductive powder was prepared.
  • the pellets of the polypropylene resin were melted, and the conductive powder of Example 1 was obtained from the side hopper. After being charged and kneaded, the sheet was extruded in a sheet shape so as to have a thickness of 30 // in to form a conductive sheet.
  • the mixing ratio of the conductive powder in the sheet was 30% by weight.
  • a sheet was produced in the same manner as in Example 2 except that the conductive powder of Comparative Example 1 was used as the conductive powder.
  • a sheet was produced in the same manner as in Example 2 except that the conductive powder of Comparative Example 2 was used as the conductive powder.
  • a test piece is sandwiched between two electrodes, and the value of the current flowing through the test piece when a DC voltage is applied is measured, and the volume resistivity (the voltage divided by the current value flowing through the unit volume of the test piece is measured) Numerical value: unit ⁇ ⁇ cm) was obtained.
  • the obtained sheet was cut into 8 cm square (thickness lmm or less) to make a test piece.
  • the total light transmittance (%) was measured using Haze Computer-1 (model number HGM-2DP: manufactured by Suga Test Instruments Co., Ltd.).
  • the solvent-containing solution-type urethane resin was mixed with the conductive powder of Example 1 at a solid content of 40% by weight in terms of solid content, mixed well with stirring, and then applied on a PET film. It was dried by heating to obtain a coating film having a dry film thickness of 10 ⁇ m.
  • a coating film was formed in the same manner as in Example 3 except that the conductive powder of Comparative Example 1 was used as the conductive powder.
  • a coating film was formed in the same manner as in Example 3 except that the conductive powder of Comparative Example 2 was used as the conductive powder.
  • Example 3 A coating film was formed in the same manner as in Example 3 except that the same conductive powder having the same titanium oxide fiber as the base used in Comparative Example 5 was used as the conductive powder.
  • the present invention can be applied to members that have conventionally been required to have transparency and conductivity, such as display device members, antistatic films and packaging materials, transparent electrodes, and transparent heating elements.

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  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne une poudre conductrice produite par traitement de fibres de silicate de calcium au moyen d'un acide et par l'enduction des fibres de silice amorphes résultantes d'au moins un oxyde métallique choisi parmi l'oxyde d'étain, l'oxyde d'antimoine, l'oxyde d'indium et l'oxyde de zinc.
PCT/JP1999/001516 1998-03-27 1999-03-24 Poudre conductrice et composition conductrice transparente WO1999050179A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002325582A CA2325582A1 (fr) 1998-03-27 1999-03-24 Poudre electriquement conductive et composition transparente conductive
EP99910702A EP1069072A1 (fr) 1998-03-27 1999-03-24 Poudre conductrice et composition conductrice transparente

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/81508 1998-03-27
JP10081508A JP2978146B2 (ja) 1998-03-27 1998-03-27 導電性粉末及び透明導電性組成物

Publications (1)

Publication Number Publication Date
WO1999050179A1 true WO1999050179A1 (fr) 1999-10-07

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Application Number Title Priority Date Filing Date
PCT/JP1999/001516 WO1999050179A1 (fr) 1998-03-27 1999-03-24 Poudre conductrice et composition conductrice transparente

Country Status (4)

Country Link
EP (1) EP1069072A1 (fr)
JP (1) JP2978146B2 (fr)
CA (1) CA2325582A1 (fr)
WO (1) WO1999050179A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4182825B2 (ja) 2002-07-01 2008-11-19 住友金属鉱山株式会社 日射遮蔽用アンチモン錫酸化物微粒子とこれを用いた日射遮蔽体形成用分散液および日射遮蔽体並びに日射遮蔽用透明基材
ITRM20020622A1 (it) * 2002-12-13 2004-06-14 Ct Sviluppo Materiali Spa Procedimento per la termospruzzatura al plasma di rivestimenti a base di ossidi semiconduttori drogati.
CN100388392C (zh) * 2005-06-20 2008-05-14 浙江大学 以层状硅酸盐矿物为基体的导电粉体
JP5284632B2 (ja) * 2007-12-12 2013-09-11 日揮触媒化成株式会社 導電性繊維状中空シリカ微粒子分散質およびその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5580715A (en) * 1978-12-11 1980-06-18 Tokuyama Soda Co Ltd Production of amorphous silica hydrate
JPS625507A (ja) * 1985-06-28 1987-01-12 住友化学工業株式会社 繊維状透明導電性物質
JPS62122005A (ja) * 1985-11-21 1987-06-03 住友化学工業株式会社 導電性に優れた繊維状白色導電性フイラ−の製造方法
JPS634503A (ja) * 1986-06-24 1988-01-09 住友化学工業株式会社 耐光性に優れた繊維状白色導電性物質の製造方法
JPH05116930A (ja) * 1991-10-22 1993-05-14 Nippon Chem Ind Co Ltd 白色導電性粉末

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5580715A (en) * 1978-12-11 1980-06-18 Tokuyama Soda Co Ltd Production of amorphous silica hydrate
JPS625507A (ja) * 1985-06-28 1987-01-12 住友化学工業株式会社 繊維状透明導電性物質
JPS62122005A (ja) * 1985-11-21 1987-06-03 住友化学工業株式会社 導電性に優れた繊維状白色導電性フイラ−の製造方法
JPS634503A (ja) * 1986-06-24 1988-01-09 住友化学工業株式会社 耐光性に優れた繊維状白色導電性物質の製造方法
JPH05116930A (ja) * 1991-10-22 1993-05-14 Nippon Chem Ind Co Ltd 白色導電性粉末

Also Published As

Publication number Publication date
JPH11278826A (ja) 1999-10-12
JP2978146B2 (ja) 1999-11-15
EP1069072A1 (fr) 2001-01-17
CA2325582A1 (fr) 1999-10-07

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