JP2006016487A - Resin composition for electric insulation, enameled wire, heat resistant resin composition and coating - Google Patents

Resin composition for electric insulation, enameled wire, heat resistant resin composition and coating Download PDF

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JP2006016487A
JP2006016487A JP2004195465A JP2004195465A JP2006016487A JP 2006016487 A JP2006016487 A JP 2006016487A JP 2004195465 A JP2004195465 A JP 2004195465A JP 2004195465 A JP2004195465 A JP 2004195465A JP 2006016487 A JP2006016487 A JP 2006016487A
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resin composition
enameled wire
coating
resin
electrical insulation
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Seiichi Yotsuya
聖一 四家
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamideimide-based resin composition for electric insulation, excellent in abrasion resistance and flexibility, and an enameled wire, a heat resistant resin composition and a coating by using the same. <P>SOLUTION: This resin composition for the electric insulation contains (A) a polyamideimide resin obtained by performing the reaction of a diisocyanate compound or a diamine compound with a tribasic acid anhydride or a tribasic acid anhydride chloride in a basic polar solvent and (B) 2-aminobenzimidazole as essential components. The enameled wire, heat resistant resin composition and coating by using the same are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、電気絶縁用樹脂組成物及びエナメル線、並びに耐熱性樹脂組成物及び塗料に関する。   The present invention relates to a resin composition for electrical insulation, an enameled wire, a heat resistant resin composition, and a paint.

ポリアミドイミド樹脂は、耐熱性、耐薬品性および耐溶剤性が優れているため、各種基材のコート剤として広く使用され、例えば、エナメル線用ワニス、耐熱塗料などとして使用されている。
近年、エナメル線を使用する電気メーカーでは、機器の製造工程の合理化のため、自動高速巻線機を導入しているが、巻線加工時にエナメル線が摩擦や衝撃等を受けてエナメル線の絶縁層に機械的損傷を生じ、レヤーショートとアース不良等が発生して製品の不良率が増加するという問題が発生している。そこでこのような機械的損傷の少ないエナメル線が要望されている。
Polyamideimide resins are excellent in heat resistance, chemical resistance and solvent resistance, and are therefore widely used as coating agents for various substrates, for example, enameled wire varnishes, heat resistant paints and the like.
In recent years, electrical manufacturers that use enameled wires have introduced automatic high-speed winding machines to streamline the manufacturing process of the equipment, but the enameled wires are subject to friction and impact during winding processing, and the enameled wires are insulated. There is a problem that mechanical damage is caused to the layer, and a layer short-circuit and a ground failure occur to increase the defective rate of the product. Therefore, an enameled wire with less mechanical damage is desired.

従来のポリアミドイミド線は、機械的強度が他のポリエステル、ポリエステルイミド線より優れるため、特に厳しい条件で作業される場合には、例えば、4,4,-ジフェニルメタンジイソシアネ-トと無水トリメリット酸との反応により得られるポリアミドイミド樹脂(例えば、特許文献1及び2など参照)が単層または多層構造で適用されていた。しかし、近年、さらに巻線機の高速化および巻線加工の複雑化が進み、上記ポリアミドイミド樹脂では充分に対応できなくなってきた。   Conventional polyamide-imide wire is superior in mechanical strength to other polyester and polyester-imide wires, so when working under severe conditions, for example, 4,4, -diphenylmethane diisocyanate and anhydrous trimellit A polyamide-imide resin obtained by a reaction with an acid (see, for example, Patent Documents 1 and 2) has been applied in a single layer or multilayer structure. However, in recent years, the speed of the winding machine and the complexity of the winding process have further increased, and the polyamide-imide resin has not been able to cope with it sufficiently.

特公昭44-19274号公報Japanese Patent Publication No. 44-19274 特公昭45-27611号公報Japanese Patent Publication No. 45-27611

本発明は、耐摩耗性および可とう性に優れたポリアミドイミド樹脂系電気絶縁用樹脂組成物及びこれを用いたエナメル線、並びに耐熱性樹脂組成物及び塗料を提供するものである。   The present invention provides a polyamide-imide resin-based electrical insulating resin composition excellent in wear resistance and flexibility, an enameled wire using the same, a heat-resistant resin composition, and a coating material.

本発明は(A)ポリアミドイミド樹脂及び、(B)2-アミノベンズイミダゾ-ルを含有してなる電気絶縁用樹脂組成物に関する。
また、本発明は、(A)ポリアミドイミド樹脂の数平均分子量が10,000〜50,000である上記の電気絶縁用樹脂組成物に関する。
さらに、本発明は、(A)ポリアミドイミド樹脂100重量部に対し、前記(B)2-アミノベンズイミダゾ-ル0.01〜10重量部である、上記の電気絶縁用樹脂組成物に関する。
さらに、本発明は、上記の電気絶縁用樹脂組成物を導体上に直接または他の絶縁物を介して塗布、焼付けたエナメル線に関する。
The present invention relates to a resin composition for electrical insulation comprising (A) a polyamideimide resin and (B) 2-aminobenzimidazole.
Moreover, this invention relates to said resin composition for electrical insulation whose number average molecular weights of (A) polyamide-imide resin are 10,000-50,000.
Furthermore, this invention relates to said resin composition for electrical insulation which is 0.01-10 weight part of said (B) 2-aminobenzimidazole with respect to 100 weight part of (A) polyamideimide resin.
Furthermore, the present invention relates to an enameled wire obtained by applying and baking the above resin composition for electrical insulation directly on a conductor or via another insulator.

また本発明は(A)ポリアミドイミド樹脂及び、(B)2-アミノベンズイミダゾ-ルを含有してなる耐熱性樹脂組成物に関する。
また、本発明は、上記の耐熱性樹脂組成物を塗膜成分として含有してなる塗料に関する。
The present invention also relates to a heat resistant resin composition comprising (A) a polyamideimide resin and (B) 2-aminobenzimidazole.
Moreover, this invention relates to the coating material containing said heat resistant resin composition as a coating-film component.

本発明の電気絶縁用樹脂組成物によれば、耐摩耗性および可とう性の良好な塗膜を形成することができ、各種基材への絶縁皮膜、保護コ-トなどに有用であり、特にエナメル線などの近年の過酷な巻線、加工、組立て作業に有用である。   According to the resin composition for electrical insulation of the present invention, it is possible to form a coating film with good wear resistance and flexibility, useful for insulating films on various substrates, protective coatings, etc. It is particularly useful for recent severe winding, processing, and assembly work such as enameled wire.

本発明に用いられる(A)ポリアミドイミド樹脂は、下記一般式(1):   The (A) polyamideimide resin used in the present invention has the following general formula (1):

Figure 2006016487
(式中、Rは3価の有機基を表し、Rは2価の有機基を表し、nは整数を表す。)で示される繰り返し構造単位を有する。
Figure 2006016487
(Wherein R 1 represents a trivalent organic group, R 2 represents a divalent organic group, and n represents an integer).

は、芳香環を有する炭素数6〜30の3価の有機基が好ましく、炭素数6〜20のものがより好ましく、炭素数6〜15のものがさらに好ましい。Rとしては、芳香環を有する炭素数6〜30の2価の有機基が好ましく、炭素数6〜20のものがより好ましく、炭素数6〜18のものがさらに好ましい。nは繰り返し構造単位(I)の数であり、R及びRの構造によって異なるが、一般的に10〜100とするのが好ましい。RおよびRの構造によって異なるが、一般的に10〜100とするのが好ましい。 R 1 is preferably a trivalent organic group having 6 to 30 carbon atoms having an aromatic ring, more preferably having 6 to 20 carbon atoms, and further preferably having 6 to 15 carbon atoms. R 2 is preferably a C 6-30 divalent organic group having an aromatic ring, more preferably 6-20 carbon atoms, and even more preferably 6-18 carbon atoms. n is the number of the repeating structural unit (I), and is preferably 10 to 100, although it varies depending on the structures of R 1 and R 2 . Although it varies depending on the structures of R 1 and R 2 , it is generally preferably 10 to 100.

本発明に用いられるポリアミドイミド樹脂は、塩基性極性溶媒中で、ジイソシアネート化合物又はジアミン化合物を、三塩基酸無水物又は三塩基酸無水物クロライドとを反応させて得られるものが好ましい。
ジイソシアネ-ト化合物又はジアミン化合物と三塩基酸無水物又は三塩基酸無水物クロライドは、いずれも芳香族化合物を使用することが好ましく、例えば以下の化合物を用いることができる。
ジイソシアネート化合物としては、4,4′−ジフェニルメタンジイソシアネ−ト、キシリレンジイソシアネ−ト、3′−ジフェニルメタンジ イソシアネ−ト、3,3′−ジメトキシビフェニル−4,4′−ジイソシアネ−ト、ビフェニル−3,4′−ジイソシアネ−ト、2,2′−ジエチルビフェニル−4,4′−ジイソシアネ−ト、フェニレンジイソシアネ−ト等が挙げられる。本発明において好ましい化合物は、4,4′−ジフェニルメタンジイソシアネ−ト、フェニレンジイソシアネ−トであり、さらに好ましくは、4,4′−ジフェニルメタンジイソシアネ−トである。
また、ジアミンとしては、4,4′−ジアミノジフェニルメタン、4,4′−ジアミノジフェニルエーテル、4,4′−ジアミノジフェニルスルホン、4,4′−ジアミノジアミノベンゾフェノン、4,4′−ジアミノジフェニルプロパン、3,3′−ジアミノジフェニルスルホン、4,4′−ジアミノジフェニルヘキサフルオロプロパン、キシリレンジアミン、フェニレンジアミン等が挙げられる。本発明において好ましい化合物は、4,4′−ジアミノジフェニルメタン、4,4′−ジアミノジフェニルエーテル、であり、さらに好ましくは、4,4′−ジアミノジフェニルメタンである。
The polyamideimide resin used in the present invention is preferably obtained by reacting a diisocyanate compound or a diamine compound with a tribasic acid anhydride or tribasic acid anhydride chloride in a basic polar solvent.
As the diisocyanate compound or diamine compound and the tribasic acid anhydride or tribasic acid chloride, it is preferable to use an aromatic compound, for example, the following compounds can be used.
Examples of the diisocyanate compound include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3'-diphenylmethane diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, Biphenyl-3,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'-diisocyanate, phenylene diisocyanate and the like can be mentioned. Preferred compounds in the present invention are 4,4'-diphenylmethane diisocyanate and phenylene diisocyanate, and more preferably 4,4'-diphenylmethane diisocyanate.
Examples of the diamine include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiaminobenzophenone, 4,4'-diaminodiphenylpropane, 3 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylhexafluoropropane, xylylenediamine, phenylenediamine and the like. Preferred compounds in the present invention are 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether, and more preferably 4,4'-diaminodiphenylmethane.

また、三塩基酸無水物としては、トリメリット酸無水物等が挙げられ、三塩基酸無水物クロライドとしては、トリメリット酸無水物クロライド等が挙げられる。   Examples of the tribasic acid anhydride include trimellitic acid anhydride and the like, and examples of the tribasic acid anhydride chloride include trimellitic acid anhydride chloride and the like.

ポリアミドイミド樹脂を合成する際に、ジカルボン酸、テトラカルボン酸二無水物等をポリアミドイミド樹脂の特性を損なわない範囲で同時に反応させることができる。   When synthesizing the polyamideimide resin, dicarboxylic acid, tetracarboxylic dianhydride, and the like can be reacted at the same time as long as the properties of the polyamideimide resin are not impaired.

ジカルボン酸としては、テレフタル酸、イソフタル酸、アジピン酸、ジクエン酸、フタルジイミドジカルボン酸、2,4′−ナフタレンジカルボン酸、2,5′−チオフェンジカルボン酸等が挙げられ、テトラカルボン酸二無水物としては、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物、ジフェニルスルホン酸二無水物等が挙げられる。本発明において好ましいジカルボン酸は、テレフタル酸、イソフタル酸、アジピン酸であり、さらに好ましくは、テレフタル酸である。また、本発明において好ましいテトラカルボン酸二無水物は、ベンゾフェノンテトラカルボン酸二無水物、ピロメリット酸二無水物、ビフェニルテトラカルボン酸二無水物であり、さらに好ましくは、ベンゾフェノンテトラカルボン酸二無水物である。   Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, dicitric acid, phthaldiimide dicarboxylic acid, 2,4′-naphthalenedicarboxylic acid, 2,5′-thiophene dicarboxylic acid, and tetracarboxylic dianhydride. Examples thereof include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, diphenylsulfonic dianhydride, and the like. Preferred dicarboxylic acids in the present invention are terephthalic acid, isophthalic acid, and adipic acid, and more preferably terephthalic acid. Further, preferred tetracarboxylic dianhydrides in the present invention are benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, and more preferably benzophenone tetracarboxylic dianhydride. It is.

本発明に用いられるポリアミドイミド樹脂は、塩基性極性溶媒中でジイソシアネート化合物またはジアミン化合物と、三塩基酸無水物又は三塩基酸無水物クロライドを反応させてえることができる。合成反応において、ジイソシアネ−ト化合物またはジアミン化合物、三塩基酸無水物または三塩基酸水物クロライド、および必要に応じて使用するジカルボン酸およびテトラカルボン酸二無水物の量は、生成されるポリアミドイミド樹脂の分子量、架橋度の観点から、酸成分の総量1.0モルに対してジイソシアネート化合物又はジアミン化合物を0.8〜1.1モルとすることが好ましく、0.95〜1.08モルとすることがより好ましく、特に、1.0〜1.08モル使用されることが好ましい。また、酸成分中、ジカルボン酸及びテトラカルボン酸二無水物は、これらの総量が0〜50モル%、さらに好ましくは0〜30モル%の範囲で使用されるのが好ましい。塩基性極性溶媒としては、N-メチル-2-ピロリドンなどの高沸点溶媒を用いるのが好ましい。また、使用量にとくに制限はないが、ジイソシアネ−ト化合物またはジアミン化合物と三塩基酸二無水物または三塩基酸二無水物の総量100重量部に対して100〜500重量部とするのが好ましい。反応温度は、通常、80〜200℃である。   The polyamideimide resin used in the present invention can be obtained by reacting a diisocyanate compound or a diamine compound with a tribasic acid anhydride or a tribasic acid anhydride chloride in a basic polar solvent. In the synthesis reaction, the amount of diisocyanate compound or diamine compound, tribasic acid anhydride or tribasic acid chloride, and dicarboxylic acid and tetracarboxylic dianhydride used as required From the viewpoint of the molecular weight of the resin and the degree of crosslinking, the diisocyanate compound or the diamine compound is preferably 0.8 to 1.1 mol with respect to 1.0 mol of the total amount of the acid component, and 0.95 to 1.08 mol. It is more preferable to use 1.0 to 1.08 mol in particular. In the acid component, the dicarboxylic acid and tetracarboxylic dianhydride are preferably used in a total amount of 0 to 50 mol%, more preferably 0 to 30 mol%. As the basic polar solvent, a high boiling point solvent such as N-methyl-2-pyrrolidone is preferably used. Moreover, although there is no restriction | limiting in particular in the usage-amount, It is preferable to set it as 100-500 weight part with respect to 100 weight part of total amounts of a diisocyanate compound or a diamine compound, and a tribasic acid dianhydride or a tribasic acid dianhydride. . The reaction temperature is usually 80 to 200 ° C.

本発明に用いられるポリアミドイミド樹脂は、数平均分子量が10,000〜50,000のものが好ましい。数平均分子量が10,000未満では、塗膜としたときの、塗膜の耐熱性や機械的特性等の諸特性が低下する傾向があり、50,0000を超えると、塗料として適正な濃度で溶媒に溶解したときに粘度が高くなり、塗装時の作業性に劣る傾向がある。このことから、数平均分子量は12,000〜30,000とすることが好ましく、18,000〜25,000とすることが特に好ましい。   The polyamideimide resin used in the present invention preferably has a number average molecular weight of 10,000 to 50,000. When the number average molecular weight is less than 10,000, the properties such as heat resistance and mechanical properties of the coating film tend to decrease when the coating film is formed. When the number average molecular weight exceeds 50,0000, the coating composition has an appropriate concentration. When dissolved in a solvent, the viscosity increases and the workability during coating tends to be poor. Therefore, the number average molecular weight is preferably 12,000 to 30,000, and particularly preferably 18,000 to 25,000.

なお、ポリアミドイミド樹脂の数平均分子量は、樹脂合成時にサンプリングし、ゲルパーミエーションクロマトグラフ(GPC)により、標準ポリスチレンの検量線を用いて測定し、目的の数平均分子量になるまで合成を継続することにより、所轄の範囲に調整することができる。   The number average molecular weight of the polyamideimide resin is sampled at the time of resin synthesis, measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve, and the synthesis is continued until the target number average molecular weight is reached. It can be adjusted to the scope of jurisdiction.

本発明に用いられる(B)2-アミノベンズイミダゾ-ルとしては、一般に下記一般式(2)   The (B) 2-aminobenzimidazole used in the present invention generally has the following general formula (2)

Figure 2006016487
で表される。
Figure 2006016487
It is represented by

2-アミノベンズイミダゾ-ルの使用量は、上記ポリアミドイミド樹脂100重量部に対して好ましくは0.01〜10重量部であり、より好ましくは0.1〜5重量部であり、さらに好ましくは0.05〜3重量部である。なお、2-アミノベンズイミダゾ-ルの使用量が上記ポリアミドイミド樹脂100重量部に対して0.01重量部未満では当該2-アミノベンゾイミダゾ-ルの効果が十分に発現せず、10重量部を超えると塗膜の耐熱性が低下する傾向がある。   The amount of 2-aminobenzimidazole used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 100 parts by weight of the polyamideimide resin. 0.05 to 3 parts by weight. When the amount of 2-aminobenzimidazole used is less than 0.01 parts by weight based on 100 parts by weight of the polyamideimide resin, the effect of the 2-aminobenzimidazole is not sufficiently exhibited, and 10 parts by weight. If it exceeds 1, the heat resistance of the coating film tends to decrease.

上記の(A)ポリアミドイミド樹脂に上記(B)成分を添加する方法は特に制限はない。例えば、有機溶剤に溶解させた(A)ポリアミドイミド樹脂に(B)2-アミノベンゾイミダゾ-ルを直接または、有機溶剤に溶解させたものを添加し、混合する方法がある。   There is no restriction | limiting in particular in the method of adding the said (B) component to said (A) polyamideimide resin. For example, there is a method of adding (B) 2-aminobenzimidazole directly or dissolved in (A) polyamide-imide resin dissolved in an organic solvent and mixing them.

本発明の電気絶縁用樹脂組成物には、有機溶媒を含むことができるが、通常、固形分を20〜40重量%含有する状態の電気絶縁用樹脂組成物として用いる。本発明の電気絶縁用樹脂組成物を導体上に直接または他の絶縁物を介して塗布、焼付けてエナメル線をえることができる。本発明の電気絶縁用樹脂組成物を用いた場合には、2-アミノベンズイミダゾ-ルを添加することにより導体との密着性が向上し、耐摩耗性および可とう性に優れたエナメル線をえることができる。   Although the resin composition for electrical insulation of the present invention can contain an organic solvent, it is usually used as a resin composition for electrical insulation in a state containing 20 to 40% by weight of a solid content. An enameled wire can be obtained by applying and baking the resin composition for electrical insulation of the present invention directly on a conductor or via another insulator. When the resin composition for electrical insulation of the present invention is used, the adhesion with the conductor is improved by adding 2-aminobenzimidazole, and an enameled wire excellent in wear resistance and flexibility is obtained. I can.

次に本発明の実施例について説明するが、本発明はこれらの実施例に制限されるものではなく、発明の主旨に基づいたこれら以外の多くの実施態様を含むことは言うまでもない。   Next, examples of the present invention will be described. However, the present invention is not limited to these examples, and it is needless to say that the present invention includes many other embodiments based on the gist of the invention.

実施例1
無水トリメリット酸194.1g(1.01モル)、4,4′−ジフェニルメタンジイソシアネート262.8g(1.05モル)、N−メチル−2−ピロリドン848.5gを温度計、攪拌機、冷却管を備えたフラスコに入れ、この混合物を乾燥させた窒素気流中で、反応により生ずる炭酸ガスの急激な発泡に注意しながら約5時間かけて徐々に昇温して140℃まで昇温した。該混合物を140℃にて8時間保温し、数平均分子量が27,000のポリアミドイミド樹脂溶液(樹脂分濃度:30%)をえた。次に、えられたポリアミドイミド樹脂溶液100重量部に2-アミノベンズイミダゾ-ル(和光純薬社製)0.09重量部を添加し、攪拌混合させ、電気絶縁用樹脂組成物をえた。
Example 1
194.1 g (1.01 mol) of trimellitic anhydride, 262.8 g (1.05 mol) of 4,4′-diphenylmethane diisocyanate, and 848.5 g of N-methyl-2-pyrrolidone were thermometer, stirrer and condenser. The mixture was placed in a equipped flask, and the mixture was gradually heated to 140 ° C. over about 5 hours in a dry nitrogen stream while paying attention to sudden foaming of carbon dioxide gas generated by the reaction. The mixture was kept at 140 ° C. for 8 hours to obtain a polyamideimide resin solution having a number average molecular weight of 27,000 (resin concentration: 30%). Next, 0.09 part by weight of 2-aminobenzimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 100 parts by weight of the obtained polyamideimide resin solution, and the mixture was stirred and mixed to obtain a resin composition for electrical insulation.

実施例2
実施例1において、4、4-ジアミノジフェニルエ-テル200.2g(1.00モル)、無水トリメリット酸192.1g(1.00モル)、N-メチル-2-ピロリドン915gおよびホウ酸3.5gを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で、約5時間かけて徐々に昇温して200℃まで昇温した。該混合物を、200℃にて20時間保温してえられた数平均分子量が20,500のポリアミドイミ樹脂溶液(樹脂分濃度:30%)100重量部を用いた以外は実施例1と同様にして電気絶縁用樹脂組成物をえた。
Example 2
In Example 1, 200.2 g (1.00 mol) of 4,4 , -diaminodiphenyl ether, 192.1 g (1.00 mol) of trimellitic anhydride, 915 g of N-methyl-2-pyrrolidone and boric acid 3.5 g was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and gradually heated up to 200 ° C. over about 5 hours in a dried nitrogen stream. The mixture was kept at 200 ° C. for 20 hours, and the same procedure as in Example 1 was conducted except that 100 parts by weight of a polyamide imi resin solution (resin content concentration: 30%) having a number average molecular weight of 20,500 was used. Thus, a resin composition for electrical insulation was obtained.

実施例3
無水トリメリット酸134.5g(0.70モル)、ベンゾフェノンテトラカルボン酸二無水物96.7g(0.3モル)4,4′−ジフェニルメタンジイソシアネート255.3g(1.02モル)、N−メチル−2−ピロリドン1135gを温度計、攪拌機、冷却管を備えたフラスコに入れ、この混合物を乾燥させた窒素気流中で、反応により生ずる炭酸ガスの急激な発泡に注意しながら約5時間かけて徐々に昇温して130℃まで昇温した。
該混合物を130℃にて7時間保温し、数平均分子量が17,000のポリアミドイミド樹脂溶液(樹脂分濃度:28%)をえた。次に、えられたポリアミドイミド樹脂溶液100重量部に2-アミノベンズイミダゾ-ル0.6166重量部添加し、攪拌混合させ、電気絶縁用樹脂組成物をえた。
Example 3
Trimellitic anhydride 134.5 g (0.70 mol), benzophenone tetracarboxylic dianhydride 96.7 g (0.3 mol) 4,4'-diphenylmethane diisocyanate 255.3 g (1.02 mol), N-methyl 2-Pyrrolidone 1135 g was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and this mixture was gradually dried over a period of about 5 hours while paying attention to the sudden foaming of carbon dioxide generated by the reaction in a nitrogen stream. The temperature was raised to 130 ° C.
The mixture was kept at 130 ° C. for 7 hours to obtain a polyamideimide resin solution (resin content concentration: 28%) having a number average molecular weight of 17,000. Next, 0.6166 parts by weight of 2-aminobenzimidazole was added to 100 parts by weight of the obtained polyamideimide resin solution and mixed by stirring to obtain a resin composition for electrical insulation.

実施例4
実施例3において、2-アミノベンズイミダゾ-ル(和光純薬社製)50重量にN-メチル-2-ピロリドン50重量部を添加し、40℃にて1h混合溶解させた溶液0.84重量部を用いた以外は実施例3と同様にして電気絶縁用樹脂組成物をえた。
Example 4
In Example 3, 50 parts by weight of N-methyl-2-pyrrolidone was added to 50 parts by weight of 2-aminobenzimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) and mixed and dissolved at 40 ° C. for 1 h, 0.84 weight A resin composition for electrical insulation was obtained in the same manner as in Example 3 except that the parts were used.

比較例1
実施例1において、2-アミノベンズイミダゾ-ル(和光純薬社製)を加えなかったことを除いては、実施例1と同様にして電気絶縁用樹脂組成物をえた。
Comparative Example 1
A resin composition for electrical insulation was obtained in the same manner as in Example 1, except that 2-aminobenzimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) was not added.

比較例2
実施例3において、2-アミノベンズイミダゾ-ル(和光純薬社製)を加えなったことを除いては、実施例3と同様にして電気絶縁用樹脂組成物をえた。
Comparative Example 2
A resin composition for electrical insulation was obtained in the same manner as in Example 3 except that 2-aminobenzimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) was not added.

実施例1〜4および比較例1〜2でえられた電気絶縁用樹脂組成物を用いて下記に示す焼付け条件にしたがって直径1.0mmの銅線に塗布、焼付けを行いエナメル線を製造した。
塗装回数:ダイス8回
焼付炉 :竪型熱風炉(炉長5m)
炉温 :入口/出口=320℃/430℃
線速 :16m/分
Using the resin compositions for electrical insulation obtained in Examples 1 to 4 and Comparative Examples 1 to 2, application and baking were performed on copper wires having a diameter of 1.0 mm according to the baking conditions shown below to produce enameled wires.
Number of paintings: 8 dice baking oven: Vertical hot air furnace (furnace length 5m)
Furnace temperature: Inlet / Outlet = 320 ° C / 430 ° C
Line speed: 16m / min

えられたエナメル線皮膜は、いずれも外観上平滑で異常が認められず、各エナメル線皮膜の特性を下記の方法により試験し、結果を表1に示した。
(1)ピンホール :JIS C 3003.36に準じて測定した。
(2)往復式摩耗性 :JIS C 3003(1966年度制定版).10.1に準じて測定した。
(3)一方向式摩耗性 :JIS C 3003.10に準じて測定した。
(4)可とう性 :JIS C 3003.8.1(1)に準じて測定した。
(5)絶縁破壊電圧 :JIS C 3003.11.(2)に準じて測定した。
(6)耐軟化性 :JIS C 3003.12(2)に準じて測定した。
None of the obtained enamel wire coatings were smooth and abnormal in appearance, and the characteristics of each enamel wire coating were tested by the following method. The results are shown in Table 1.
(1) Pinhole: Measured according to JIS C 3003.36.
(2) Reciprocating wear resistance: JIS C 3003 (established in 1966). Measured according to 10.1.
(3) Unidirectional wear: Measured according to JIS C 3003.10.
(4) Flexibility: Measured according to JIS C 3003.8.1 (1).
(5) Dielectric breakdown voltage: JIS C 3003.11. It measured according to (2).
(6) Softening resistance: Measured according to JIS C 3003.12 (2).

Figure 2006016487
Figure 2006016487

表1から、本発明の電気絶縁用樹脂組成物を用いてえられたエナメル線は、比較例1および2と比べて耐摩耗性に優れており、しかも可とう性および耐軟化性もほぼ同等に良好であることが分かる。


From Table 1, the enameled wire obtained using the resin composition for electrical insulation of the present invention is superior in wear resistance as compared with Comparative Examples 1 and 2, and is also substantially equivalent in flexibility and softening resistance. It turns out that it is favorable.


Claims (6)

(A)ポリアミドイミド樹脂及び、(B)2-アミノベンズイミダゾ-ルを含有してなる電気絶縁用樹脂組成物。 A resin composition for electrical insulation, comprising (A) a polyamideimide resin and (B) 2-aminobenzimidazole. (A)ポリアミドイミド樹脂の数平均分子量が10,000〜50,000である請求項1記載の電気絶縁用樹脂組成物。 The number average molecular weight of (A) polyamideimide resin is 10,000-50,000, The resin composition for electrical insulation of Claim 1 characterized by the above-mentioned. (A)ポリアミドイミド樹脂100重量部に対し、(B)2-アミノベンズイミダゾ-ル0.01〜10重量部を含む請求項1〜2いずれか1項記載の電気絶縁用樹脂組成物。 The resin composition for electrical insulation according to any one of claims 1 to 2, comprising 0.01 to 10 parts by weight of (B) 2-aminobenzimidazole with respect to 100 parts by weight of (A) polyamideimide resin. 請求項1〜3のいずれか1項記載の電気絶縁用樹脂組成物を導体上に直接または他の絶縁物を介して塗布、焼付けたエナメル線。 An enameled wire obtained by applying and baking the resin composition for electrical insulation according to any one of claims 1 to 3 on a conductor directly or via another insulator. (A)ポリアミドイミド樹脂及び、(B)2-アミノベンズイミダゾ-ルを含有してなる耐熱性樹脂組成物。 A heat-resistant resin composition comprising (A) a polyamideimide resin and (B) 2-aminobenzimidazole. 請求項5記載の耐熱性樹脂組成物を塗膜成分として含有してなる塗料。

A paint comprising the heat-resistant resin composition according to claim 5 as a coating film component.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012171979A (en) * 2011-02-17 2012-09-10 Hitachi Chemical Co Ltd Resin composition for electric insulation, and enamel wire

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01182364A (en) * 1988-01-14 1989-07-20 Hitachi Chem Co Ltd Heat resistant resin composition
JPH02218722A (en) * 1989-02-20 1990-08-31 Hitachi Chem Co Ltd Heat-resistant resin composition
JPH1160670A (en) * 1997-08-08 1999-03-02 Hitachi Chem Co Ltd Polyamideimide resin, its preparation therefor and coating material
JP2003045238A (en) * 2001-08-03 2003-02-14 Hitachi Cable Ltd Self-lubricating insulating cable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01182364A (en) * 1988-01-14 1989-07-20 Hitachi Chem Co Ltd Heat resistant resin composition
JPH02218722A (en) * 1989-02-20 1990-08-31 Hitachi Chem Co Ltd Heat-resistant resin composition
JPH1160670A (en) * 1997-08-08 1999-03-02 Hitachi Chem Co Ltd Polyamideimide resin, its preparation therefor and coating material
JP2003045238A (en) * 2001-08-03 2003-02-14 Hitachi Cable Ltd Self-lubricating insulating cable

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012171979A (en) * 2011-02-17 2012-09-10 Hitachi Chemical Co Ltd Resin composition for electric insulation, and enamel wire

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