JP2758092B2 - Self-lubricating insulated wire - Google Patents
Self-lubricating insulated wireInfo
- Publication number
- JP2758092B2 JP2758092B2 JP3283793A JP28379391A JP2758092B2 JP 2758092 B2 JP2758092 B2 JP 2758092B2 JP 3283793 A JP3283793 A JP 3283793A JP 28379391 A JP28379391 A JP 28379391A JP 2758092 B2 JP2758092 B2 JP 2758092B2
- Authority
- JP
- Japan
- Prior art keywords
- lubricating
- reactive
- compound
- insulating layer
- insulated wire
- 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.)
- Expired - Fee Related
Links
Landscapes
- Insulated Conductors (AREA)
- Organic Insulating Materials (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
- Paints Or Removers (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、導体上に形成された絶
縁層自体が良好な滑性を有する自己潤滑性絶縁電線に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-lubricating insulated wire in which an insulating layer itself formed on a conductor has good lubricity.
【0002】[0002]
【従来の技術】一般に、絶縁電線はその製造及び加工時
に加わる負荷によって絶縁層の損傷や断線を生じ易い
が、この負荷を軽減するには絶縁電線の表面の滑り性を
高めて摩擦抵抗を低下させることが有効である。このた
め、従来より滑り性を高める手段として、絶縁層の表面
に潤滑油、パラフィン類、ワックス等の滑性成分を塗布
する方法、ナイロンやポリエチレンの如き摩擦係数の低
い樹脂からなる上塗り層を設ける方法、上記潤滑成分を
絶縁層中に含有させる方法等が採用されていた。2. Description of the Related Art Generally, insulated wires are liable to damage or break the insulation layer due to a load applied during manufacturing and processing. However, in order to reduce the load, the slip resistance of the surface of the insulated wire is increased to reduce the frictional resistance. It is effective to do so. For this reason, as a means for improving the slipperiness, a method of applying a lubricating oil, a paraffin, a wax or the like to the surface of the insulating layer, or providing an overcoat layer made of a resin having a low coefficient of friction such as nylon or polyethylene is conventionally used as a means for improving the slipperiness. A method, a method of including the lubricating component in the insulating layer, and the like have been adopted.
【0003】しかるに、近年においては、製造及び加工
工程全体の高速化と空間効率の向上を目的として、巻線
速度並びに占有率つまり一定空間内に配位させる電線量
をますます大きくする傾向にあり、これに伴って必然的
に絶縁電線に加わる負荷が増大することになり、前記の
如き方法では最早、近年の苛酷な条件には対処し得なく
なっている。However, in recent years, there has been a tendency to increase the winding speed and occupancy, that is, the amount of electric wires to be arranged in a certain space, for the purpose of speeding up the entire manufacturing and processing steps and improving space efficiency. Accordingly, the load applied to the insulated wire is inevitably increased, and the above-mentioned method can no longer cope with severe conditions in recent years.
【0004】そこで、前記方法に代わるものとして、絶
縁層中に平均粒子径10μm以下のポリエチレン粉末、
ポリプロピレン粉末、四フッ化エチレン粉末の如き滑性
樹脂微粉末を配合する手段(特公平2−199710号
公報、特公昭63−59482号公報等)や、分子鎖の
末端に直鎖アルキル基を付加した変性ポリアミドイミド
を含むポリアミドイミド樹脂を主成分とする絶縁層を設
ける手段(特公昭63−51193号公報)等が提案さ
れている。Therefore, as an alternative to the above method, polyethylene powder having an average particle diameter of 10 μm or less in the insulating layer,
Means for blending fine lubricating resin powder such as polypropylene powder and ethylene tetrafluoride powder (Japanese Patent Publication No. 2-199710, Japanese Patent Publication No. 63-59482, etc.), and adding a linear alkyl group to the terminal of the molecular chain Means for providing an insulating layer mainly composed of a modified polyamideimide containing a polyamideimide resin (Japanese Patent Publication No. Sho 63-51193) and the like have been proposed.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、前記の
絶縁層中に滑性樹脂微粉末を配合する手段では、絶縁層
の形成に用いる絶縁塗料中において該微粉末が均一に分
散しにくく、塗料の安定性が悪くなると共に、絶縁層の
機械的及び物理的特性の低下や、上記微粉末の分散不均
一に起因した外観低下を招き易いという問題があった。
また、前記のポリアミドイミド樹脂を主成分とする絶縁
層を設ける手段では、変性ポリアミドイミドの重合度を
大きくできないため、絶縁層の可撓性が不充分になると
共に、該変性ポリアミドイミドの構造上から絶縁層表面
の滑性向上作用に自ずと限界があり、巻線速度及び占有
率を更に大きくする場合に充分に対処できないという難
点があった。However, in the above-mentioned means of blending the lubricating resin fine powder into the insulating layer, the fine powder is difficult to be uniformly dispersed in the insulating paint used for forming the insulating layer, and the There is a problem that the stability is deteriorated, the mechanical and physical properties of the insulating layer are reduced, and the appearance is easily reduced due to the uneven dispersion of the fine powder.
Further, in the means for providing an insulating layer containing a polyamide-imide resin as a main component, the degree of polymerization of the modified polyamide-imide cannot be increased, so that the flexibility of the insulating layer becomes insufficient and the structure of the modified polyamide-imide is reduced. Therefore, the effect of improving the smoothness of the surface of the insulating layer is naturally limited, and it is difficult to sufficiently cope with a case where the winding speed and the occupancy are further increased.
【0006】本発明は、上述の状況に鑑み、ポリアミド
イミド絶縁層を備えるものとして、該絶縁層自体の滑性
が極めて高く、巻線速度及び占有率を非常に大きくして
も絶縁被膜の損傷や断線を生じにくく、もって近年の製
造及び加工工程全体の高速化と空間効率の向上の要望に
充分に対処し得る上、該絶縁層の耐熱性及び可撓性、安
定性、耐加工性、外観に優れ、且つ該絶縁層の形成に用
いる絶縁塗料の安定性も良好となる自己潤滑性絶縁電線
を提供することを目的としている。In view of the above situation, the present invention, provided with a polyamide-imide insulating layer, has extremely high slipperiness of the insulating layer itself. Hardly cause disconnection, and can sufficiently cope with recent demands for speeding up the entire manufacturing and processing steps and improving space efficiency. In addition, heat resistance and flexibility of the insulating layer, stability, processing resistance, It is an object of the present invention to provide a self-lubricating insulated wire having excellent appearance and good stability of an insulating paint used for forming the insulating layer.
【0007】[0007]
【課題を解決するための手段】本発明に係る自己潤滑性
絶縁電線は、上記目的を達成する手段として、導体上に
直接又は下地絶縁層を介してポリアミドイミド樹脂を主
成分とする絶縁層が形成され、前記ポリアミドイミド樹
脂は、3価以上の無水カルボン酸と、イソシアネート基
と反応し得る少なくとも2個の反応性基と炭素数17以
上の直鎖アルキル基とを含む反応性滑性化合物と、ジイ
ソシアネート化合物との反応物からなり、ポリアミドイ
ミドの主鎖の複数箇所に側鎖として末端側が前記直鎖ア
ルキル基よりなる複数の滑性基を結合したグラフトポリ
マー形態のポリマー分子であることを特徴とする構成を
採用するものである。The self-lubricating insulated wire according to the present invention comprises, as a means for achieving the above object, an insulating layer mainly composed of a polyamideimide resin on a conductor directly or via a base insulating layer. The polyamideimide resin formed is a trivalent or more carboxylic anhydride, a reactive slip compound containing at least two reactive groups capable of reacting with an isocyanate group and a linear alkyl group having 17 or more carbon atoms. And a polymer molecule in the form of a graft polymer comprising a reaction product with a diisocyanate compound and having a plurality of lubricating groups consisting of the above-mentioned straight-chain alkyl group bonded to a plurality of positions of the main chain of the polyamideimide as side chains at the terminal side. Is adopted.
【0008】また、請求項2の発明は、上記請求項1の
自己潤滑性絶縁電線において、前記ポリアミドイミド樹
脂は、3価以上の多価カルボン酸無水物と、この多価カ
ルボン酸無水物1モルに対して0.03〜0.6モルの
反応性滑性化合物と、これら多価カルボン酸無水物と反
応性滑性化合物の両者に対して実質的に等モルのジイソ
シアネート化合物との反応物からなる構成を採用したも
のである。According to a second aspect of the present invention, there is provided the self-lubricating insulated wire according to the first aspect, wherein the polyamideimide resin comprises a trivalent or more polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid anhydride. A reaction product of 0.03 to 0.6 moles of the reactive slip compound with respect to the mole, and a diisocyanate compound substantially equimolar to both the polycarboxylic anhydride and the reactive slip compound. Is adopted.
【0009】[0009]
【発明の細部構成と作用】本発明の絶縁電線における絶
縁層の主成分をなすポリアミドイミド樹脂は、前記のよ
うにポリアミドイミドの主鎖の複数箇所に側鎖として末
端側が直鎖アルキル基からなる滑性基が結合したグラフ
トポリマー形態であり、これら側鎖によって該絶縁層に
優れた自己潤滑性をもたらす。しかして、このようなポ
リアミドイミド樹脂では、その合成時に上記の直鎖アル
キル基を有する側鎖をグラフト化する形で一分子中に数
多く導入可能であるため、形成される絶縁層の表面滑性
を著しく高くできる上、合成反応の機構から滑性成分の
導入による重合度の制約がないので、高重合度で可撓性
に優れた絶縁被膜を形成できる。また該ポリアミドイミ
ド樹脂を主体とする絶縁塗料には格別な固形微粒子等を
配合する必要がないため、当然にその安定性が良好であ
ると共に、形成される絶縁層は均一でポリアミドイミド
樹脂本来の優れた耐熱性及び耐加工性を具備するものと
なる。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyamide-imide resin, which is the main component of the insulating layer in the insulated wire of the present invention, has a linear alkyl group on the terminal side as a side chain at a plurality of positions in the main chain of the polyamide-imide as described above. It is in the form of a graft polymer with lubricating groups attached, and these side chains provide the insulating layer with excellent self-lubricating properties. However, in such a polyamide-imide resin, it is possible to introduce a large number of such side chains having a straight-chain alkyl group into one molecule during the synthesis thereof in one molecule, so that the surface lubricity of the formed insulating layer is reduced. Can be significantly increased, and there is no restriction on the degree of polymerization due to the introduction of a lubricating component due to the mechanism of the synthesis reaction, so that an insulating film having a high degree of polymerization and excellent flexibility can be formed. In addition, since it is not necessary to mix special solid fine particles and the like in the insulating paint mainly composed of the polyamide-imide resin, the stability is naturally good, and the formed insulating layer is uniform and the polyamide-imide resin has an inherent property. It has excellent heat resistance and processing resistance.
【0010】これに対し、例えば直鎖アルキル基等の滑
性基を分子末端に導入したポリアミドイミド樹脂では、
滑性に寄与する部分が一分子当たり2箇所にとどまるた
め、絶縁層の表面滑性をある程度以上に高めることがで
きず、しかもポリマー合成において分子末端に滑性基が
付加した時点でポリマー分子末端の重合反応が停止する
ことから、重合度は大きくならず、これを用いて形成さ
れる絶縁層の可撓性が既述のように不充分となる。On the other hand, in a polyamideimide resin having a lubricating group such as a linear alkyl group introduced at a molecular terminal,
Since the number of parts that contribute to lubrication is limited to two per molecule, the surface lubricity of the insulating layer cannot be increased to a certain degree or more, and the polymer molecule ends when a lubricating group is added to the molecular end in polymer synthesis. Since the polymerization reaction is stopped, the degree of polymerization does not increase, and the flexibility of the insulating layer formed using the polymerization becomes insufficient as described above.
【0011】本発明で用いる前記のグラフトポリマー形
態のポリアミドイミド樹脂は、3価以上の無水カルボン
酸と、イソシアネート基と反応し得る少なくとも2個の
反応性基とと炭素数17以上の直鎖アルキル基とを含む
反応性滑性化合物と、ジイソシアネート化合物との反応
物からなるものである。すなわち、上記の反応性滑性化
合物はイソシアネート基と反応し得る少なくとも2個の
反応性基を有するため、3価以上の多価カルボン酸無水
物とジイソシアネート化合物との反応による一般的なポ
リアミドイミドの合成において該反応性滑性化合物を存
在させることにより、上記反応性基がジイソシアネート
化合物のイソシアネート基と反応し、該反応性滑性化合
物の反応性基を有する部分がポリアミドイミドの主鎖中
に取り込まれ、その滑性基を含む部分は主鎖より枝別れ
した側鎖を構成することになり、ポリアミドイミドの主
鎖の複数箇所に側鎖として滑性基が結合したグラフトポ
リマー形態のポリアミドイミドポリマー分子を生成す
る。[0011] The polyamideimide resin in the form of a graft polymer used in the present invention is a carboxylic anhydride having a valency of 3 or more, at least two reactive groups capable of reacting with an isocyanate group, and a linear alkyl having 17 or more carbon atoms. And a reactive product of a reactive lubricating compound containing a group and a diisocyanate compound. That is, since the above-mentioned reactive lubricating compound has at least two reactive groups capable of reacting with an isocyanate group, a general polyamideimide obtained by a reaction between a trivalent or higher polycarboxylic acid anhydride and a diisocyanate compound is used. By the presence of the reactive slip compound in the synthesis, the reactive group reacts with the isocyanate group of the diisocyanate compound, and the moiety having the reactive group of the reactive slip compound is incorporated into the main chain of the polyamideimide. The portion containing the lubricating group constitutes a side chain branched from the main chain, and a polyamideimide polymer in the form of a graft polymer in which a lubricating group is bonded as a side chain to a plurality of positions of the main chain of the polyamideimide. Generate molecules.
【0012】ここで、上記の反応性滑性化合物として
は、ポリアミドイミドの特性を維持させる上で、イソシ
アネート基と反応し得る少なくとも2個の反応性基がカ
ルボキシル基と水酸基の一方又は両方であるものが好適
である。すなわち、ポリアミドイミドの合成において、
ジイソシアネート化合物のイソシアネート基との反応に
より、カルボキシル基はアミド結合、水酸基はウレタン
結合をそれぞれ形成する。また、この反応性滑性化合物
における直鎖アルキル基は、最終的に合成されるポリア
ミドイミド樹脂に充分な滑性を付与する上で、炭素数が
17以上であることを必要とする。Here, as the reactive lubricating compound, at least two reactive groups capable of reacting with an isocyanate group are one or both of a carboxyl group and a hydroxyl group in order to maintain the properties of the polyamideimide. Those are preferred. That is, in the synthesis of polyamideimide,
The carboxyl group forms an amide bond and the hydroxyl group forms a urethane bond by the reaction of the diisocyanate compound with the isocyanate group. The linear alkyl group in the reactive lubricating compound needs to have 17 or more carbon atoms in order to impart sufficient lubrication to the polyamideimide resin finally synthesized.
【0013】しかして、このような反応性滑性化合物と
しては、特に制約されないが、イソシアネート基と反応
し得る反応性基を3個以上有する多価化合物と、炭素数
17以上の直鎖アルキル基及びイソシアネート基を有す
る化合物(以下、直鎖アルキル基含有イソシアネート化
合物という)との反応物が、その合成の容易さより好適
である。すなわち、上記の直鎖アルキル基含有イソシア
ネート化合物と多価化合物とは、後者の反応性基が少な
くとも2個残るようにモル比を設定して反応させればよ
い。The reactive lubricating compound is not particularly limited, but may be a polyvalent compound having three or more reactive groups capable of reacting with an isocyanate group, and a linear alkyl group having 17 or more carbon atoms. And a compound having an isocyanate group (hereinafter, referred to as a linear alkyl group-containing isocyanate compound) are more preferable because of their ease of synthesis. That is, the linear alkyl group-containing isocyanate compound and the polyvalent compound may be reacted at a molar ratio such that at least two reactive groups remain.
【0014】反応性滑性化合物の合成に用いる一方の原
料成分である、イソシアネート基に対して反応し得る反
応性基を3個以上有する多価化合物としては、例えば、
グリセリン、トリメチロールプロパン、ペンタエリスリ
トール、トリメリット酸、ピロメリット酸、3・3’・
4・4’−ジフェニルエーテルテトラカルボン酸、ナフ
タレンテトラカルボン酸等、分子中にカルボキシル基又
は/及び水酸基を3個以上有する化合物が挙げられる。Examples of the polyvalent compound having three or more reactive groups capable of reacting with an isocyanate group, which is one of the raw material components used in the synthesis of the reactive lubricating compound, include:
Glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, pyromellitic acid, 3.3 '
Compounds having three or more carboxyl groups and / or hydroxyl groups in the molecule, such as 4,4′-diphenylethertetracarboxylic acid and naphthalenetetracarboxylic acid, may be mentioned.
【0015】反応性滑性化合物の合成に用いる他方の原
料成分である、直鎖アルキル基含有イソシアネート化合
物としては、特に制約はないが、片末端にイソシアネー
ト基を有し、反対側の末端に炭素数17以上の直鎖アル
キル基より構成されるものがよい。しかして、このよう
な直鎖アルキル基含有イソシアネート化合物を得るに
は、例えば、ステアリン酸、モンタン酸、ドコサン酸等
の高級脂肪酸、高級脂肪族アルコール等の片末端にカル
ボキシル基や水酸基を有する脂肪族化合物と、ジイソシ
アネート化合物とを等モル反応させればよい。The linear alkyl group-containing isocyanate compound, which is the other raw material component used in the synthesis of the reactive lubricating compound, is not particularly limited, but has an isocyanate group at one end and a carbon atom at the other end. Those composed of linear alkyl groups having the number of 17 or more are preferred. Thus, in order to obtain such a linear alkyl group-containing isocyanate compound, for example, stearic acid, montanic acid, higher fatty acids such as docosanoic acid, aliphatic acids having a carboxyl group or a hydroxyl group at one end such as higher aliphatic alcohols, etc. What is necessary is just to make an equimolar reaction of a compound and a diisocyanate compound.
【0016】反応性滑性化合物の合成は、前記の如く、
イソシアネート基に対して反応し得る反応性基を3個以
上有する多価化合物と、直鎖アルキル基含有イソシアネ
ート化合物とを、前者の反応性基を少なくとも2個残す
ように反応させる。例えば、後者の化合物が脂肪族モノ
カルボン酸とジイソシアネート化合物との反応生成物で
あるとき、該反応生成物は両原料成分が一つのアミド結
合を介して結合して両末端の一方にイソシアネート基を
有して他方に直鎖アルキル基を有する構造であるから、
これを前者の化合物が3個の反応性基を有するものであ
るときにはその1モルに対して2モル、また4個の反応
性基を有するものであるときには等モルを反応させるこ
とにより、前者の反応性基が2個残った形で両末端又は
片末端に直鎖アルキル基を有する構造の反応性滑性化合
物が得られる。The synthesis of the reactive lubricating compound is as described above,
A polyvalent compound having three or more reactive groups capable of reacting with an isocyanate group is reacted with a linear alkyl group-containing isocyanate compound so as to leave at least two of the former reactive groups. For example, when the latter compound is a reaction product of an aliphatic monocarboxylic acid and a diisocyanate compound, the reaction product has an isocyanate group at one of both ends by combining both raw material components via one amide bond. Since it has a structure having a straight-chain alkyl group on the other side,
When the former compound has three reactive groups, it is reacted with 2 moles per mole of the former compound, and when it has four reactive groups, it is reacted with an equimolar amount. A reactive lubricating compound having a structure having a linear alkyl group at both terminals or at one terminal with two reactive groups remaining is obtained.
【0017】ポリアミドイミドの合成における反応性滑
性化合物の使用量は、3価以上の多価カルボン酸無水物
1モルに対して0.03〜0.6モルの範囲とするのが
よく、少なすぎては充分な滑性向上効果が得られず、逆
に多すぎては絶縁電線の耐熱性が低下する。しかして、
ポリアミドイミドを合成するには、N−メチル−2−ピ
ロリドン等の適当な溶媒中において、110〜140℃
程度の加熱下で、上記の多価カルボン酸無水物と反応性
滑性化合物の両者に対し、実質的に等モルのジイソシア
ネート化合物を反応させればよい。The amount of the reactive lubricating compound to be used in the synthesis of the polyamideimide is preferably in the range of 0.03 to 0.6 mol per mol of the trivalent or higher polycarboxylic acid anhydride. If the amount is too large, a sufficient effect of improving lubricity cannot be obtained, and if the amount is too large, the heat resistance of the insulated wire decreases. Then
In order to synthesize polyamideimide, 110-140 ° C in a suitable solvent such as N-methyl-2-pyrrolidone.
Under a certain degree of heating, both the polycarboxylic acid anhydride and the reactive lubricating compound may be reacted with a substantially equimolar diisocyanate compound.
【0018】ポリアミドイミドの合成に使用する3価以
上の多価カルボン酸無水物としては、例えば、無水トリ
メリット酸、無水ピロメリット酸、無水ベンゾフェノン
テトラカルボン酸等が挙げられ、特に無水トリメリット
酸が好適である。Examples of the trivalent or higher polycarboxylic anhydride used in the synthesis of polyamideimide include trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and the like. In particular, trimellitic anhydride Is preferred.
【0019】ジイソシアネート化合物としては、例え
ば、エチレンジイソシアネート、1・4−テトラメチレ
ンジイソシアネート、1・3−フェニレンジイソシアネ
ート、1・4−フェニレンジイソシアネート、ジフェニ
ルメタン−2・4’−ジイソシアネート、ジフェニルメ
タン−4・4’−ジイソシアネート、ジフェニルエーテ
ル−4・4’−ジイソシアネート、ナフタレン−1・4
−ジイソシアネート、ナフタレン−1・5−ジイソシア
ネート等が挙げられるが、これら以外でもポリアミドイ
ミドの合成原料として知られる各種のジイソシアネート
化合物をいずれも使用可能である。Examples of the diisocyanate compound include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, diphenylmethane-2.4'-diisocyanate, and diphenylmethane-4.4 '. -Diisocyanate, diphenyl ether-4.4'-diisocyanate, naphthalene-1.4
-Diisocyanate, naphthalene-1.5-diisocyanate, etc., and other than these, any of various diisocyanate compounds known as raw materials for synthesizing polyamideimide can be used.
【0020】絶縁電線を製造するには、上記の合成反応
後のポリアミドイミドを含む溶液そのもの、もしくは該
溶液に必要に応じて他の樹脂成分や着色剤、充填剤等の
各種添加剤をポリアミドイミドとしての性能を阻害しな
い範囲で配合したものを絶縁塗料として用い、この塗料
を軟銅線等の導体上に直接、あるいは該導体上に予め形
成された下地絶縁層を介して、塗布、焼き付けして所要
の厚みの滑性絶縁層を形成すればよい。また、下地絶縁
層としては、ポリエステル、ポリエステルイミド、ポリ
アミドイミド、ポリイミド等、種々の耐熱性樹脂からな
る絶縁層を採用できる。In order to manufacture an insulated wire, a solution containing the polyamideimide after the above-described synthesis reaction itself, or various additives such as a resin component, a coloring agent, and a filler, if necessary, are added to the solution. As a coating that does not impair the performance as a coating used as an insulating paint, this paint is applied directly on a conductor such as soft copper wire or through a base insulating layer formed in advance on the conductor, and applied and baked. What is necessary is just to form the slippery insulating layer of required thickness. Further, as the base insulating layer, an insulating layer made of various heat-resistant resins such as polyester, polyesterimide, polyamideimide, and polyimide can be employed.
【0021】[0021]
【実施例】以下に、本発明の実施例を比較例と対比して
詳細に説明するが、本発明はこれら実施例に限定される
ものではない。EXAMPLES Examples of the present invention will be described in detail below in comparison with comparative examples, but the present invention is not limited to these examples.
【0022】実施例1 4リットルの四つ口フラスコに、ジフェニルメタン−4
・4’−ジイソシアネート250gとモンタン酸480
g及びN−メチル−2−ピロリドン2,500gを収容
し、100℃にて2時間反応させたのち、60℃まで冷
却してピロメリット酸130gを徐々に添加し、温度を
100℃に昇温して5時間反応させ、液温が室温になる
まで降温したのち、ジメチルホルムアミドにより結晶化
を行い、この結晶を濾過して採取することにより、分子
中間部に2個のカルボキシル基を有して両末端側が炭素
数28の直鎖アルキル基にて構成された反応性滑性化合
物Aを得た。Example 1 Diphenylmethane-4 was placed in a four-liter four-necked flask.
-250 g of 4'-diisocyanate and 480 montanic acid
g and 2,500 g of N-methyl-2-pyrrolidone, reacted at 100 ° C. for 2 hours, cooled to 60 ° C., and gradually added with 130 g of pyromellitic acid, and the temperature was raised to 100 ° C. Then, the mixture was allowed to react for 5 hours. After the temperature was lowered until the liquid temperature reached room temperature, crystallization was performed with dimethylformamide, and the crystals were collected by filtration to obtain two carboxyl groups in the middle of the molecule. There was obtained a reactive lubricating compound A in which both terminal sides were composed of a linear alkyl group having 28 carbon atoms.
【0023】次に、4リットルの四つ口フラスコに、無
水トリメリット酸3.2モル、ジフェニルメタン−4・
4’−ジイソシアネート3.4モル、反応性滑性化合物
A0.096モル、及びN−メチル−2−ピロリドン
1,760gを収容し、100℃にて2時間、次いで1
25℃にて1.5時間、更に150℃にて1時間反応さ
せ、ポリアミドイミドを合成した。そして、この合成後
の反応液を絶縁塗料として用い、1.0mmの軟銅線に
複数回繰り返して塗布、焼き付けて滑性絶縁層を形成す
ることにより、自己潤滑性絶縁電線を製造した。Next, 3.2 moles of trimellitic anhydride and diphenylmethane-4.
It contains 3.4 mol of 4'-diisocyanate, 0.096 mol of reactive lubricating compound A and 1,760 g of N-methyl-2-pyrrolidone, and is heated at 100 ° C. for 2 hours and then at 1 ° C.
The reaction was carried out at 25 ° C. for 1.5 hours and further at 150 ° C. for 1 hour to synthesize polyamideimide. Then, the self-lubricating insulated wire was manufactured by using the reaction solution after the synthesis as an insulating coating material, and repeatedly applying and baking it to a 1.0 mm soft copper wire to form a lubricating insulating layer.
【0024】実施例2 ポリアミドイミドの合成におけるジフェニルメタン−4
・4’−ジイソシアネートの使用量を3.9モル、反応
性滑性化合物Aの使用量を0.64モルにそれぞれ変更
した以外は、実施例1と同様にして自己潤滑性絶縁電線
を製造した。Example 2 Diphenylmethane-4 in the synthesis of polyamideimide
-A self-lubricating insulated wire was manufactured in the same manner as in Example 1, except that the amount of 4'-diisocyanate used was changed to 3.9 mol and the amount of reactive lubricating compound A was changed to 0.64 mol. .
【0025】実施例3 ポリアミドイミドの合成におけるジフェニルメタン−4
・4’−ジイソシアネートの使用量を4.5モル、反応
性滑性化合物Aの使用量を1.28モルにそれぞれ変更
した以外は、実施例1と同様にして自己潤滑性絶縁電線
を製造した。Example 3 Diphenylmethane-4 in the synthesis of polyamideimide
-A self-lubricating insulated wire was manufactured in the same manner as in Example 1, except that the amount of 4'-diisocyanate used was changed to 4.5 mol and the amount of the reactive slip compound A was changed to 1.28 mol. .
【0026】実施例4 モンタン酸に代えてステアリン酸284gを使用した以
外は実施例1と同様にして、分子中間部に二つのカルボ
キシル基を有して両末端側が炭素数17の直鎖アルキル
基にて構成された反応性滑性化合物Bを得た。そして、
この反応性滑性化合物Bを反応性滑性化合物Aに代えて
0.64モル使用すると共に、ジフェニルメタン−4・
4’−ジイソシアネートの使用量を3.9モルに変更し
てポリアミドイミドを合成した以外は、実施例1と同様
にして自己潤滑性絶縁電線を製造した。Example 4 The procedure of Example 1 was repeated, except that 284 g of stearic acid was used instead of montanic acid. The reactive lubricating compound B constituted by was obtained. And
0.64 mol of the reactive lubricating compound B was used in place of the reactive lubricating compound A, and diphenylmethane-4 ·
A self-lubricating insulated wire was manufactured in the same manner as in Example 1, except that the amount of 4′-diisocyanate was changed to 3.9 mol to synthesize a polyamideimide.
【0027】実施例5 ピロメリット酸に代えてトリメリット酸70gを使用し
た以外は実施例1と同様にして、分子の片末端側に二つ
のカルボキシル基を有して残りの末端側が炭素数28の
直鎖アルキル基にて構成された反応性滑性化合物Cを得
た。そして、この反応性滑性化合物Cを反応性滑性化合
物Aに代えて0.64モル使用すると共に、ジフェニル
メタン−4・4’−ジイソシアネートの使用量を3.9
モルに変更してポリアミドイミドを合成した以外は、実
施例1と同様にして自己潤滑性絶縁電線を製造した。Example 5 In the same manner as in Example 1 except that 70 g of trimellitic acid was used instead of pyromellitic acid, the molecule had two carboxyl groups at one terminal and the other terminal had 28 carbon atoms. A reactive lubricating compound C comprising a linear alkyl group was obtained. Then, 0.64 mol of the reactive lubricating compound C was used instead of the reactive lubricating compound A, and the amount of diphenylmethane-4,4'-diisocyanate used was 3.9.
A self-lubricating insulated wire was manufactured in the same manner as in Example 1, except that the mole was changed to a polyamideimide.
【0028】実施例6 ピロメリット酸に代えてトリメチロールプロパン121
gを使用し、且つジフェニルメタン−4・4’−ジイソ
シアネートを使用せず、モンタン酸とトリメチロールプ
ロパンとを直接にエステル交換反応させた以外は実施例
1と同様にして、分子の片末端側に二つのカルボキシル
基を有して反対の末端側が炭素数28の直鎖アルキル基
にて構成された反応性滑性化合物Dを得た。そして、こ
の反応性滑性化合物Dを反応性滑性化合物Aに代えて
0.64モル使用すると共に、ジフェニルメタン−4・
4’−ジイソシアネートの使用量を3.9モルに変更し
てポリアミドイミドを合成した以外は、実施例1と同様
にして自己潤滑性絶縁電線を製造した。Example 6 Trimethylolpropane 121 in place of pyromellitic acid
g, and without using diphenylmethane-4,4'-diisocyanate, except that montanic acid and trimethylolpropane were directly transesterified to give one end of the molecule in the same manner as in Example 1. A reactive lubricating compound D having two carboxyl groups and having the opposite terminal side constituted by a linear alkyl group having 28 carbon atoms was obtained. Then, 0.64 mol of the reactive lubricating compound D was used instead of the reactive lubricating compound A, and diphenylmethane-4 ·
A self-lubricating insulated wire was manufactured in the same manner as in Example 1, except that the amount of 4′-diisocyanate was changed to 3.9 mol to synthesize a polyamideimide.
【0029】実施例7 0.20mmの軟銅線に予め市販のポリエステルイミド
絶縁塗料(スケネクタディー社製の商品名ISOMID
40ST)を複数回繰り返して塗布、焼き付けして下地
絶縁層を形成し、この下地絶縁層上に合成後のポリアミ
ドイミド絶縁塗料を複数回繰り返して塗布、焼き付けて
滑性絶縁層を形成した以外は、実施例1と同様にして自
己潤滑性絶縁電線を製造した。Example 7 A commercially available polyesterimide insulating paint (ISOMID manufactured by Schenectady Co., Ltd.) was previously applied to a 0.20 mm soft copper wire.
40ST) is repeatedly applied and baked a plurality of times to form a base insulating layer, and the synthesized polyamideimide insulating paint is repeatedly applied and baked on the base insulating layer a plurality of times to form a slip insulating layer. A self-lubricating insulated wire was manufactured in the same manner as in Example 1.
【0030】比較例1 反応性滑性化合物Aを使用せず、ジフェニルメタン−4
・4’−ジイソシアネートの使用量を3.2モルに変更
してポリアミドイミドを合成した以外は、実施例1と同
様にして絶縁電線を製造した。Comparative Example 1 Diphenylmethane-4 was used without using the reactive lubricating compound A.
-An insulated wire was manufactured in the same manner as in Example 1 except that the amount of 4'-diisocyanate was changed to 3.2 mol to synthesize a polyamideimide.
【0031】比較例2 4リットルの四つ口フラスコに、無水トリメリット酸
3.2モル、ジフェニルメタン−4・4’−ジイソシア
ネート3.9モル、モンタン酸6.3モル、、及びN−
メチル−2−ピロリドン1,760gを収容し、80℃
にて2時間反応させたのち、5時間かけて170℃まで
昇温し、この温度で2時間反応させ、分子末端に直鎖ア
ルキル基からなる滑性基を有するポリアミドイミドを合
成した。そして、この合成後の反応液を絶縁塗料として
用いて実施例1と同様にして絶縁電線を製造した。Comparative Example 2 3.2 mol of trimellitic anhydride, 3.9 mol of diphenylmethane-4,4'-diisocyanate, 6.3 mol of montanic acid, and N-
80 ℃ containing 1,760 g of methyl-2-pyrrolidone
After heating for 2 hours at 170 ° C., the temperature was raised to 170 ° C. over 5 hours, and the reaction was carried out at this temperature for 2 hours to synthesize a polyamideimide having a lubricating group consisting of a linear alkyl group at a molecular terminal. Then, an insulated wire was manufactured in the same manner as in Example 1 using the reaction solution after the synthesis as an insulating paint.
【0032】以上の実施例及び比較例で得られた各絶縁
電線の特性を表1に示す。なお、表中の耐軟化は、JI
S C 3003の12(2)の条件より測定した。Table 1 shows the characteristics of the insulated wires obtained in the above Examples and Comparative Examples. The softening resistance in the table is based on JI
It was measured under the conditions of SC 3003 12 (2).
【0033】[0033]
【表1】 [Table 1]
【0034】[0034]
【発明の効果】請求項1の発明によれば、絶縁層の材料
としてポリアミドイミドポリマーの主鎖の複数箇所に側
鎖として末端側が炭素数17以上の直鎖アルキル基より
なる滑性基を結合した特定のグラフトポリマー形態のポ
リアミドイミド樹脂を用いることから、絶縁層自体の滑
性が極めて高く、巻線速度及び占有率を非常に大きくし
ても絶縁層の損傷や断線を生じにくく、もって近年の製
造及び加工工程全体の高速化と空間効率の向上の要望に
充分に対処し得る上、該絶縁層の耐熱性及び可撓性、安
定性、耐加工性、外観に優れ、且つ該絶縁層の形成に用
いる絶縁塗料の安定性も良好となる自己潤滑性絶縁電線
を提供できる。According to the first aspect of the present invention, as a material of the insulating layer, a slip group having a linear alkyl group having 17 or more carbon atoms at the terminal side is bonded as a side chain to a plurality of positions of the main chain of the polyamideimide polymer. The use of a polyamide-imide resin in the form of a specific graft polymer, the insulating layer itself has extremely high lubricity, and even if the winding speed and the occupancy are very large, the insulating layer is unlikely to be damaged or disconnected. In addition to being able to sufficiently cope with the demand for speeding up the entire manufacturing and processing steps and improving space efficiency, the insulating layer is excellent in heat resistance, flexibility, stability, processing resistance, appearance, and the insulating layer A self-lubricating insulated wire can be provided which also has good stability of the insulating paint used for forming the wire.
【0035】請求項2の発明によれば、上記の自己潤滑
性絶縁電線として、特に絶縁層表面の滑性に優れて且つ
耐熱性のよいものが提供される。According to the second aspect of the present invention, as the above-mentioned self-lubricating insulated wire, there is provided a wire having particularly excellent surface smoothness of the insulating layer and good heat resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田井 誠 兵庫県尼崎市猪名寺2丁目19番1号 第 一電工株式会社 技術部内 (72)発明者 渡部 潤一郎 兵庫県尼崎市猪名寺2丁目19番1号 第 一電工株式会社 技術部内 (56)参考文献 特開 昭56−106308(JP,A) 特開 昭58−26409(JP,A) 特開 平3−115478(JP,A) ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Tai 2-9-1-1, Inaji, Amagasaki-shi, Hyogo Pref. Technical Department, No. 1 Electric Works Co., Ltd. (72) Inventor Junichiro Watanabe 2-9-1-1, Inaji, Amagasaki-shi, Hyogo Technical Department, Daiichi Denko Co., Ltd. (56) References JP-A-56-106308 (JP, A) JP-A-58-26409 (JP, A) JP-A-3-115478 (JP, A)
Claims (2)
リアミドイミド樹脂を主成分とする絶縁層が形成され、 前記ポリアミドイミド樹脂は、3価以上の無水カルボン
酸と、イソシアネート基と反応し得る少なくとも2個の
反応性基と炭素数17以上の直鎖アルキル基とを有する
反応性滑性化合物と、ジイソシアネート化合物との反応
物からなり、ポリアミドイミドの主鎖の複数箇所に側鎖
として末端側が前記直鎖アルキル基よりなる複数の滑性
基を結合したグラフトポリマー形態のポリマー分子であ
ることを特徴とする自己潤滑性絶縁電線。1. A dielectric layer mainly composed of polyamide-imide resin directly or via an underlying insulating layer on the conductor is formed, the polyamide-imide resin, a trivalent or higher carboxylic anhydride
An acid and at least two of the
Has a reactive group and a linear alkyl group having 17 or more carbon atoms
Reaction of reactive lubricating compound with diisocyanate compound
And side chains at several places in the main chain of polyamideimide
As a plurality of lubricating ends comprising the linear alkyl group
A self-lubricating insulated wire, characterized in that it is a polymer molecule in the form of a graft polymer having attached groups .
の多価カルボン酸無水物と、この多価カルボン酸無水物
1モルに対して0.03〜0.6モルの反応性滑性化合
物と、これら多価カルボン酸無水物と反応性滑性化合物
の両者に対して実質的に等モルのジイソシアネート化合
物との反応物からなる請求項1記載の自己潤滑性絶縁電
線。2. The polyamide-imide resin has a valence of 3 or more.
A polycarboxylic anhydride and a polycarboxylic anhydride
0.03-0.6 mole of reactive slip compound per mole
And these polyvalent carboxylic anhydrides and reactive lubricating compounds
A substantially equimolar amount of diisocyanate compound to both
2. The self-lubricating insulated wire according to claim 1, comprising a reaction product with a product .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3283793A JP2758092B2 (en) | 1991-10-03 | 1991-10-03 | Self-lubricating insulated wire |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3283793A JP2758092B2 (en) | 1991-10-03 | 1991-10-03 | Self-lubricating insulated wire |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05101713A JPH05101713A (en) | 1993-04-23 |
JP2758092B2 true JP2758092B2 (en) | 1998-05-25 |
Family
ID=17670217
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3283793A Expired - Fee Related JP2758092B2 (en) | 1991-10-03 | 1991-10-03 | Self-lubricating insulated wire |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2758092B2 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001059791A1 (en) * | 2000-02-10 | 2001-08-16 | The Furukawa Electric Co., Ltd. | Insulated wire |
JP4844992B2 (en) * | 2000-03-01 | 2011-12-28 | 古河電気工業株式会社 | Insulated wire |
EP1176611B1 (en) * | 2001-02-13 | 2006-05-03 | The Furukawa Electric Co., Ltd. | Insulated wire |
FR2844801A1 (en) * | 2002-09-20 | 2004-03-26 | Nexans | An autolubricating enamel varnish used for electric motor windings comprises a base polymer such as a polyamide-imide to which is attached a pendant aliphatic chain comprising at least 15 carbon atoms |
DE102010039168A1 (en) | 2010-08-10 | 2012-02-16 | Schwering & Hasse Elektrodraht Gmbh | Electro-insulating varnishes of modified polymers and electrical conductors made therefrom with improved lubricity |
JP6962548B2 (en) * | 2016-08-22 | 2021-11-05 | ユニチカ株式会社 | Polyamide-imide solution for power storage element electrodes, manufacturing method of power storage element electrodes, and power storage element electrodes |
JP6835348B2 (en) * | 2016-09-06 | 2021-02-24 | ユニチカ株式会社 | Polyamide-imide solution for power storage element separator and power storage element separator |
CN110799559B (en) * | 2017-07-03 | 2022-04-29 | 东丽株式会社 | Resin, resin composition, nonwoven fabric, fiber product, separator, secondary battery, electric double layer capacitor, and method for producing nonwoven fabric |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56106308A (en) * | 1980-01-24 | 1981-08-24 | Sumitomo Electric Industries | Insulated wire |
JPS5826409A (en) * | 1981-08-07 | 1983-02-16 | 住友電気工業株式会社 | Insulated wire |
JPH03115478A (en) * | 1989-09-29 | 1991-05-16 | Showa Electric Wire & Cable Co Ltd | Insulating coating material and insulated wire |
-
1991
- 1991-10-03 JP JP3283793A patent/JP2758092B2/en not_active Expired - Fee Related
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JPH05101713A (en) | 1993-04-23 |
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