JPS6317012A - Manufacture of electrically-conductive polymer resin molded product - Google Patents
Manufacture of electrically-conductive polymer resin molded productInfo
- Publication number
- JPS6317012A JPS6317012A JP16258786A JP16258786A JPS6317012A JP S6317012 A JPS6317012 A JP S6317012A JP 16258786 A JP16258786 A JP 16258786A JP 16258786 A JP16258786 A JP 16258786A JP S6317012 A JPS6317012 A JP S6317012A
- Authority
- JP
- Japan
- Prior art keywords
- polymer resin
- copper
- molded product
- electrically
- polymer
- 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
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 26
- 229920001940 conductive polymer Polymers 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 14
- 239000010410 layer Substances 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000002344 surface layer Substances 0.000 abstract description 7
- 150000001879 copper Chemical class 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 abstract description 4
- 150000007524 organic acids Chemical class 0.000 abstract description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 abstract description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000001767 cationic compounds Chemical class 0.000 abstract description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 3
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 229920000178 Acrylic resin Polymers 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 abstract description 2
- 229910000365 copper sulfate Inorganic materials 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Moulding By Coating Moulds (AREA)
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野コ
本発明は導電性ｔ−有する高分子樹脂成型物の製法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a polymer resin molded product having electrical conductivity.
電気、電子機器分野においては、電磁波障害、静電気障
害が大きな問題となっており、かかる分野で使用さｎる
高分子成型物として低コストの導電性高分子成型物の開
発が強く要望さｎている。Electromagnetic interference and static electricity interference have become major problems in the electrical and electronic equipment fields, and there is a strong demand for the development of low-cost conductive polymer moldings for use in these fields. There is.
従来よ？）高分子成型物に導電性全付与する技術として
、カーボンフラッフや金属粉末等の導電性フィラーを高
分子に練り込む方法や銅塩と還元性硫黄化合物を用いニ
トリル基等の特定官能基を含有する高分子成型物、又は
表面を多孔化しｔ高分子成型物の表面に硫化鋼を生成さ
せて導電層を形成させる方法が矧らｎている。Conventional? ) Techniques for fully imparting electrical conductivity to polymer molded products include methods of kneading conductive fillers such as carbon fluff and metal powder into polymers, and methods of incorporating specific functional groups such as nitrile groups using copper salts and reducing sulfur compounds. There are several methods of forming a conductive layer by forming a polymer molded product, or by making the surface porous and producing sulfide steel on the surface of the polymer molded product.
しかるに、導電性フィラーを練り込む方法拡成型物の物
性が低下する欠点を有し、又成型物表面に硫化鋼を生成
させる方法は、成型物の状態で処理されるため、成型物
の形状によっては処理不可能であったり、不十分な導電
性しか得らｎないという欠点を有している。However, the method of kneading a conductive filler has the disadvantage of degrading the physical properties of the expanded molded product, and the method of generating sulfide steel on the surface of the molded product is processed in the molded state, so it may vary depending on the shape of the molded product. They have the disadvantage that they cannot be processed or provide insufficient conductivity.
本発明はかかる従来技術による導電性高分子成型物の製
造における問題点を解決し、安価にして容易に導電性に
優ｆ′した高分子成型物を得る方法を提供することにあ
る。The object of the present invention is to solve the problems in the production of conductive polymer molded articles according to the prior art and to provide a method for easily obtaining a polymer molded article with excellent conductivity f' at low cost.
本発明は１表層に硫化銅からなる導電層が形成された高
分子樹脂粉宋と該高分子樹脂の溶剤上混合し溶液とし、
流延成型、脱溶剤処理全おこなうことを特徴とする導電
性高分子樹脂成型物の製法にある。The present invention involves mixing a polymer resin powder with a conductive layer made of copper sulfide on the surface layer and a solution of the polymer resin in a solvent;
A method for producing a conductive polymer resin molded product characterized by performing casting and solvent removal treatment.
本発明で用いる高分子樹脂としては、例えばアクリル樹
脂、ポリ塩化ビニル樹脂、ポリエステル樹脂、ポリ−ス
チレン樹脂、ポリカーボネート樹脂、ＡＢ８樹脂等が挙
げらｎ、公知の技術により粉末化されたものが用いらｎ
る。Examples of the polymer resin used in the present invention include acrylic resin, polyvinyl chloride resin, polyester resin, polystyrene resin, polycarbonate resin, AB8 resin, and the like. n
Ru.
本発明で高分子樹脂粉末の表層に硫化鋼からなる導電層
を形成させる方法は、高分子樹脂粉末を無機酸又は有機
酸の銅塩と還元性硫黄化合物、好ましくは更に水溶性の
カチオン性化合物を含有する水溶液中に浸漬し、こ：ｒ
ｔｔ−加熱処理することにより得らｎる。In the present invention, the method for forming a conductive layer made of sulfurized steel on the surface layer of polymer resin powder is to combine polymer resin powder with a copper salt of an inorganic or organic acid and a reducing sulfur compound, preferably further with a water-soluble cationic compound. immersed in an aqueous solution containing
tt-obtained by heat treatment.
硫化鋼の生成に用いる無機酸又は有機酸の銅塩としては
１例えば硫酸第２鋼、塩化第２銅、硝駿第２銅、酢酸第
２銅等が挙げらｎる。Examples of copper salts of inorganic or organic acids used to produce sulfurized steel include sulfuric acid (II), cupric chloride, cupric nitrate, cupric acetate, and the like.
又、還元性化合物としては１例えばチオ硫酸ナトリウム
、酸性亜硫酸ナトリウム、ピロ亜硫酸ナトリウム、硫化
ナトリウム、硫化水素ナトリウム等が挙げらｎる。Examples of reducing compounds include sodium thiosulfate, acidic sodium sulfite, sodium pyrosulfite, sodium sulfide, and sodium hydrogen sulfide.
又、好ましく用いらｎる水溶性のカチオン性化合物とし
ては、例えばオクタデシルトリメチルアンモニウムクロ
ライド、ヘキサデシルトリメチルアンモニウムクロライ
ド等のカチオン界面活性剤、 Ｏ，工、ベーシックブル
ー５、Ｃ０工、ベーシックバイオレット１．Ｃ０工、ベ
ーシックグリーン４等のカチオン染料等が挙げらｎる。Preferably used water-soluble cationic compounds include cationic surfactants such as octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride; Examples include cationic dyes such as C0 dye and Basic Green 4.
高分子樹脂粉末の表層に生成させる硫化鋼の量は成型物
に導電性を付与する丸めには、５×１０−’ ９７ｃｍ
”以上であることが必要であり、こｎ未満でに導電性が
付与さｎず好１しくない。The amount of sulfurized steel produced on the surface layer of the polymer resin powder is 5 x 10-'97cm for rounding to impart conductivity to the molded product.
If it is less than this, conductivity will not be imparted, which is not preferable.
本発明においては、硫化鋼の生成により導電化さｎ友高
分子樹脂粉末を高分子樹脂の溶剤にてその高分子樹脂分
を溶解させて溶液とし、こ２′Ｌｔ−流延法により成型
し几のち脱溶剤処理することにより優ｎ窺導電性高分子
樹脂成型物が得らｎる。In the present invention, a polymer resin powder made conductive by the formation of sulfurized steel is dissolved in a polymer resin solvent to form a solution, and then molded by the 2'Lt-casting method. Afterwards, a highly conductive polymer resin molded product is obtained by removing the solvent.
本発明では導電化さｎ７’ｃ高分子樹脂粉末を単独で使
用してもよいし、又未処理の高分子樹脂粉末を適量混合
して使用してもよい。In the present invention, the conductive N7'C polymer resin powder may be used alone, or an appropriate amount of untreated polymer resin powder may be mixed therewith.
又、流延成型の方式は、特に限定さｎず１通常の公知の
方式がそのまま用いらｎる。成型機の脱溶剤処理は湿式
又は乾式の公知の方式が用いらｎる。Further, the casting method is not particularly limited, and any conventional known method may be used as is. For the solvent removal treatment in the molding machine, a known wet or dry method may be used.
本発明に２いてな、硫化鋼の生成により導電化さｎｔ高
高分子樹脂粉圧溶剤を添加し溶液とし１ζ場合、高分子
樹脂分ｅ工溶剤に溶解するが粉末の表層に形成された硫
化銅からなる導電層は溶解せず、この導電層が流延成型
後の成型物中で互に接触し合い、連続した導電層が形成
し、優れ良導電性が付与さｎる。2. In the present invention, when a polymer resin powder is made conductive by the formation of sulfurized steel and made into a solution, the polymer resin dissolves in the processing solvent, but the sulfurization formed on the surface layer of the powder does not occur. The conductive layer made of copper does not melt, and the conductive layers come into contact with each other in the molded product after casting, forming a continuous conductive layer and providing excellent conductivity.
以下、実施例により本発明を更に詳しく説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
ポリカーボネイト樹脂粉末（三菱ガス化学社製）１に９
を硫酸第２銅（５Ｔ１２０ ） ４重量係、チオ硫酸ナ
トリウム（５Ｈ，Ｏ）４重量％及びオクタデシルトリメ
チルアンモニウムクロライド（１０４重量ｌ１ｊｔ−含
有する３０ｔの温度２５℃の水溶液に浸漬し、攪拌しな
がら１℃／分の速度で９０℃まで昇温し、引続き３０分
間加熱しに後、水洗、脱水、乾燥し、ポリカーボネート
樹脂粉末の表層に硫化鋼からなる導電層が形成された黒
色の粉末１得た。Example 1 Polycarbonate resin powder (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1 to 9
was immersed in an aqueous solution containing 4 parts by weight of cupric sulfate (5T120), 4 parts by weight of sodium thiosulfate (5H,O) and 104 parts by weight of octadecyltrimethylammonium chloride (104 parts by weight) at a temperature of 25°C, and 1 part with stirring. The temperature was raised to 90 °C at a rate of °C/min, and then heated for 30 minutes, washed with water, dehydrated, and dried to obtain black powder 1 in which a conductive layer made of sulfurized steel was formed on the surface layer of polycarbonate resin powder. .
この粉末２０重量部に塩化メチレン８０重量部を添加し
て攪拌し、粘稠溶液とし、流延フィルム成型機を用い、
厚さ４０μ−のフィルムを得た＠
このフィルムの電気抵抗は５ｘ１ｏｚΩ／口（２０℃、
４０９６ＲＨ）であり、優ｎた導電性含有してい次。80 parts by weight of methylene chloride was added to 20 parts by weight of this powder, stirred to form a viscous solution, and using a casting film forming machine,
A film with a thickness of 40 μ- was obtained @ The electrical resistance of this film was 5 x 1 ozΩ/mouth (at 20°C,
4096RH) and contains excellent conductivity.
実施例２
塩化ビニル樹脂粉末（東洋ソーダ社製、ニーロンペース
ト７２０）ＩＫｇを硫酸第２銅（５Ｈ，Ｏ）４重量％、
チオ硫酸ナトリウム（５Ｈ７Ｏ） ４重量％及びヘキサ
デシルトリメチルアンモニウムクロライド（ＬＯ４重量
％’ｔ−含有する３０ｔの温度２５℃の水溶液に浸漬し
、攪拌しながら１℃／分の速度で９０℃まで昇温し、引
続３！３０分間加熱処理した後、水洗、脱水、乾燥し、
塩化ビニル樹脂粉末の表層に硫化鋼からなる導電層が形
成された黒色の粉末を得た。Example 2 I kg of vinyl chloride resin powder (manufactured by Toyo Soda Co., Ltd., Neelon Paste 720) was mixed with 4% by weight of cupric sulfate (5H, O),
Immerse 30 tons in an aqueous solution containing 4% by weight of sodium thiosulfate (5H7O) and 4% by weight of hexadecyltrimethylammonium chloride (LO) at a temperature of 25°C, and raise the temperature to 90°C at a rate of 1°C/min while stirring. Then, after heat treatment for 3!30 minutes, washing with water, dehydration, drying,
A black powder was obtained in which a conductive layer made of sulfurized steel was formed on the surface layer of vinyl chloride resin powder.
この粉末１０！を部にジメチルホルムアミド９０ｇ量部
を添加して攪拌し、粘稠溶液とじ几後、流延フィルム取
型機を用いフィルム化し、水洗、乾燥して厚さ５０μｍ
のフィルムを得友。This powder is 10! 90 g of dimethylformamide was added to the mixture, stirred, and the viscous solution was made into a film using a cast film molding machine, washed with water, and dried to a thickness of 50 μm.
I got a film from a friend.
このフィルムの電気抵抗は２Ｘ１０”Ω／口（２０℃、
４０１ＲＨ）であり、優ｎた導電性を有してい友。The electrical resistance of this film is 2X10”Ω/mouth (20℃,
401RH) and has excellent conductivity.
本発明の方法は導電性に優′ｎ尺谷棟の高分子底型換金
安価に提供することｔ可能にするものであり、特に電子
関連機器分野での使用にきわめて有用なるものである。The method of the present invention makes it possible to provide a high-conductivity polymer base type at low cost, and is particularly useful in the field of electronic equipment.
Claims (1)
粉末と該高分子樹脂の溶剤を混合して溶液とし、流延成
型、脱溶剤処理をおこなうことを特徴とする導電性高分
子樹脂成型物の製法。Conductive polymer resin molding characterized by mixing a polymer resin powder with a conductive layer made of copper sulfide on its surface and a solvent for the polymer resin to form a solution, followed by casting and solvent removal treatment. How to make things.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16258786A JPS6317012A (en) | 1986-07-10 | 1986-07-10 | Manufacture of electrically-conductive polymer resin molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16258786A JPS6317012A (en) | 1986-07-10 | 1986-07-10 | Manufacture of electrically-conductive polymer resin molded product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6317012A true JPS6317012A (en) | 1988-01-25 |
Family
ID=15757425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16258786A Pending JPS6317012A (en) | 1986-07-10 | 1986-07-10 | Manufacture of electrically-conductive polymer resin molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6317012A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005008889A (en) * | 2003-06-20 | 2005-01-13 | Crf Soc Consortile Per Azioni | Method for manufacturing polymeric composite of metal or semiconductor |
-
1986
- 1986-07-10 JP JP16258786A patent/JPS6317012A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005008889A (en) * | 2003-06-20 | 2005-01-13 | Crf Soc Consortile Per Azioni | Method for manufacturing polymeric composite of metal or semiconductor |
| JP4663260B2 (en) * | 2003-06-20 | 2011-04-06 | チ・エレ・エッフェ・ソシエタ・コンソルティーレ・ペル・アチオニ | Method for producing polymer composite of metal or metal sulfide |
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