JPH03167714A - Conductive compound material - Google Patents
Conductive compound materialInfo
- Publication number
- JPH03167714A JPH03167714A JP30730189A JP30730189A JPH03167714A JP H03167714 A JPH03167714 A JP H03167714A JP 30730189 A JP30730189 A JP 30730189A JP 30730189 A JP30730189 A JP 30730189A JP H03167714 A JPH03167714 A JP H03167714A
- Authority
- JP
- Japan
- Prior art keywords
- conductive
- carbon black
- compound material
- filling agent
- resistance
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 title abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002923 metal particle Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000011231 conductive filler Substances 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 9
- 229920000728 polyester Polymers 0.000 abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 3
- -1 acrylic ester Chemical class 0.000 abstract description 3
- 229920002678 cellulose Polymers 0.000 abstract description 3
- 239000001913 cellulose Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract 4
- 239000002657 fibrous material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
こ産業上の利用分野〕
本発明はポリドデノルアクリレートを基本成分とする高
分子化合物と、カーボンプラック、金属粒子などの導電
性充填剤からなる導電性複合体に関する。[Detailed Description of the Invention] This Industrial Application Field] The present invention relates to a conductive composite consisting of a polymer compound having polydodenol acrylate as a basic component and a conductive filler such as carbon plaque or metal particles. .
Ｅ従来の技術〕
従来、高分子化合物と導電性充填剤とからなる導電性複
合体において、特にポリエチレンやボリブロピレンなど
の結晶性高分子を用いた場合には、含まれる戊分の鴇膨
張差により、転移点厘度で複合体の抵抗が急激に大きく
なる現象がみられる。E. Prior Art] Conventionally, in conductive composites made of a polymer compound and a conductive filler, especially when crystalline polymers such as polyethylene and polypropylene are used, due to the difference in expansion of the contained components, , a phenomenon is observed in which the resistance of the composite increases rapidly at the transition point.
この財料を発も体として利用する場合には、その抵抗変
化によって電力制御か可能辷なり、従って、自己温度制
御型発無体の製作か可能となる。またヒューズとして利
用すれば、自己復帰型ヒューズが可能となる。When this material is used as a generator, it becomes possible to control the power by changing its resistance, and therefore it becomes possible to produce a self-temperature-controlling generator. Furthermore, if used as a fuse, a self-resetting type fuse becomes possible.
本発明は、ポリドデシルアクリレートが、０℃でその結
晶が融解する特異な高分子であることに着目し、これを
各種導電性充填剤と適当ぢ方法で混合成形することによ
り目的に合致する機能性材料を提供することを技術的課
題とする。The present invention focuses on the fact that polydodecyl acrylate is a unique polymer whose crystals melt at 0°C, and by mixing and molding it with various conductive fillers in an appropriate manner, a function that meets the purpose is obtained. The technical challenge is to provide a material with a high degree of elasticity.
本発明の要旨は、共重合成分又はブレンド成分としてポ
リドデシルアクリレートを用いた高分子化合物と、カー
ボンブラック、金属粒子などの導電性充填剤とから成る
導電性複合体に係るものである。The gist of the present invention relates to a conductive composite comprising a polymer compound using polydodecyl acrylate as a copolymerization component or a blend component, and a conductive filler such as carbon black or metal particles.
〔作 用］
ポリドデシルアクリレートのＯ′Ｃにおける融解により
導電性複合体の抵抗か急激に変化する。[Function] Melting of polydodecyl acrylate in O'C causes a sudden change in the resistance of the conductive composite.
本発明において言うポリドデシルアクリレートは分子ｊ
３１１０００〜２０００００程度の広い範囲全さすが、
その一方、各種アクリル酸エステルやスチレン、酢酸ビ
ニル、またポリエステル、ボリアミド、セルロースなど
とのランダム、ブロックグラフトいず礼の共重合体の状
態でし利用できる。In the present invention, polydodecyl acrylate has a molecule j
As expected, the wide range is from 311,000 to 200,000.
On the other hand, it can be used in the form of random or block graft copolymers with various acrylic esters, styrene, vinyl acetate, polyester, polyamide, cellulose, etc.
この場合ポリドデシルアクリレートは高分子重量当たり
、少なくとも３０重量％以上含むことが必要で、またそ
の高分子が全体の中で占める量が多い程目的の性質が強
く得られる。また、ポリアクリルアミド酸エステル誘導
体、ボリスチレン誘導体、ボリアミド誘導体、ポリエス
テル誘導体、セルロース誘導体、フッソ樹指、シリコン
樹脂等を直接ブレンドして使用することができる。この
場合も共重合体と同様に少なくとも３０重量％以上含む
ことが必要である。In this case, it is necessary to contain polydodecyl acrylate in an amount of at least 30% by weight based on the weight of the polymer, and the higher the amount of the polymer in the whole, the stronger the desired properties can be obtained. Further, polyacrylamic acid ester derivatives, polystyrene derivatives, polyamide derivatives, polyester derivatives, cellulose derivatives, fluorine resins, silicone resins, etc. can be directly blended and used. In this case as well, it is necessary to contain at least 30% by weight as in the case of the copolymer.
導電性充填剤としては、カーボンブラック、各種金属粉
、金属酸化物粉、およびそれらのフレーク状物、短繊維
物、異形導電性充填剤などである。Examples of the conductive filler include carbon black, various metal powders, metal oxide powders, flakes thereof, short fibers, irregularly shaped conductive fillers, and the like.
これらの導電率は、大きければ問題ないか、１０４ΩＧ
究以上あれば良い。If the conductivity of these is large, there is no problem, or 104ΩG
It is good to have at least 100 degrees.
カーボンブラックとしては、アセチレンブランク、ケチ
ェンブラック等の導電性カーホンブラノクの他にファー
ネスブラック、サーマルブラックむどのカーボンも使用
できる。カーボンブラ・ソクと混合する場合には、上記
の高分子を溶剤を用いて混合するか、ドライの状態で混
合して熔融してから利用する方法がある。また、カーボ
ンブラ・ノク存在下てドデシルアクリレートを主成分と
するモノマーをラジカル触媒（Ｎ，Ｎ′アゾイソブチロ
ニトリル）を用いて、重合させ、高分子の一部をカーボ
ンブラックの表面に化学的に結びつけることが可能であ
る。As the carbon black, in addition to conductive carbon black such as acetylene blank and Kechen black, carbon such as furnace black and thermal black can also be used. In the case of mixing with Carbon Bra Soc, there is a method of mixing the above-mentioned polymers using a solvent, or mixing them in a dry state and melting them before use. In addition, in the presence of carbon black, a monomer mainly composed of dodecyl acrylate is polymerized using a radical catalyst (N, N' azoisobutyronitrile), and a part of the polymer is chemically attached to the surface of carbon black. It is possible to connect the
導電性充填剤としては、金属粒子や金属酸化物粒子粉も
カーボンブラック同様の手法で用いる事ができる。粒子
粉の直径は１−５μ次位が適当であるが、ｌμｌ以下の
ものや５μス以上のものも高分子の種類によって適宜利
用できる。As the conductive filler, metal particles and metal oxide particles can also be used in the same manner as carbon black. The diameter of the particles is suitably on the order of 1 to 5 μl, but diameters of less than 1 μl and diameters of 5 μl or more can also be used depending on the type of polymer.
このようにして作製した複合物は円盤型、棒状、シート
状など色々の形で直接ＩＩ＋田できるが、アルミナ基板
等の絶縁性セラミノク基板、ガラス布、ポリエステル布
、綿布等の各種織物状のものに塗布して利用できる。ま
た、糸状のもの棒状のものにも塗布して利用できる。Composites produced in this way can be directly processed into various shapes such as discs, rods, and sheets, but they can also be made into insulating ceramic substrates such as alumina substrates, and various fabrics such as glass cloth, polyester cloth, and cotton cloth. It can be used by applying it. It can also be applied to thread-like and rod-like objects.
以下に具体的実施例を示す。Specific examples are shown below.
実施例ｌ グラフト法による場合
ドデシルアクリレートモノマーを出発原料として複合体
を作製する。Example 1 In the case of grafting method, a composite is prepared using dodecyl acrylate monomer as a starting material.
２００ｉｆｆのナス型フラスコに第１図の組成に従って
、（グラフト法１〜５）トデノルアクリレートモノマー
共重合成分のグリンジルメタクリレートモノマーまた
はアクリル酸モノマー カーポンプラックを入れ、これ
に溶媒としてシクロへキサノン＋５３１１２を加え、モ
ノマー及びカーボンブラックを溶解分散させる。その後
、Ｎ，＼゜アゾヒスイソブチロニトリル（ ＡＩＢＮ）
をモノマー量の２ｗｔ％量加え、９０゜Ｃまで昇温し、
撹拌しながら重合反応を行った。According to the composition shown in Figure 1, (grafting methods 1 to 5) todenol acrylate monomer, copolymerization component grindyl methacrylate monomer or acrylic acid monomer, and carpon rack were placed in a 200iff eggplant-shaped flask, and cyclohexanone + 53112 was added as a solvent. is added to dissolve and disperse the monomer and carbon black. Then, N, ＼゜Azohisisobutyronitrile (AIBN)
was added in an amount of 2 wt% of the monomer amount, and the temperature was raised to 90°C.
The polymerization reaction was carried out while stirring.
反応後、溶液を冷却し、″：ｆ！化剤（エチレノジアミ
ンまたはエボキノ樹脂）を加え、１時間撹拌して、抵抗
塗料原液を作った。After the reaction, the solution was cooled, a ``:f!'' converting agent (ethylenediamine or evoquino resin) was added, and stirred for 1 hour to prepare a resistance paint stock solution.
この塗料をセラミックス基板、ガラス基板、ガラス布、
ポリエステル布、ガラス糸、各種の糸に含浸または塗布
して、予備乾燥（８０゜Ｃ．１時間）硬化後に本発明品
が出来上がった。This paint can be applied to ceramic substrates, glass substrates, glass cloth,
The product of the present invention was completed by impregnating or coating polyester cloth, glass thread, or various threads, and after pre-drying (80°C, 1 hour) and curing.
抵抗体の抵抗値は用いられるカーボノブラノク含有量に
よって異なるが、本実施例では１８ｋΩ〜４６０ｋΩの
範囲のものが得られた。The resistance value of the resistor varies depending on the carbon content used, but in this example, a resistance value in the range of 18 kΩ to 460 kΩ was obtained.
また、抵抗値はＯ′Ｃ付近で急激に上力くり出し、ｌ５
゜Ｃでは−１５°Ｃの４．７〜３７倍の変化に達した。In addition, the resistance value suddenly increases upward near O'C, and l5
At °C, the change reached 4.7 to 37 times that of -15 °C.
尚、グラフト法は実施例２のブレント沃より抵抗値変化
か若干少なくなるが、均一性ではブレンド法より優れて
いる。It should be noted that although the graft method results in a slightly smaller change in resistance value than the blended method of Example 2, it is superior to the blend method in terms of uniformity.
実施例１の試料ＮＯＩの抵抗温度特性を第２艷に示した
。この図からからわかるように抵抗値｝ヨｌ５゜Ｃか与
昇温すると０゜Ｃ付近から急上昇しｆ二。The resistance temperature characteristics of sample NOI of Example 1 are shown in the second column. As can be seen from this figure, when the temperature is increased by 5°C, the resistance value rises rapidly from around 0°C to f2.
これはポリデノルアクリレート成分の部分的触解に壊づ
く
これを再び冷却するとヒステリシスを持ちながら抵抗は
０゜Ｃ付近から急激に小さくなる。This breaks down due to partial catalysis of the polydenol acrylate component, and when it is cooled again, the resistance decreases rapidly from around 0°C, with hysteresis.
実施例２ ブレンド法による場合
ポリドデンルアクリレートポリマーま几はその共重合体
を出発原料として複合体を作製する。Example 2 In the case of a blending method, a polydodenyl acrylate polymer or copolymer is used as a starting material to prepare a composite.
第１図の配合比（ブレンド法６〜８）に従ってポリドデ
シルアクリレートまたはその共重合体とカーボンブラン
クとを．溶媒として用いたシクロヘキサノンによって，
ボールミルを使って湿式混合した。Polydodecyl acrylate or its copolymer and carbon blank were mixed according to the blending ratios shown in FIG. 1 (blending methods 6 to 8). With cyclohexanone used as a solvent,
Wet mixing was performed using a ball mill.
この混合溶液に硬化剤のエチレンジアミン（第１図参照
）を加え、実施例ｌと同様な過程を経て抵抗塗料を作製
した。A hardening agent, ethylenediamine (see FIG. 1), was added to this mixed solution, and a resistance paint was produced through the same process as in Example 1.
抵抗値はグラフト法と大差ないが、０℃〜１５℃にかけ
ての抵抗値変化はグラフト法より、相対的に大きかった
。Although the resistance value was not much different from that of the graft method, the change in resistance value from 0°C to 15°C was relatively larger than that of the graft method.
本発明は上述のように構成したから０℃における抵抗の
急激な変化を生じさせることが可能な導電性複合体を提
供し得ることになり、従って、寒冷地で本発明を例えば
ヒーター、センサー等に利用する等機能的な商品開発が
可能となる。Since the present invention is configured as described above, it is possible to provide a conductive composite that can cause a rapid change in resistance at 0°C. Therefore, the present invention can be used in cold regions, such as heaters, sensors, etc. It becomes possible to develop functional products that can be used for
図面は本発明の一実施例を示すもので、第１図はポリド
デシルアクリレートを成分とする導電性複合体の作製条
件とその電気的特性を示した表、第２図は実施例ｌのＮ
ｏｔ試料の抵抗温度特性を示したグラフである。
平Ｔｆｔ．１年１１月２７日The drawings show an example of the present invention, and FIG. 1 is a table showing the preparation conditions and electrical properties of a conductive composite containing polydodecyl acrylate as a component, and FIG.
It is a graph showing resistance temperature characteristics of an ot sample. Flat Tft. November 27, 1 year
Claims (1)
リレートを用いた高分子化合物と、カーボンブラック、
金属粒子などの導電性充填剤とから成る導電性複合体。A polymer compound using polydodecyl acrylate as a copolymerization component or blend component, carbon black,
A conductive composite consisting of a conductive filler such as metal particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30730189A JPH03167714A (en) | 1989-11-27 | 1989-11-27 | Conductive compound material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30730189A JPH03167714A (en) | 1989-11-27 | 1989-11-27 | Conductive compound material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03167714A true JPH03167714A (en) | 1991-07-19 |
| JPH0557682B2 JPH0557682B2 (en) | 1993-08-24 |
Family
ID=17967499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30730189A Granted JPH03167714A (en) | 1989-11-27 | 1989-11-27 | Conductive compound material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03167714A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004046257A3 (en) * | 2002-11-15 | 2004-07-29 | Timcal Sa | Metal coated carbon black, carbon black compositions and their applications |
| JP2006321833A (en) * | 2005-05-17 | 2006-11-30 | Kaneka Corp | Thermoplastic elastomer composition |
-
1989
- 1989-11-27 JP JP30730189A patent/JPH03167714A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004046257A3 (en) * | 2002-11-15 | 2004-07-29 | Timcal Sa | Metal coated carbon black, carbon black compositions and their applications |
| JP2006513120A (en) * | 2002-11-15 | 2006-04-20 | ティムカル・ソシエテ・アノニム | Carbon black composition and application examples thereof |
| JP2006321833A (en) * | 2005-05-17 | 2006-11-30 | Kaneka Corp | Thermoplastic elastomer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0557682B2 (en) | 1993-08-24 |
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