JPH0494009A - Conductive compound - Google Patents
Conductive compoundInfo
- Publication number
- JPH0494009A JPH0494009A JP21028990A JP21028990A JPH0494009A JP H0494009 A JPH0494009 A JP H0494009A JP 21028990 A JP21028990 A JP 21028990A JP 21028990 A JP21028990 A JP 21028990A JP H0494009 A JPH0494009 A JP H0494009A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- fine particles
- copper
- conductive composition
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title abstract 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 56
- 239000004332 silver Substances 0.000 claims abstract description 56
- 239000010419 fine particle Substances 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052737 gold Inorganic materials 0.000 claims abstract description 12
- 239000010931 gold Substances 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 46
- 229910052802 copper Inorganic materials 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 45
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- -1 cupper Chemical compound 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000010954 inorganic particle Substances 0.000 abstract 1
- 238000007738 vacuum evaporation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 20
- 238000007747 plating Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 238000004453 electron probe microanalysis Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 241000972773 Aulopiformes Species 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- VZOPRCCTKLAGPN-UHFFFAOYSA-L potassium;sodium;2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O VZOPRCCTKLAGPN-UHFFFAOYSA-L 0.000 description 5
- 235000019515 salmon Nutrition 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は導電性組成物に係り、繊維製品、フィルム、プ
ラスチック成型品、ペイント等の製造に際して添加され
、これらの製品に導電性をもたらすために利用される導
電性微粒子に関するものである。[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a conductive composition, which is added during the production of textile products, films, plastic molded products, paints, etc. to bring conductivity to these products. The present invention relates to conductive fine particles used for.
（従来の技術）
上記のような導電性の繊維製品等を製造するために添加
される従来の導電性微粒子としては、種々の金属粒子、
カーボンブラックなどが知られている。また酸化チタン
の微粒子に酸化亜鉛または酸化錫被膜を形成させ−た微
粒子により最高１０−２Ω αが得られている（特公平
１−２２３６５号）。(Prior Art) Conventional conductive fine particles added to produce the above-mentioned conductive textile products include various metal particles,
Carbon black and the like are known. Furthermore, a maximum resistance of 10<-2 >[Omega][alpha] has been obtained using fine particles of titanium oxide coated with zinc oxide or tin oxide (Japanese Patent Publication No. 1-22365).
（発明が解決しようとする課題及び発明の目的）上記の
金属粒子は高価であり、比重が大であるため、マトリッ
クスとの比重差が大であり、混練時に沈降し易いという
欠点がある。またカーボンブラックを導電性組成物とし
て使用すると混練成型品が黒色のものしか得られないと
いう問題がある。(Problems to be Solved by the Invention and Objects of the Invention) The metal particles described above are expensive and have a large specific gravity, so there is a large difference in specific gravity from the matrix, and there is a drawback that they tend to settle during kneading. Furthermore, when carbon black is used as a conductive composition, there is a problem in that only black kneaded and molded products can be obtained.
そして上記の特公平１−２２３６５号により提案されて
いるものがあるが、更に優れた導電性のものが待望され
ている。Although there is a method proposed in the above-mentioned Japanese Patent Publication No. 1-22365, there is a long-awaited demand for one with even better conductivity.
本発明は上記の問題に鑑みてなされたものであり、その
目的は導電性組成物を混練した成型品の着色が少なく、
製造が容易で高導電性であり、かつ廉価な導電性組成物
を提供することにある。The present invention was made in view of the above-mentioned problems, and its purpose is to reduce the coloring of molded products made by kneading conductive compositions.
The object of the present invention is to provide a conductive composition that is easy to manufacture, has high conductivity, and is inexpensive.
（課題を解決し、目的を達成する手段及び作用）本発明
によれば、上記の課題は無機質の微粒子の表面に導電性
金属被膜が１０重量％以上２５重量％未満均均斉形成せ
しめられていることを特徴とする導電性組成物により基
本的に解決されると共に、上記の目的が達成される。(Means and effects for solving the problem and achieving the object) According to the present invention, the above problem is solved by uniformly forming a conductive metal coating of 10% by weight or more and less than 25% by weight on the surface of the inorganic fine particles. This is basically solved and the above objects are achieved by an electrically conductive composition characterized by the following.
本発明に使用する導電性金属被膜の金属としては金、銀
、銅、アルミニウム等の金属を用いることが出来る。導
電性の点では銀、銅、金、アルミニウムの順に好ましい
が、金、銀は高価である為、第１層として銅又はアルミ
ニウム被膜を形成させた後、更に第２層として金又は銀
被膜を形成させても良い。As the metal of the conductive metal coating used in the present invention, metals such as gold, silver, copper, and aluminum can be used. In terms of conductivity, silver, copper, gold, and aluminum are preferred in this order, but since gold and silver are expensive, it is preferable to form a copper or aluminum film as the first layer, and then apply a gold or silver film as the second layer. It may be formed.
金属被膜が酸化され易い条件下にある場合には第２層に
金又は銀を使用することが望ましい、また着色度の点で
３層以上の組み合せでも良い。When the metal coating is under conditions where it is easily oxidized, it is desirable to use gold or silver for the second layer, and a combination of three or more layers may be used in terms of the degree of coloration.
担体としての微粒子上に導電性金属を付着させて本発明
による導電性組成物を製造するためには、自体周知の真
空蒸着法や還元析出法を用いることができる。In order to produce the conductive composition according to the present invention by depositing a conductive metal on fine particles as a carrier, a well-known vacuum deposition method or a reduction precipitation method can be used.
これらのうちで真空蒸着法は担体微粒子を蒸着装買のチ
ャンバー内にセットし、蒸着源をタングステン製バスケ
ットに乗せて上記のチャンバー内にセットし、該チャン
バー内を減圧しく約２×１０−’ Ｔｏｒｒ程度迄）、
次いで上記の担体微粒子を振動させながら上記のタング
ステンバスケ・ントを加熱して上記の蒸発源金属を蒸発
せしめることにより実施することができる。Among these methods, in the vacuum evaporation method, carrier fine particles are set in the chamber of the evaporation equipment, the evaporation source is placed on a tungsten basket and set in the above-mentioned chamber, and the pressure inside the chamber is reduced to approximately 2 x 10-' Torr level),
This can then be carried out by heating the tungsten basket while vibrating the fine carrier particles to evaporate the evaporation source metal.
一方、還元析出法は担体微粒子を純水中に分散させ、こ
の分散液とめつき液とを混合し、次いで、攪拌しながら
この混合液にめっき用還元液を添加することにより実施
することができる。On the other hand, the reduction precipitation method can be carried out by dispersing fine carrier particles in pure water, mixing this dispersion with a plating solution, and then adding a reducing solution for plating to this mixed solution while stirring. .
これらの両方法の内で真空蒸着法は蒸発金属の照射方向
が限定されるために、導電性金属を担体微粒子上に均斉
に付着させる目的で担体微粒子に振動を与えて転勤させ
る必要性があり、従って担体微粒子の粒径が揃っていな
いと導電性金属の付着量に差が生じるが、一方、還元析
出法によれば分散した状態の担体微粒子上に導電性金属
が析出してゆくので均斉な付着が可能であり、付着量の
制御も容易なので前者よりも後者の方法が望ましい。Of these two methods, the vacuum evaporation method is limited in the direction of irradiation of the evaporated metal, so it is necessary to vibrate and transfer the conductive metal to the carrier particles in order to uniformly deposit the conductive metal onto the carrier particles. Therefore, if the particle size of the carrier particles is not uniform, there will be a difference in the amount of conductive metal deposited.On the other hand, in the reduction precipitation method, the conductive metal is deposited on the dispersed carrier particles, so it is not uniform. The latter method is preferable to the former method because it allows for more precise adhesion and easier control of the amount of adhesion.
導電性金属被膜が１０重量％未満の場合は導電性が充分
でない為、１０重量％以上の導電性金属被膜形成が必要
であり、２５重量％以上の場合はその増加分に見合った
導電性の向上が見られなくなる。If the amount of the conductive metal coating is less than 10% by weight, the conductivity will not be sufficient, so it is necessary to form a conductive metal coating of 10% by weight or more, and if it is 25% by weight or more, the amount of conductivity will be No improvement will be seen.
導電性被膜を担持させる微粒子は平均粒径２μｍ以下で
あればマトリックスに混練する際、実用上使用できる。The fine particles supporting the conductive film can be practically used when kneaded into the matrix if they have an average particle size of 2 μm or less.
また担体微粒子は球に近い形状の方が混練する際には容
易であるが、マトリックスを配向させた場合、針状であ
る方が導電性としては好ましい。Further, it is easier to knead the carrier fine particles when the shape is close to a sphere, but when the matrix is oriented, the needle-like shape is preferable in terms of conductivity.
担体微粒子としては無電解めっきをする際に変化しない
物であれば何でも良く、水不溶性の金属酸化物、例えば
酸化チタン、酸化アルミニウム、又は硫酸バリウム又は
炭酸カルシウム等を使用することが出来る。Any carrier fine particles may be used as long as they do not change during electroless plating, and water-insoluble metal oxides such as titanium oxide, aluminum oxide, barium sulfate, or calcium carbonate can be used.
本発明の導電性組成物は各種ポリマー（ポリエステル、
ナイロン、アクリル）、繊維、フィルム、プラスチック
成型品、ペイント等に添加され静電気防止、電磁波シー
ルド、低温発熱体等に使用出来る。The conductive composition of the present invention can be applied to various polymers (polyester,
It can be added to fibers, films, plastic molded products, paints, etc., and used for static electricity prevention, electromagnetic shielding, low-temperature heating elements, etc.
（実施例等）
次に、本発明による導電性組成物の製造例及び使用例に
より、本発明を更に詳細に説明する。(Examples etc.) Next, the present invention will be explained in more detail with reference to manufacturing examples and usage examples of the conductive composition according to the present invention.
尚、下記において言及する％及び部は、別設の定めがな
い限り重量基準によるものである。Note that the percentages and parts mentioned below are based on weight unless otherwise specified.
１１匠Ｌ （１）下記の３種類の液を調整した。11 Takumi L (1) The following three types of liquids were prepared.
（Ａ）担体微粒子分散液 担体微粒子１００ｇを純水５００−に分散させたもの。(A) Carrier fine particle dispersion liquid 100 g of fine carrier particles are dispersed in 500 g of pure water.
（Ｂ）銀めっき液
硝酸銀２２．０ｇを純水に溶解して１，０００−とじた
後に水酸化アンモニウムを添加してｐＨを１１に調整し
たもの。(B) Silver plating solution: 22.0 g of silver nitrate was dissolved in pure water and the pH was adjusted to 11 by adding ammonium hydroxide.
（Ｃ）銀めっき用還元液
酒石酸カリウムナトリウム（４水和物）７５ｇを純水に
より溶解して５００−となし、液温を３０°Ｃに保った
もの。(C) Reducing solution for silver plating 75 g of potassium sodium tartrate (tetrahydrate) was dissolved in pure water to give a solution of 500-, and the solution temperature was maintained at 30°C.
（２）操作
担体微粒子として酸化チタン（平均粒径１．５μｍ）を
用い、上記の分散液（Ａ）に銀めっき液（Ｂ）を添加し
て混合し、液温を３０°Ｃで攪拌しながら上記の銀めっ
き用還元液（Ｃ）を添加して攪拌を続けることにより銀
イオンを完全に還元させ、次いで更に１時間攪拌を継続
した。その後に攪拌を中止し、Ｎａ２Ｏ濾紙を用いて吸
引濾過し、純水で充分に洗浄し、さらに、この粉末を純
水中に分散させ攪拌しながらヒドラジンヒトラードを加
えて液温を８０℃にして１０分間処理した。(2) Operation Using titanium oxide (average particle size 1.5 μm) as carrier fine particles, silver plating solution (B) was added to the above dispersion solution (A) and mixed, and the solution was stirred at a temperature of 30°C. Meanwhile, the above-mentioned reducing solution for silver plating (C) was added and stirring was continued to completely reduce the silver ions, and then stirring was continued for an additional hour. After that, stirring was stopped, suction filtration was carried out using Na2O filter paper, and the powder was thoroughly washed with pure water. Further, this powder was dispersed in pure water, and while stirring, hydrazine hydrogen hydroxide was added and the liquid temperature was raised to 80°C. and treated for 10 minutes.
その後に攪拌を中止し、ＮＬ５Ｃろ紙を用いて吸引ろ過
し、純水で充分に洗浄し、８０℃の空気乾燥機内で１２
時間乾燥することにより所望の導電性組成物を得た。こ
の導電性組成物における銀の付着状態をＥＰＭＡにて観
察した処、酸化チタン粉末の表面に銀が均斉に付着して
いることが判明しな、化学分析によれば銀の付着量は１
２．２％であった。After that, stirring was stopped, suction filtered using NL5C filter paper, thoroughly washed with pure water, and placed in an air dryer at 80°C for 12 hours.
A desired conductive composition was obtained by drying for a period of time. When observing the state of silver adhesion in this conductive composition using EPMA, it was found that silver was uniformly adhered to the surface of the titanium oxide powder, and according to chemical analysis, the amount of silver adhesion was 1.
It was 2.2%.
製ゑｌ」工
銀めっき液中の硝酸銀溶解量を４０．２ｇとし、銀めっ
き用還元液中の酒石酸カリウムナトリウム（４水和物）
量を１４０ｇとしたこと以外は製造例１と全く同様にし
て導電性組成物を得た。The amount of silver nitrate dissolved in the silver plating solution was 40.2 g, and the amount of potassium sodium tartrate (tetrahydrate) in the reducing solution for silver plating was 40.2 g.
A conductive composition was obtained in exactly the same manner as in Production Example 1 except that the amount was 140 g.
この導電性組成物における銀の付着状態をＥＰＭＡにて
観察した処、酸化チタン粉末の表面に銀が均斉に付着し
ていることが判明した。化学分析によれば銀の付着量は
２０．２％であった。When the state of silver adhesion in this conductive composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the titanium oxide powder. According to chemical analysis, the amount of silver deposited was 20.2%.
１１九り
担体微粒子として酸化アルミニウム（平均粒径１．５μ
ｍ）を用いたこと以外は製造例１と全く同様にして導電
性組成物を得た。Aluminum oxide (average particle size 1.5μ
A conductive composition was obtained in exactly the same manner as in Production Example 1 except that m) was used.
この導電性組成物における銀の付着状態をＥＰＭＡにて
観察した処、酸化アルミニウム粉末の表面に銀が均斉に
付着していることが判明した。化学分析によれば銀の付
着量は１２．１％であった。When the state of silver adhesion in this conductive composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the aluminum oxide powder. According to chemical analysis, the amount of silver deposited was 12.1%.
１皮鮭支
担体微粒子として前記の酸化アルミニウムを用いたこと
以外は製造例２と全く同様にして導電性組成物を得た。A conductive composition was obtained in exactly the same manner as in Production Example 2, except that the aluminum oxide described above was used as the salmon support fine particles.
この導電性組成物における銀の付着状態をＥＰＭＡにて
観察した処、酸化アルミニウム粉末の表面に銀が均斉に
付着していることが判明した。化学分析によれば銀の付
着量は２０．１％であった。When the state of silver adhesion in this conductive composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the aluminum oxide powder. According to chemical analysis, the amount of silver deposited was 20.1%.
１逢匠ｉ
担体微粒子として硫酸バリウム（平均粒径１．５μｍ）
を用いたこと以外は製造例１と全く同様にして導電性組
成物を得た。1. Barium sulfate as carrier fine particles (average particle size 1.5 μm)
A conductive composition was obtained in exactly the same manner as in Production Example 1 except that .
この導電性組成物における銀の付着状態をＥＰＭＡにて
観察した処、硫酸バリウム粉末の表面に銀が均斉に付着
していることが判明した。化学分析によれば銀の付着量
は１２．０％であった。When the state of silver adhesion in this conductive composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the barium sulfate powder. According to chemical analysis, the amount of silver deposited was 12.0%.
設ｆｆｉ
担体微粒子として前記の硫酸バリウムを用いたこと以外
は製造例２と全く同様にして導電性組成物を得た。Setting ffi A conductive composition was obtained in exactly the same manner as in Production Example 2, except that the above barium sulfate was used as the carrier fine particles.
この導電性組成物における銀の付着状態をＥＰＭＡにて
観察した処、硫酸バリウム粉末の表面に銀が均斉に付着
していることが判明した。化学分析によれば銀の付着量
は２０．０％であった。When the state of silver adhesion in this conductive composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the barium sulfate powder. According to chemical analysis, the amount of silver deposited was 20.0%.
１１匠り
担体微粒子として炭酸カルシウム（平均粒径１゜５μｍ
）を用いたこと以外は製造例１と全く同様にして導電性
組成物を得た。11 Calcium carbonate (average particle size 1°5 μm) as fine carrier particles
A conductive composition was obtained in exactly the same manner as in Production Example 1 except that ) was used.
この導電性組成物における銀の付着状態をＥＰＭＡにて
観察した処、炭酸カルシウム粉末の表面に銀が均斉に付
着していることが判明した。化学分析によれば銀の付着
量は１２，２％であった。When the state of silver adhesion in this conductive composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the calcium carbonate powder. According to chemical analysis, the amount of silver deposited was 12.2%.
艷り匹比
担体微粒子として前記の硫酸カルシウムを用いたこと以
外は製造例２と全く同様にして導電性組成物を得た。A conductive composition was obtained in exactly the same manner as in Production Example 2, except that the calcium sulfate described above was used as the carrier fine particles.
この導電性組成物における銀の付着状態をＥＰＭＡにて
観察した処、炭酸カルシウム粉末の表面に銀が均斉に付
着していることが判明した。化学分析によれば銀の付着
量は２０．２％であった。When the state of silver adhesion in this conductive composition was observed using EPMA, it was found that silver was uniformly adhered to the surface of the calcium carbonate powder. According to chemical analysis, the amount of silver deposited was 20.2%.
１１鮭史
（１）次の銅めっき液及び銅めっき用還元液を調整した
。11 History of Salmon (1) The following copper plating solution and reducing solution for copper plating were prepared.
（Ｂ′）銅めっき液
硫酸銅（５水和物）５４．９ｇ、酒石酸カリウムナトリ
ウム（４水和物）１１０ｇ及び水酸化ナトリウム３１ｇ
を純水により溶解して６５０ ｄとなしたもの。(B') Copper plating solution Copper sulfate (pentahydrate) 54.9g, potassium sodium tartrate (tetrahydrate) 110g and sodium hydroxide 31g
Dissolved in pure water to obtain 650 d.
（Ｃ′）銅めっき用還元液
３７％ホルムアルデヒド溶液２４０−であって、液温３
０℃に保たれたもの。(C') Reducing solution for copper plating 37% formaldehyde solution 240-, liquid temperature 3
kept at 0℃.
（２）操作
担体微粒子として前記の酸化チタンを用い製造例１と同
様に調製した分散液（Ａ）に銅めっき液（Ｂ′）を添加
して混合し、液温を３０℃で攪拌しながら上記の銅めっ
き用還元液（Ｃ′）を添加して攪拌を続けることにより
銅イオンを完全に還元させ、次いで更に１時間攪拌を継
続した。その後に攪拌を中止し、１１１［Ｌ５ｃ濾紙を
用いて吸引濾過し、純水で充分に洗浄し、さらに、この
粉末を純水中に分散させ攪拌しながらＳＢＨを加えて液
温を８０℃にして１０分間処理した。(2) Operation Copper plating solution (B') was added to the dispersion (A) prepared in the same manner as in Production Example 1 using the titanium oxide as the carrier fine particles and mixed, and the solution temperature was kept at 30°C while stirring. The above-mentioned reducing solution for copper plating (C') was added and stirring was continued to completely reduce the copper ions, and then stirring was continued for an additional hour. After that, stirring was stopped, suction filtration was performed using 111 [L5c filter paper, and the powder was thoroughly washed with pure water. Furthermore, this powder was dispersed in pure water, and while stirring, SBH was added and the liquid temperature was raised to 80°C. and treated for 10 minutes.
その後に攪拌を中止し、Ｎ［Ｌ５Ｃのろ紙を用いて吸引
ろ過し、純水で充分に洗浄し、８０℃の空気乾燥機内で
１２時間乾燥することにより所望の導電性組成物を得た
。この導電性組成物における銅の付着状態をＥＰＭＡに
て観察した処、酸化チタン粉末の表面に銅が均斉に付着
していることが判明した。化学分析によれば銅の付着量
は１２．２％であった。Thereafter, stirring was stopped, and the mixture was suction-filtered using N[L5C filter paper, thoroughly washed with pure water, and dried in an air dryer at 80° C. for 12 hours to obtain a desired conductive composition. When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the titanium oxide powder. According to chemical analysis, the amount of copper deposited was 12.2%.
艮ｎ吐１表−
銅めっき液中の硫酸銅溶解量を１００゜４ｇとし、銅め
つき用還元液中の酒石酸カリウムナトリウム（４水和物
）量を２７５ｇとしたこと以外は製造例９と全く同様に
して導電性組成物を得た。Table 1 - Same as Production Example 9 except that the amount of copper sulfate dissolved in the copper plating solution was 100°4g, and the amount of potassium sodium tartrate (tetrahydrate) in the reducing solution for copper plating was 275g. A conductive composition was obtained in exactly the same manner.
この導電性組成物における銅の付着状態をＥＰＭＡにて
観察した処、酸化チタン粉末の表面に銅が均斉に付着し
ていることが判明した。化学分析によれば銅の付着量は
２０．２％であった。When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the titanium oxide powder. According to chemical analysis, the amount of copper deposited was 20.2%.
数４」は」−
担体微粒子として前記の酸化アルミニウムを用いたこと
以外は製造例９と全く同様にして導電性組成物を得た。A conductive composition was obtained in exactly the same manner as in Production Example 9 except that the aluminum oxide described above was used as the carrier fine particles.
この導電性組成物における銅の付着状態をＥＰＭＡにて
観察した処、酸化アルミニウム粉末の表面に銅が均斉に
付着していることが判明した。化学分析によれば銅の付
着量は１２．０％であった。When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the aluminum oxide powder. According to chemical analysis, the amount of copper deposited was 12.0%.
１１鮭り工
担体微粒子として前記の酸化アルミニウムを用いたこと
以外は製造例１０と全く同様にして導電性組成物を得た
。11 A conductive composition was obtained in exactly the same manner as in Production Example 10 except that the aluminum oxide described above was used as the salmon carrier fine particles.
この導電性組成物における銅の付着状態をＥＰＭＡにて
観察した処、酸化アルミニウム粉末の表面に銅が均斉に
付着していることが判明した。化学分析によれば銀の付
着量は２０．１％であった。When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the aluminum oxide powder. According to chemical analysis, the amount of silver deposited was 20.1%.
１遭匠ＬΣ
担体微粒子として前記の硫酸バリウムを用いたこと以外
は製造例９と全く同様にして導電性組成物を得た。A conductive composition was obtained in exactly the same manner as in Production Example 9 except that the barium sulfate described above was used as the carrier fine particles.
この導電性組成物における銅の付着状態をＥＰＭＡにて
観察した処、硫酸バリウム粉末の表面に銅が均斉に付着
していることが判明した。化学分析によれば銅の付着量
は１２．１％であった。When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the barium sulfate powder. According to chemical analysis, the amount of copper deposited was 12.1%.
１１鮭り先
担体微粒子として前記の硫酸バリウムを用いたこと以外
は製造例１０と全く同様にして導電性組成物を得た。11 A conductive composition was obtained in exactly the same manner as in Production Example 10 except that the barium sulfate described above was used as the salmon tip carrier particles.
この導電性組成物における銅の付着状態をＥＰＭＡにて
観察した処、硫酸バリウム粉末の表面に銅が均斉に付着
していることが判明した。化学分析によれば銅の付着量
は２０．０％であった。When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the barium sulfate powder. According to chemical analysis, the amount of copper deposited was 20.0%.
１１漣１５
担体微粒子として前記の炭酸カルシウムを用いたこと以
外は製造例９と全く同様にして導電性組成物を得た。11 Ren 15 A conductive composition was obtained in exactly the same manner as in Production Example 9 except that the calcium carbonate described above was used as the carrier fine particles.
この導電性組成物における銅の付着状態をＥＰＭＡにて
観察した処、炭酸カルシウム粉末の表面に銅が均斉に付
着していることが判明した。化学分析によれば銅の付着
量は１２．１％であった。When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the calcium carbonate powder. According to chemical analysis, the amount of copper deposited was 12.1%.
１１匹り恒
担体微粒子として前記の炭酸カルシウムを用いたこと以
外は製造例１０と全く同様にして導電性組成物を得た。A conductive composition was obtained in exactly the same manner as in Production Example 10, except that the above-mentioned calcium carbonate was used as the constant carrier fine particles.
この導電性組成物における銅の付着状態をＥＰＭＡにて
観察した処、炭酸カルシウム粉末の表面に銅が均斉に付
着していることが判明した。化学分析によれば銅の付着
量は２０．２％であった。When the state of copper adhesion in this conductive composition was observed using EPMA, it was found that copper was uniformly adhered to the surface of the calcium carbonate powder. According to chemical analysis, the amount of copper deposited was 20.2%.
１逢ＬＬ７−
製造例９で得られた、銅１２．２ ｗｔ％付着させた酸
化チタン微粒子１１４．０ ｇに製造例１と同様の方法
で、銀めっき液の硝酸銀を９．６ｇとして、銀めっき用
還元液の酒石酸カリウムナトリウム（４水和物）を５０
ｇとして操作した後に攪拌を中止し、Ｎ１５Ｃ濾紙を用
いて吸引濾過し、純水で充分に洗浄し、さらに、この粉
末を純水中に分散させ攪拌しながらヒドラジンヒトラー
ドを加えて液温を８０°Ｃにして１０分間処理したとこ
ろ、暗銀灰色の微粒子を得た。1逢LL7- Using the same method as in Production Example 1, 114.0 g of titanium oxide fine particles to which 12.2 wt% copper was attached, obtained in Production Example 9, was coated with 9.6 g of silver nitrate in the silver plating solution. 50% potassium sodium tartrate (tetrahydrate), a reducing solution for plating.
After the operation as g, stop stirring, suction filtrate using N15C filter paper, wash thoroughly with pure water, and further disperse this powder in pure water and add hydrazine hydrogen tride while stirring to cool the liquid temperature. When treated at 80°C for 10 minutes, dark silver-gray fine particles were obtained.
この微粒子を化学分析により、銅および銀の含有率を分
析したところ、銅は１１．６ ｗＬ％、銀は５．１ｗｔ
％であった。Chemical analysis of these fine particles revealed that the content of copper and silver was 11.6 wL% and 5.1 wL% of silver.
%Met.
製Ｊゴ九１」−
製造例１３で得られた、銅１２．１ ｗｔ％付着させた
硫酸バリウム微粒子１１４．０ ｇに製造例１と同様−
の方法で、銀めっき液の硝酸銀を１９ｇとして、銀めっ
き用還元液の酒石酸カリウムナトリウム（４水和物）を
１００ ｇとして操作した後に撹拌を中止し、Ｎ［Ｌ
５ Ｃ濾紙を用いて吸引濾過し、純水で充分に洗浄し、
さらに、この粉末を純水中に分散させ攪拌しながらＳＢ
Ｈを加えて液温を８０℃にして１０分間処理したところ
、銀灰色の微粒子を得た。114.0 g of barium sulfate fine particles to which 12.1 wt% copper was attached, obtained in Production Example 13, were treated in the same manner as in Production Example 1.
Using the method described above, the silver plating solution containing 19 g of silver nitrate and the reducing solution for silver plating containing potassium sodium tartrate (tetrahydrate) was used as 100 g, then stirring was stopped and N[L
5 Suction filter using C filter paper, wash thoroughly with pure water,
Furthermore, this powder was dispersed in pure water and SB was added while stirring.
When H was added to raise the liquid temperature to 80°C and the mixture was treated for 10 minutes, silver-gray fine particles were obtained.
この微粒子を化学分析により、銅および銀の含有率を分
析したところ、銅は１０．８ ｗｔ％、銀は９．６ｗｔ
％であった。Chemical analysis of these fine particles revealed that the content of copper and silver was 10.8 wt%, and 9.6 wt% silver.
%Met.
釈ｊ目１１ｊ−
製造例１７で得られた、銅１１．６ｗｔ％、銀５．１ｗ
ｔ％を付着させた酸化チタン微粒子１２０．０ ｇを純
水５００ ｄ中に分散させ、ついで、塩化金酸１６．３
ｇを純水１０００−に溶解しアンモニア水を加えてｐＨ
を１１に調整した溶液を加えて約６０℃に加温しながら
、攪拌下でヒドラジンヒトラード５％水溶液１５０ｍ１
を加えて反応させたところ、褐色の微粒子を得た。Copper 11.6wt%, silver 5.1w obtained in Production Example 17
120.0 g of titanium oxide fine particles to which t% was attached were dispersed in 500 d of pure water, and then 16.3 g of chloroauric acid was dispersed in 500 d of pure water.
Dissolve g in pure water 1000- and add ammonia water to adjust the pH.
Add a solution adjusted to 11 and add 150 ml of a 5% hydrazine hydrogen hydrazine aqueous solution under stirring while heating to about 60°C.
When the mixture was added and reacted, brown fine particles were obtained.
この微粒子を化学分析により、銅、銀および金の含有率
を分析したところ、銅１１．１ ｗｔ％、銀４．９ ｗ
ｔ％、金４．Ｏｗｔ％であった。Chemical analysis of these fine particles revealed that the content of copper, silver, and gold was 11.1 wt% copper and 4.9 wt% silver.
t%, gold4. It was Owt%.
製造例２０
酸化チタン微粒子（平均粒径１，５μｍ ＞ ２００
ｇを蒸着装置のチャンバー内にセットし、蒸着源（アル
ミニウム切片）をタングステン製バスケットに乗せて上
記のチャンバー内にセットし、該チャンバー内を減圧し
、（２Ｘ １０−’ Ｔｏｒｒ ）、次いで上記の酸化
チタン微粒子を振動させながら上記のタングステンバス
ケットを加熱して上記の蒸着源金属を２５ｇ分蒸発した
ところ灰白色の微粒子を得た。Production Example 20 Titanium oxide fine particles (average particle size 1.5 μm > 200
g is set in the chamber of the evaporation apparatus, the evaporation source (aluminum section) is placed on a tungsten basket and set in the above chamber, the pressure inside the chamber is reduced (2X 10-' Torr), and then the above The tungsten basket was heated while vibrating the titanium oxide fine particles to evaporate 25 g of the vapor deposition source metal, yielding gray-white fine particles.
この微粒子を化学分析により、アルミニウムの含有率を
分析したところ、アルミニウム１２ ｗｔ％であった。When the aluminum content of these fine particles was analyzed by chemical analysis, the aluminum content was 12 wt%.
上記で得たアルミニウムを付着した酸化チタン微粒子を
６５ｇずつ２個取り、それぞれ純水５００Δに分散させ
て、一方には実施例１７と同様に銀を付着させ、他方は
実施例１９と同様の方法で塩化金酸を２２．９ ｇとし
、ヒドラジンヒトラード５％水溶液を２１５−とじた以
外は同一として金を付着させた。Two pieces of 65 g each of the aluminum-attached titanium oxide fine particles obtained above were dispersed in 500 Δ of pure water, and one was coated with silver in the same manner as in Example 17, and the other was in the same manner as in Example 19. Gold was deposited using the same method except that 22.9 g of chloroauric acid and 215-g of a 5% aqueous solution of hydrazine hydrogen chloride were used.
上記で得た、銀を付着させた微粒子の銀とアルミニウム
の含有率は、銀８．６ｗｔ％、アルミニウム１１、Ｏｗ
ｔ％であった。The silver and aluminum content of the silver-attached fine particles obtained above was 8.6 wt% silver, 11 wt% aluminum, and Ow
It was t%.
また、金を付着させた微粒子の金とアルミニウムの含有
率は、金９．７ｗｔ％、アルミニウム１０．８ｗｔ％で
あった。Further, the content of gold and aluminum in the fine particles to which gold was attached was 9.7 wt% gold and 10.8 wt% aluminum.
そして製造例１〜２０で調整した微粒子の比抵抗は０．
８Ω口〜１．２Ω口に入るものであった。The specific resistance of the fine particles prepared in Production Examples 1 to 20 was 0.
The resistance was 8Ω to 1.2Ω.
使月１０−
製造例１〜２０にて調製した比抵抗０．８Ω口〜１．２
ΩΩの導電性組成物を５０％、７０％夫々分子量約１７
．０００、融点２１５℃のナイロン２６に混練したポリ
マーを芯に、同じナイロン６ポリマーを鞘に用い、複合
比１：１０で複合し、直径０．３龍のオリフィスから２
８０°Ｃで押し出し、１．０００ ｍ ／ ｗｉｎの速
度で巻き取った。Usage 10 - Specific resistance 0.8Ω~1.2 prepared in Production Examples 1 to 20
50% and 70% of the conductive composition of ΩΩ each have a molecular weight of about 17.
．． 000, a polymer kneaded with nylon 26 with a melting point of 215°C is used as the core, and the same nylon 6 polymer is used as the sheath, composited at a composite ratio of 1:10, and 2
It was extruded at 80 °C and wound up at a speed of 1.000 m/win.
このナイロン繊維をホットビンを用い３倍に延伸し、２
０デニールのナイロンフィラメントを得た。得られたフ
ィラメントの比抵抗は全て、１０２ΩＣ以下の優れた導
電性を示した。This nylon fiber was stretched 3 times using a hot bottle, and
A 0 denier nylon filament was obtained. All of the obtained filaments exhibited excellent electrical conductivity with a specific resistance of 102 ΩC or less.
１１鮭り
製造例１と同様の方法にて銀被膜８％を形成せしめた酸
化チタン微粒子（比抵抗５Ｘ１０’ΩＣ１１）を７０％
混練したナイロン２６を芯にしたフィラメントの比抵抗
は１０６ΩＣと好ましい導電性を示さなかった。11 70% titanium oxide fine particles (specific resistance 5 x 10'ΩC11) on which 8% silver coating was formed by the same method as in Salmon Production Example 1
The filament having a kneaded nylon 26 core had a specific resistance of 106 ΩC, which did not show desirable electrical conductivity.
（発明の効果）
上述のことから、本発明により次の効果がもたらされる
。(Effects of the Invention) From the above, the present invention provides the following effects.
（１）導電性が優れ且つ銀や銅の使用量が従来品に比較
して少なくてすむので相対的に廉価に供給することがで
きる。(1) It has excellent conductivity and requires less silver and copper than conventional products, so it can be supplied at a relatively low price.
（２）無機質微粒子に銅や銀の被膜を形成せしめるもの
であるから、従来品に比べて比重が小であるので混練時
の沈降性も軽減される。(2) Since a coating of copper or silver is formed on inorganic fine particles, the specific gravity is lower than that of conventional products, so sedimentation during kneading is also reduced.
（３）また混練成型品の着色が少なく、かつ製造が容易
である。さらに無機質微粒子の表面に銀や銅の被膜が形
成されているので、従来品の銀粉や銅粉のみの粒子に比
較して表面積が大である。(3) Furthermore, the kneaded and molded product has little coloring and is easy to manufacture. Furthermore, since a coating of silver or copper is formed on the surface of the inorganic fine particles, the surface area is larger than that of conventional particles made of only silver powder or copper powder.
Claims (5)
量％以上２５重量％未満均斉に形成せしめられているこ
とを特徴とする導電性組成物。(1) A conductive composition characterized in that a conductive metal coating is uniformly formed on the surface of inorganic fine particles in an amount of 10% by weight or more and less than 25% by weight.
ちの少なくとも一つよりなる請求項（１）記載の導電性
組成物。(2) The conductive composition according to claim (1), wherein the conductive metal film is made of at least one of gold, silver, copper, and aluminum.
は炭酸カルシウムのうち少なくとも一つよりなる請求項
（１）記載の導電性組成物。(3) The conductive composition according to claim (1), wherein the inorganic fine particles are made of at least one of metal oxide, barium sulfate, and calcium carbonate.
である請求項（１），（３）記載の導電性組成物。(4) The conductive composition according to claims (1) and (3), wherein the inorganic fine particles have an average particle size of 2 μm or less.
のうちの一つである請求項（１），（３）記載の導電性
組成物。(5) The conductive composition according to claims (1) and (3), wherein the metal oxide is one of titanium oxide and aluminum oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21028990A JPH0494009A (en) | 1990-08-10 | 1990-08-10 | Conductive compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21028990A JPH0494009A (en) | 1990-08-10 | 1990-08-10 | Conductive compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0494009A true JPH0494009A (en) | 1992-03-26 |
Family
ID=16586934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21028990A Pending JPH0494009A (en) | 1990-08-10 | 1990-08-10 | Conductive compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0494009A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003023787A1 (en) * | 2001-09-06 | 2003-03-20 | Fraunhofer Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrically conductive particles, especially for introducing in liquid media and method for the production thereof |
| WO2004073400A3 (en) * | 2003-02-19 | 2004-10-28 | Fraunhofer Ges Forschung | Material, in particular to be introduced into binder systems |
-
1990
- 1990-08-10 JP JP21028990A patent/JPH0494009A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003023787A1 (en) * | 2001-09-06 | 2003-03-20 | Fraunhofer Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrically conductive particles, especially for introducing in liquid media and method for the production thereof |
| WO2004073400A3 (en) * | 2003-02-19 | 2004-10-28 | Fraunhofer Ges Forschung | Material, in particular to be introduced into binder systems |
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