JPH0453904B2 - - Google Patents
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- Publication number
- JPH0453904B2 JPH0453904B2 JP59201452A JP20145284A JPH0453904B2 JP H0453904 B2 JPH0453904 B2 JP H0453904B2 JP 59201452 A JP59201452 A JP 59201452A JP 20145284 A JP20145284 A JP 20145284A JP H0453904 B2 JPH0453904 B2 JP H0453904B2
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- metal
- carbonaceous particles
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Description
【発明の詳細な説明】
本発明は、電気抵抗の正温度係数特性（PTC）
の顕著な感熱抵抗性導電性組成物に関する。[Detailed Description of the Invention] The present invention is characterized by positive temperature coefficient characteristic (PTC) of electrical resistance.
The present invention relates to a remarkable heat-sensitive resistive conductive composition.
従来から正温度係数特性を有する材料、特に一
定の温度領域に達すると急激に電気抵抗値が増大
する特性を有する材料は、様々なものが知られて
いる（特公昭36−16338号公報，50−33707号公
報，同56−10352号公報など）。 A variety of materials have been known that have positive temperature coefficient characteristics, particularly materials that have the characteristic of rapidly increasing electrical resistance when reaching a certain temperature range (Japanese Patent Publication No. 16338/1983, 50 -33707 Publication, Publication No. 56-10352, etc.).
しかしながら、これら従来の材料では、一定の
温度領域に達した際の抵抗増大倍率を大きくする
と、室温での電気抵抗も大きくなり実用上問題が
あつた。 However, with these conventional materials, when the resistance increase factor is increased when a certain temperature range is reached, the electrical resistance at room temperature also increases, which poses a practical problem.
そこで本発明者は、上記従来の材料の問題点を
解消し、常温での電気抵抗が小さく、しかも一定
温度領域に達した際の電気抵抗値の増大倍率が著
しく大きい材料を開発すべく鋭意研究を重ねた。
その結果、結晶性樹脂をベースとし、これに導電
性充填材として金属を付着した炭素質粒子を配合
するとともに、結晶性樹脂の架橋化を行なうこと
によつて、目的とする物性を有する組成物が得ら
れることを見出した。本発明はかかる知見に基い
て完成したものである。すなわち本発明は、結晶
性樹脂と、粒径が10mμ〜1μmのカーボンブラツ
ク粒子に化学メツキにより金属を付着した炭素質
粒子よりなる架橋化組成物であつて、前記結晶性
樹脂100容量部に、前記金属を付着した炭素質粒
子を20〜70容量部配合してなる感熱抵抗性導電性
組成物を提供するものである。 Therefore, the inventor of the present invention has conducted extensive research in order to solve the above-mentioned problems with conventional materials and to develop a material that has low electrical resistance at room temperature and has a significantly large increase in electrical resistance when a certain temperature range is reached. layered.
As a result, by blending carbonaceous particles with metal attached as a conductive filler to a crystalline resin base and crosslinking the crystalline resin, a composition having the desired physical properties was created. was found to be obtained. The present invention was completed based on this knowledge. That is, the present invention provides a crosslinked composition comprising a crystalline resin and carbonaceous particles having a metal attached to carbon black particles having a particle size of 10 mμ to 1 μm by chemical plating, in which 100 parts by volume of the crystalline resin: The present invention provides a heat-sensitive resistive conductive composition containing 20 to 70 parts by volume of carbonaceous particles to which the metal is attached.
本発明に用いる結晶性樹脂は様々なものを挙げ
ることができるが、通常は高密度ポリエチレン，
低密度ポリエチレン，ポリプロピレン，エチレン
−プロピレンコポリマーなどのポリオレフイン、
オレフイン系共重合体、各種のポリアミド、ポリ
エステルあるいはフツ素系重合体さらにはこれら
の変性物などである。 Various crystalline resins can be used in the present invention, but usually high-density polyethylene,
polyolefins such as low-density polyethylene, polypropylene, and ethylene-propylene copolymers;
These include olefin copolymers, various polyamides, polyesters, fluorine-based polymers, and modified products thereof.
次に、本発明では導電性の充填材として金属を
付着した炭素質粒子を用いるが、ここで付着すべ
き金属としては銅，ニツケル，スズ，金，銀，白
金などの導電性の良好な金属が好ましく、一方、
炭素質粒子としては粒径10mμ〜1μ程度、特に
15mμ〜100mμのオイルフアーネスブラツク，サ
ーマルブラツク，アセチレンブラツク等のカーボ
ンブラツクを用いる。 Next, in the present invention, carbonaceous particles to which a metal is attached are used as a conductive filler, and the metal to be attached here is a metal with good conductivity such as copper, nickel, tin, gold, silver, or platinum. is preferred, while
The carbonaceous particles have a particle size of about 10mμ to 1μ, especially
Use carbon black such as oil furnace black, thermal black, acetylene black, etc. of 15 mμ to 100 mμ.
また、この金属を付着した炭素質粒子における
金属付着量は、特に制限はなく各種の条件に応じ
て適宜選定すればよいが、通常は炭素質粒子に対
して５〜30重量％が好ましい。 Further, the amount of metal attached to the carbonaceous particles to which the metal is attached is not particularly limited and may be appropriately selected depending on various conditions, but it is usually preferably 5 to 30% by weight based on the carbonaceous particles.
なお、この金属を付着した炭素質粒子を製造す
るには、化学メツキにより炭素質粒子表面に所定
の金属を付着せしめればよい。ここで、化学メツ
キは通常は炭素質粒子にスズやパラジウムのイオ
ンを吸着させて活性化した後、これを付着させる
べき所定の金属のイオンを含むヘツキ液に浸漬し
て、金属を析出させることにより行なう。 In addition, in order to manufacture carbonaceous particles to which this metal is attached, a predetermined metal may be attached to the surface of the carbonaceous particles by chemical plating. Here, chemical plating usually involves adsorbing and activating tin or palladium ions onto carbonaceous particles, and then immersing them in a plating solution containing ions of the specified metal to be deposited to deposit the metal. This is done by
本発明の組成物は、前述の結晶性樹脂と金属を
付着した炭素質粒子よりなるものであるが、その
配合割合は、結晶性樹脂100容量部に対して、金
属を付着した炭素質粒子20〜70容量部、好ましく
は30〜65容量部の範囲とすべきである。この金属
を付着した炭素質粒子の配合割合が20容量部未満
では、室温での電気抵抗が大きくなり、また、70
容量部を超えると、一定温度に達した際の電気抵
抗の増大倍率が小さくなり、実用上問題がある。 The composition of the present invention is composed of the above-mentioned crystalline resin and carbonaceous particles to which metal is attached, and the blending ratio is 20 parts by volume of carbonaceous particles to which metal is attached to 100 parts by volume of crystalline resin. It should range from ~70 parts by volume, preferably from 30 to 65 parts by volume. If the blending ratio of carbonaceous particles to which this metal is attached is less than 20 parts by volume, the electrical resistance at room temperature will increase;
If the capacitance is exceeded, the increase factor of the electrical resistance becomes small when a certain temperature is reached, which poses a practical problem.
本発明の組成物は、結晶性樹脂と金属を付着し
た炭素質粒子を一定割合で配合すると同時に、こ
れを混練し、さらに架橋化させることによつて製
造される。この際の混練は、種々の条件にて行な
うことができるが、通常は130〜250℃の温度にて
５分間以上行なえばよく、また用いる混練機とし
ては、バンバリーミキサー，ミキシングロールな
どがあげられる。 The composition of the present invention is produced by blending a crystalline resin and metal-attached carbonaceous particles in a fixed ratio, kneading the same, and further crosslinking the mixture. Kneading at this time can be carried out under various conditions, but it is usually sufficient to carry out the kneading at a temperature of 130 to 250°C for 5 minutes or more, and examples of the kneading machine used include a Banbury mixer, a mixing roll, etc. .
混練後に行なう架橋化処理にあたつては、様々
な手段により行なうことができ、例えば有機パー
オキサイドなどの架橋剤を加えて行なう方法，オ
ゾンを用いる方法，電子線等の活性エネルギー線
を照射する方法などを挙げることができる。ここ
で有機パーオキサイドとしては、ベンゾイルパー
オキサイド，ｔ−ブチルパーオキシベンゾエー
ト，ジクミルパーオキサイド，ｔ−ブチルクミル
パーオキサイド，ｔ−ブチルパーオキサイド，
２，５−ジメチル−２，５−ジ（ｔ−ブチルパー
オキシ）ヘキシン−３などを例示することができ
る。 The crosslinking treatment carried out after kneading can be carried out by various means, such as adding a crosslinking agent such as an organic peroxide, using ozone, or irradiating active energy rays such as electron beams. Examples include methods. Examples of the organic peroxide include benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, t-butyl peroxide,
Examples include 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3.
上述の架橋の程度は、特に制限はなくそれぞれ
の状況に応じて適宜定めればよいが、一般には用
いる結晶性樹脂に対してゲル分率が15〜60重量％
程度となるように調節すべきである。 The degree of crosslinking mentioned above is not particularly limited and may be determined as appropriate depending on each situation, but generally the gel fraction is 15 to 60% by weight based on the crystalline resin used.
It should be adjusted to the desired degree.
このようにして得られる本発明の感熱抵抗性導
電性組成物は、常温における電気抵抗が小さく、
しかも昇温時の抵抗増大倍率が大きく、感熱抵抗
材料としてきわめて有利な特性を示す。 The heat-sensitive resistive conductive composition of the present invention obtained in this way has a low electrical resistance at room temperature,
In addition, the resistance increases at a high rate when the temperature rises, and exhibits extremely advantageous characteristics as a heat-sensitive resistance material.
特に、炭素質粒子含量の少ない組成物は、昇温
時の電気抵抗の増大倍率が著しく大きく、また炭
素質粒子含量の多い組成物は常温での電気抵抗が
非常に小さいという特性を有する。 In particular, a composition with a small content of carbonaceous particles has a significantly large increase in electrical resistance when the temperature is increased, and a composition with a large content of carbonaceous particles has a property that the electrical resistance at room temperature is extremely small.
したがつて、本発明の組成物は、感熱抵抗素
子，自己温度制御発熱体などに用いられる感熱抵
抗性導電性材料として有効に利用することができ
る。 Therefore, the composition of the present invention can be effectively used as a heat-sensitive resistive conductive material used in heat-sensitive resistance elements, self-temperature control heating elements, and the like.
次に本発明を実施例によりさらに詳しく説明す
る。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
平均粒径43mμのカーボンブラツク（三菱化成
工業(株)製：ダイアブラツクＥ）50ｇを、塩化パラ
ジウムと塩化第一錫を含有するキヤタリスト液
（奥野製薬工業(株)製：コンデイシヨナーEPC）10
mlと塩酸30mlおよび水160mlからなる液に５分間
浸漬し、濾過した後水洗した。次いで、このカー
ボンブラツクを濃度10vol％の希硫酸に浸漬した
後、水洗してカーボンブラツクを活性化し、水
300mlに分散し、これに硫酸銅とホルムアルデヒ
ド，酒石酸塩などを含む無電解銅メツキ液460ml
を滴下して銅メツキを施し、水洗して乾燥した。
得られた銅メツキカーボンブラツクは、銅の含有
量が12.5wt％であり、比重が2.07であつた。Example 1 50 g of carbon black (manufactured by Mitsubishi Chemical Industries, Ltd.: Diablack E) with an average particle size of 43 mμ was mixed with a catalyst solution containing palladium chloride and stannous chloride (manufactured by Okuno Pharmaceutical Industries, Ltd.: Conditioner EPC). Ten
ml, 30 ml of hydrochloric acid, and 160 ml of water for 5 minutes, filtered, and washed with water. Next, this carbon black is immersed in dilute sulfuric acid with a concentration of 10 vol%, washed with water to activate the carbon black, and then soaked in water.
460ml of electroless copper plating solution containing copper sulfate, formaldehyde, tartrate, etc.
was applied dropwise to perform copper plating, washed with water, and dried.
The resulting copper-plated carbon black had a copper content of 12.5 wt% and a specific gravity of 2.07.
このようにして得られた銅メツキカーボンブラ
ツク31.9ｇと、高密度ポリエチレン（出光石油化
学(株)製：出光ポリエチレン550B）38.1ｇをラボ
プラストミルにより170℃において20分間混練し、
架橋剤として２，５−ジメチル−２，５−ジ（ｔ
−ブチルパーオキシ）ヘキシン−３を0.21ｇ添加
して２分間混練して架橋化した。 31.9 g of the copper-plated carbon black thus obtained and 38.1 g of high-density polyethylene (manufactured by Idemitsu Petrochemical Co., Ltd.: Idemitsu Polyethylene 550B) were kneaded at 170°C for 20 minutes using a laboplast mill.
2,5-dimethyl-2,5-di(t
0.21 g of -butylperoxy)hexyne-3 was added and kneaded for 2 minutes to effect crosslinking.
次にこのようにして得られた架橋化組成物（こ
れは、高密度ポリエチレン100容量部に対して銅
メツキカーボンブラツク38.9容量部からなる。）
を肉厚１mmのシートに成形し、次いでシート両面
に電解銅箔を圧着した。得られたシートから一辺
１cmの正方形の切片を取出し、25℃における比抵
抗を測定したところ、4.7Ω・cmであつた。また、
このものを150℃に昇温した際の抵抗値は、25℃
における抵抗値の109.3倍であつた。 Next, the crosslinked composition thus obtained (which consisted of 38.9 parts by volume of copper-plated carbon black per 100 parts by volume of high-density polyethylene).
was formed into a sheet with a wall thickness of 1 mm, and then electrolytic copper foil was crimped onto both sides of the sheet. A square section of 1 cm on a side was taken out from the obtained sheet, and its specific resistance at 25°C was measured, and it was found to be 4.7 Ω·cm. Also,
When this thing is heated to 150℃, the resistance value is 25℃
The resistance value was 10 9.3 times the resistance value at .
比較例 １
実施例１において、銅メツキカーボンブラツク
の代わりに平均粒径43mμのカーボンブラツク
（ダイアブラツクＥ）31.9ｇをそのまま用いたこ
と以外は実施例１と同様に高密度ポリエチレンと
混練し、架橋して組成物を得た。このものの25℃
における比抵抗は4.7Ω・cmであり、150℃に昇温
した際の抵抗値は、25℃における抵抗値の104.9倍
であつた。Comparative Example 1 In the same manner as in Example 1, except that 31.9 g of carbon black (Diabrak E) with an average particle size of 43 mμ was used as it was instead of the copper-plated carbon black, it was kneaded with high-density polyethylene and crosslinked. A composition was obtained. 25℃ of this
The specific resistance was 4.7Ω·cm, and the resistance value when the temperature was raised to 150°C was 10 4.9 times the resistance value at 25°C.
実施例 ２
実施例１において、高密度ポリエチレン100容
量部に対して銅メツキカーボンブラツクを47.0容
量部となるように配合したこと以外は、実施例１
と同様の操作を行なつた。得られた架橋化組成物
の25℃における比抵抗は1.8Ω・cmであり、150℃
に昇温した際の抵抗値は、25℃における抵抗値の
106.2倍であつた。Example 2 Example 1 was repeated except that 47.0 parts by volume of copper-plated carbon black was blended with 100 parts by volume of high-density polyethylene.
The same operation was performed. The specific resistance of the obtained crosslinked composition at 25°C was 1.8Ω・cm, and at 150°C
The resistance value when the temperature is raised to 25℃ is the resistance value at 25℃.
10 It was 6.2 times higher.
実施例 ３
実施例１において、高密度ポリエチレン100容
量部に対して銅メツキカーボンブラツクを53.6容
量部となるように配合したこと以外は、実施例１
と同様の操作を行なつた。得られた架橋組成物の
25℃における比抵抗は0.82Ω・cmであり、150℃
に昇温した際の抵抗値は、25℃における抵抗値の
104倍であつた。Example 3 Same as Example 1 except that 53.6 parts by volume of copper-plated carbon black was mixed with 100 parts by volume of high-density polyethylene.
The same operation was performed. of the obtained crosslinked composition
The specific resistance at 25℃ is 0.82Ω・cm, and at 150℃
The resistance value when the temperature is raised to 25℃ is the resistance value at 25℃.
It was 10 4 times as hot.
Claims (1)
ンブラツク粒子に化学メツキにより金属を付着し
た炭素質粒子よりなる架橋化組成物であつて、前
記結晶性樹脂100容量部に、前記金属を付着した
炭素質粒子を20〜70容量部配合してなる感熱抵抗
性導電性組成物。 ２ 金属を付着した炭素質粒子が、銅メツキカー
ボンブラツクである特許請求の範囲第１項記載の
組成物。 ３ 金属を付着した炭素質粒子の金属付着量が、
炭素質粒子に対して５〜30重量％である特許請求
の範囲第１項記載の組成物。[Scope of Claims] 1. A crosslinked composition comprising a crystalline resin and carbonaceous particles having metal attached by chemical plating to carbon black particles having a particle size of 10 mμ to 1 μm, the composition comprising 100 parts by volume of the crystalline resin. and 20 to 70 parts by volume of carbonaceous particles to which the metal is attached. 2. The composition according to claim 1, wherein the carbonaceous particles to which metal is attached are copper-plated carbon black. 3 The amount of metal attached to the carbonaceous particles with metal attached is
The composition according to claim 1, wherein the amount is 5 to 30% by weight based on the carbonaceous particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20145284A JPS6181460A (en) | 1984-09-28 | 1984-09-28 | Electrically conductive composition having heat-sensitive resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20145284A JPS6181460A (en) | 1984-09-28 | 1984-09-28 | Electrically conductive composition having heat-sensitive resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6181460A JPS6181460A (en) | 1986-04-25 |
| JPH0453904B2 true JPH0453904B2 (en) | 1992-08-27 |
Family
ID=16441320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20145284A Granted JPS6181460A (en) | 1984-09-28 | 1984-09-28 | Electrically conductive composition having heat-sensitive resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6181460A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63278303A (en) * | 1987-05-11 | 1988-11-16 | Nippon Mektron Ltd | Ptc element |
| JP3122000B2 (en) * | 1994-12-16 | 2001-01-09 | ソニーケミカル株式会社 | PTC element, protection circuit and circuit board using the same |
| CN100381493C (en) * | 2006-05-19 | 2008-04-16 | 浙江大学 | Method for preparing conductive polymer composite material by metal particle modified carbon black |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5610352B2 (en) * | 1972-12-13 | 1981-03-07 | ||
| JPS5190338A (en) * | 1975-02-06 | 1976-08-07 | ||
| US4545926A (en) * | 1980-04-21 | 1985-10-08 | Raychem Corporation | Conductive polymer compositions and devices |
| JPS6033133B2 (en) * | 1982-10-28 | 1985-08-01 | 工業技術院長 | Method for producing mica with metal coating |
-
1984
- 1984-09-28 JP JP20145284A patent/JPS6181460A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6181460A (en) | 1986-04-25 |
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