JP5080915B2 - Heat-resistant self-bonding coating composition and heat-resistant self-bonding enameled wire - Google Patents

Heat-resistant self-bonding coating composition and heat-resistant self-bonding enameled wire Download PDF

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JP5080915B2
JP5080915B2 JP2007239493A JP2007239493A JP5080915B2 JP 5080915 B2 JP5080915 B2 JP 5080915B2 JP 2007239493 A JP2007239493 A JP 2007239493A JP 2007239493 A JP2007239493 A JP 2007239493A JP 5080915 B2 JP5080915 B2 JP 5080915B2
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孝彦 花田
健次 浅野
英行 菊池
謙吾 室内
雄二 高野
公 菅原
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Auto Chemical Industry Co Ltd
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Description

本発明は、産業用及び自動車用モータ、発電機など耐熱性を要求される電機コイルに好適に使用されるエナメル線の耐熱自己融着性塗料組成物及び耐熱自己融着性エナメル線に関する。 TECHNICAL FIELD The present invention relates to a heat-resistant self-bonding coating composition for enameled wire and a heat-resistant self-bonding enameled wire that are suitably used for electric coils that require heat resistance such as industrial and automotive motors and generators.

自己融着性エナメル線は、含浸ワニスレスによる工数低減、環境対応及びブラウン管の偏向ヨークに代表される異型コアレスコイルの製造に大いに貢献してきた。融着方法も通電、恒温槽、熱風による熱融着、アルコール、酢酸エチル、メチルエチルケトン等の低沸点溶剤による溶剤融着など多岐に亘るが、その用途は主に民生機器に限定されてきた。   Self-bonding enameled wires have greatly contributed to the reduction of man-hours by impregnating varnishless, environmental friendliness, and the manufacture of deformed coreless coils represented by cathode ray tube deflection yokes. There are various fusing methods such as energization, thermostatic bath, heat fusing with hot air, solvent fusing with a low boiling point solvent such as alcohol, ethyl acetate, methyl ethyl ketone, etc., but their uses have been mainly limited to consumer equipment.

これは、自己融着性エナメル線における融着層にポリビニルブチラール樹脂、共重合ポリアミド樹脂、ポリヒドロキシポリエーテル樹脂などの比較的耐熱性、軟化温度の低い熱可塑性樹脂材料を主剤とする塗料を使用してきたことによる。   This uses a coating mainly composed of thermoplastic resin materials with relatively low heat resistance and softening temperature, such as polyvinyl butyral resin, copolymerized polyamide resin, and polyhydroxy polyether resin, for the fused layer of self-bonding enameled wire. It depends on what has been done.

しかし近年、環境対策、VOC(Volatile Organic Compounds)規制により、産業用及び自動車用モータ、発電機等の高温雰囲気下で使用される電気機器への適用が要求されるようになった。そこで主剤としてポリスルホン樹脂、ポリエーテルスルホン樹脂等の高耐熱エンジニアリングプラスチックを用いた塗料についての検討は行われているものの、これらの熱可塑性樹脂は軟化温度が高く、240℃以上の温度をかけなければ所定の融着力を発現しないという欠点を有している。   However, in recent years, due to environmental measures and VOC (Volatile Organic Compounds) regulations, application to electric devices used in high-temperature atmospheres such as industrial and automobile motors and generators has been required. Therefore, although investigations have been made on paints using high heat-resistant engineering plastics such as polysulfone resins and polyethersulfone resins as main ingredients, these thermoplastic resins have a high softening temperature and must be applied at a temperature of 240 ° C. or higher. There is a disadvantage that the predetermined fusing force is not exhibited.

また、架橋による熱硬化性を付与する試みとして、官能基を持つ主材料に各種の硬化剤を添加した融着ワニスを、半硬化させた状態、すなわちBステージ状態で焼付け、熱融着時に硬化させ、耐熱性を向上させる検討も行われている。つまり、主剤としての樹脂に硬化剤を添加し、これを導体に塗布した後、Bステージ状態で焼付けして自己融着性エナメル線とし、これをコイル状に巻きつけた後に熱融着及び熱硬化させることで、VOCを発生せず耐熱性を向上させる検討も行われている。   In addition, as an attempt to impart thermosetting properties by crosslinking, a fusion varnish obtained by adding various curing agents to a main material having a functional group is baked in a semi-cured state, that is, in a B-stage state, and cured at the time of thermal fusion. The heat resistance is also being studied. In other words, a curing agent is added to the resin as the main agent, and this is applied to the conductor, and then baked in a B-stage state to form a self-bonding enameled wire, which is wound into a coil and then heat-sealed and heated. Studies have been made to improve heat resistance without causing VOC by curing.

この融着ワニスの一例としては、ポリヒドロキシポリエーテルまたはスルホン基を含有するポリヒドロキシポリエーテルに、安定化イソシアネート、各種エポキシ樹脂、レゾール型フェノール樹脂、メラミン樹脂、酸無水物などの硬化剤を添加する手法が取られているが、焼き付け時の熱により硬化反応が進行し所定の初期融着力を発現しない。また、官能基同士が常温において徐々に反応し、経日変化により初期融着力が大きく低下する、または、硬化が不十分で高温雰囲気での融着力が大幅に低下しコイルの変形、線のほつれを生ずる等の問題を有していた。   As an example of this fusion varnish, a curing agent such as stabilized isocyanate, various epoxy resins, resol type phenol resin, melamine resin, acid anhydride, etc. is added to polyhydroxy polyether or polyhydroxy polyether containing sulfone group. However, the curing reaction proceeds by heat during baking, and a predetermined initial fusing force is not exhibited. In addition, functional groups react gradually at room temperature, and the initial fusing power is greatly reduced due to changes over time, or the fusing power in a high-temperature atmosphere is greatly reduced due to insufficient curing, resulting in coil deformation and wire fraying. Have problems such as.

このように高温中で自己融着性エナメル線を使用する場合、高軟化点の樹脂を使用する手法は採れるものの、融着工程の温度が非常に高いことから、自己融着性エナメル線の絶縁層及び自己融着性エナメル線以外の絶縁材料の劣化を招く、融着工程自体の作業性を低下させるなどの問題を有している。   In this way, when using self-bonding enameled wires at high temperatures, although a method using a resin with a high softening point can be taken, the temperature of the fusing process is very high, so insulation of self-bonding enameled wires There are problems such as deterioration of insulating materials other than the layer and the self-bonding enameled wire, and deterioration of workability of the bonding process itself.

また、熱硬化手法に関しては、自己融着性エナメル線自体の熱融着力の温度バラツキなど信頼性に問題を有していた。   Further, regarding the thermosetting method, there is a problem in reliability such as temperature variation of the heat fusion force of the self-bonding enameled wire itself.

そこで本発明は、上記問題を解決し、高温雰囲気下においても、実用上問題のない融着力を保持する耐熱自己融着性塗料組成物及び耐熱自己融着性エナメル線を提供することを目的とする。 Accordingly, the present invention has an object to provide a heat-resistant self-bonding coating composition and a heat-resistant self-bonding enameled wire that can solve the above-mentioned problems and maintain a fusing force that has no practical problem even in a high-temperature atmosphere. To do.

本発明は上記目的を達成するために創案されたものであり、請求項1の発明は、化学式(1)に示すスルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、ビスマレイミドを10〜50重量部含有してなることを特徴とする耐熱自己融着性塗料組成物である。

Figure 0005080915
The present invention was devised to achieve the above object, and the invention of claim 1 is characterized in that bismaleimide is added in an amount of 10 to 10 parts by weight per 100 parts by weight of the sulfone group-containing polyhydroxy polyether resin represented by the chemical formula (1). A heat-resistant self-fusing coating composition characterized by containing 50 parts by weight.
Figure 0005080915

請求項2の発明は、化学式(1)に示すスルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、ビスマレイミドを10〜50重量部含有し、さらに上記スルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、滑剤を1〜10重量部含有することを特徴とする耐熱自己融着性塗料組成物である。 Invention of Claim 2 contains 10-50 weight part of bismaleimide with respect to 100 weight part of sulfone group containing polyhydroxy polyether resins shown in Chemical formula (1) , Furthermore, the said sulfone group containing polyhydroxy polyether resin 100 1 to 10 parts by weight of a lubricant with respect to parts by weight.

請求項の発明は、上記滑剤が、ポリエチレンワックス、シリコーン樹脂、フッ素樹脂などの合成系、蜜蝋、カルナウバ蝋、キャンデリラワックスなどの天然系のいずれか単独または複数の組み合わせからなる請求項2記載の耐熱自己融着性塗料組成物である。 According to a third aspect of the present invention, in the second aspect, the lubricant is composed of one or more combinations of synthetic systems such as polyethylene wax, silicone resin and fluororesin, and natural systems such as beeswax, carnauba wax and candelilla wax. It is a heat-resistant self-fusing coating composition .

請求項の発明は、上記スルホン基含有ポリヒドロキシポリエーテル樹脂は、分子骨格中にスルホン基が30〜50%含有されていると共に、上記ビスマレイミドと溶剤に溶解されている請求項1〜3いずれかに記載の耐熱自己融着性塗料組成物である。 A fourth aspect of the present invention, the sulfonic-group-containing polyhydroxy polyether resin, together with a sulfonic group is contained 30-50% in a molecular skeleton, claims are dissolved in the bismaleimide and the solvent 1-3 The heat-resistant self-fusing coating composition according to any one of the above.

請求項の発明は、上記溶剤が、飽和脂環式ケトン類、フェノール類、ジエチレングリコールモノアルキルエーテル類から選ばれる少なくとも1種以上からなる請求項記載の耐熱自己融着性塗料組成物である。 The invention according to claim 5 is the heat-resistant self-fusing coating composition according to claim 4 , wherein the solvent comprises at least one selected from saturated alicyclic ketones, phenols, and diethylene glycol monoalkyl ethers. .

請求項の発明は、導体上に直接または他の絶縁物を介して、融着層を設けてなる耐熱自己融着性エナメル線において、請求項1〜5いずれかに記載の耐熱自己融着性塗料組成物を形成する塗料を塗布焼き付けし、上記融着層を形成してなることを特徴とする耐熱自己融着性エナメル線である。 The invention of claim 6 is a heat resistant self-bonding enameled wire in which a fusion layer is provided directly on a conductor or via another insulator, and the heat resistant self-bonding according to any one of claims 1 to 5. A heat-resistant self-bonding enameled wire, which is formed by coating and baking a coating material that forms a heat-resistant coating composition to form the above-mentioned fused layer.

本発明によれば、200℃の高温雰囲気下において、実用上問題のない融着力を保持することができる耐熱自己融着性塗料を提供できる。   According to the present invention, it is possible to provide a heat-resistant self-fusing paint that can maintain a fusing force having no practical problem in a high-temperature atmosphere of 200 ° C.

以下、本発明の好適な実施形態を説明する。   Hereinafter, preferred embodiments of the present invention will be described.

本発明の好適な第1の実施形態に係る耐熱自己融着性塗料は、上述した化学式(1)に示すスルホン基含有ポリヒドロキシポリエーテル樹脂と、ビスマレイミドとを含有してなる。   A heat-resistant self-fusing paint according to the first preferred embodiment of the present invention comprises a sulfone group-containing polyhydroxy polyether resin represented by the above chemical formula (1) and bismaleimide.

スルホン基含有ポリヒドロキシポリエーテル樹脂は、工業的に実用化されているものならば特に限定されないが、より好ましくは熱融着性と耐熱性のバランスから分子骨格中に占めるスルホン基の含有量が30〜50%のものが適切である。   The sulfone group-containing polyhydroxy polyether resin is not particularly limited as long as it is industrially practical, but more preferably, the content of the sulfone group in the molecular skeleton is from the balance of heat-fusibility and heat resistance. 30-50% is suitable.

ビスマレイミドとしては、4,4’−ジフェニルメタンビスマレイミド、m−フェニレンビスマレイミド、ビスフェノールAジフェニルエーテルビスマレイミド、3,3’−ジメチル−5,5’ジエチル−4,4’−ジフェニルメタンビスマレイミド、4,4’−ジフェニルエーテルビスマレイミド、4,4’−ジフェニルスルホンビスマレイミド、1,3−ビス(3−マレイミドフェノキシ)ベンゼン、1,3−ビス(4−マレイミドフェノキシ)ベンゼン、1,6’−ビスマレイミド−(2,2,4−トリメチル)ヘキサン、ポリフェニルメタンマレイミドなどがあり、特に限定されないが、材料の入手性およびスルホン基含有ポリヒドロキシポリエーテル樹脂との適切な反応性から4,4’−ジフェニルメタンビスマレイミドが最も好ましく、m−フェニレンビスマレイミドも好適である。   As the bismaleimide, 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′diethyl-4,4′-diphenylmethane bismaleimide, 4, 4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,6′-bismaleimide -(2,2,4-trimethyl) hexane, polyphenylmethanemaleimide, and the like. Although not particularly limited, 4,4'- is preferred because of availability of materials and appropriate reactivity with sulfone group-containing polyhydroxypolyether resins. Diphenylmethane bismaleimide is most preferred Properly, m- phenylene bismaleimide are also suitable.

ビスマレイミドの添加量は、スルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して10〜100重量部が望ましく、さらには10〜50重量部が好ましい。10重量部未満では、スルホン基含有ポリヒドロキシポリエーテル樹脂との反応が不十分であり200℃の高温中での融着力が低下する。100重量部を超えると、融着層が硬く脆くなる、ワニス塗料でビスマレイミドが析出する、初期融着力が低下するなどの問題を生ずることによる。   The amount of bismaleimide added is desirably 10 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the sulfone group-containing polyhydroxy polyether resin. If the amount is less than 10 parts by weight, the reaction with the sulfone group-containing polyhydroxypolyether resin is insufficient, and the fusing force at a high temperature of 200 ° C. decreases. If the amount exceeds 100 parts by weight, problems such as the fusion layer becoming hard and brittle, bismaleimide being precipitated in the varnish coating, and the initial fusion force being lowered.

第1の実施形態に係る耐熱自己融着性塗料の溶剤としては、スルホン基含有ポリヒドロキシポリエーテル樹脂およびビスマレイミドを溶解できる溶剤ならよく、シクロヘキサノンなどの飽和脂環式ケトン類、クレゾールなどのフェノール類、メチルカルビトールなどのジエチレングリコールモノアルキルエーテル類から選ばれる少なくとも1種以上からなるものを使用できるが、焼き付け後の融着皮膜の残留溶剤および臭気対策からシクロヘキサノンが好ましい。また、キシレン、高沸点アルキルベンゼンなどで適宜希釈することができる。   The solvent for the heat-resistant self-fusing paint according to the first embodiment may be any solvent that can dissolve the sulfone group-containing polyhydroxypolyether resin and bismaleimide, such as saturated alicyclic ketones such as cyclohexanone, and phenol such as cresol. And at least one selected from diethylene glycol monoalkyl ethers such as methyl carbitol can be used, but cyclohexanone is preferred from the standpoint of residual solvent and odor control in the fused film after baking. Further, it can be appropriately diluted with xylene, high boiling point alkylbenzene or the like.

第1の実施形態に係る耐熱自己融着性塗料は、上述した溶剤に、スルホン基含有ポリヒドロキシポリエーテル樹脂とビスマレイミドとを溶解して得られる。   The heat-resistant self-fusing paint according to the first embodiment is obtained by dissolving a sulfone group-containing polyhydroxy polyether resin and bismaleimide in the solvent described above.

次に、第1の実施形態に係る耐熱自己融着性塗料を使用した耐熱自己融着性エナメル線の一例を図1を用いて説明する。   Next, an example of the heat-resistant self-bonding enameled wire using the heat-resistant self-bonding paint according to the first embodiment will be described with reference to FIG.

図1に示すように、第1の実施形態に係る耐熱自己融着性エナメル線10は、導体1上に、他の絶縁物としての絶縁層(例えば、ポリアミドイミドからなる)2を設け、その絶縁層2上に、上述した耐熱自己融着性塗料を塗布し、焼き付けて融着層(融着皮膜)3を形成することにより、得られる。   As shown in FIG. 1, the heat-resistant self-bonding enameled wire 10 according to the first embodiment is provided with an insulating layer (for example, made of polyamideimide) 2 as another insulator on the conductor 1, It is obtained by applying the above-mentioned heat-resistant self-bonding paint on the insulating layer 2 and baking it to form a bonding layer (fusion film) 3.

第1の実施形態の作用を説明する。   The operation of the first embodiment will be described.

第1の実施形態に係る耐熱自己融着性塗料は、化学式(1)に示すスルホン基含有ポリヒドロキシポリエーテル樹脂と、ビスマレイミドとを含有してなる。   The heat-resistant self-fusing paint according to the first embodiment comprises a sulfone group-containing polyhydroxy polyether resin represented by chemical formula (1) and bismaleimide.

このため、第1の実施形態に係る耐熱自己融着性塗料を塗布、焼き付けして耐熱自己融着性エナメル線10の融着層3として用いると、焼き付け時に溶剤がほぼ気化し、Bステージ状態で絶縁層2上に焼付けされて耐熱自己融着性エナメル線10が得られる。この耐熱自己融着性エナメル線10は、産業用及び自動車用モータ、発電機など耐熱性を要求される電機コイルとしての巻線に使用できる。   For this reason, when the heat-resistant self-bonding coating material according to the first embodiment is applied and baked and used as the bonding layer 3 of the heat-resistant self-bonding enameled wire 10, the solvent is almost vaporized during baking, and the B stage state The heat-resistant self-bonding enameled wire 10 is obtained by baking on the insulating layer 2. This heat-resistant self-bonding enameled wire 10 can be used for winding as an electric coil that requires heat resistance, such as industrial and automobile motors and generators.

耐熱自己融着性エナメル線10を巻線に使用すると、通電、恒温槽、熱風による熱融着などの融着方法により、従来よりも低い240℃未満の温度、好ましくは220℃で隣接するエナメル線同士が十分な融着力を発現すると共に、同温度にて熱硬化反応を生じて融着層3が架橋構造をとる。   When the heat-resistant self-bonding enameled wire 10 is used for the winding, the enamel adjacent at a temperature lower than 240 ° C., preferably 220 ° C., lower than the prior art, by a fusing method such as energization, thermostatic bath, hot fusing with hot air, etc. The wires express a sufficient fusing force and cause a thermosetting reaction at the same temperature, so that the fusing layer 3 has a crosslinked structure.

これにより、第1の実施形態に係る耐熱自己融着性塗料によれば、耐熱自己融着性エナメル線10に用いると、200℃の高温雰囲気下において、実用上問題のない融着力を保持することができる。   Thereby, according to the heat-resistant self-bonding coating material according to the first embodiment, when used in the heat-resistant self-bonding enameled wire 10, it retains a bonding force that has no practical problem in a high temperature atmosphere of 200 ° C. be able to.

また、第1の実施形態に係る耐熱自己融着性塗料では、融着工程の温度が従来よりも低くなるため、耐熱自己融着性エナメル線10の絶縁層2や、エナメル線以外の絶縁材料の劣化を防止でき、融着工程自体の作業性も向上する。   In the heat-resistant self-bonding paint according to the first embodiment, the temperature of the fusing process is lower than that of the conventional one. Therefore, the insulating layer 2 of the heat-resistant self-bonding enameled wire 10 or an insulating material other than the enameled wire is used. Deterioration can be prevented, and the workability of the fusing process itself is improved.

さらに、第1の実施形態に係る耐熱自己融着性塗料は、耐熱自己融着性エナメル線10自体の融着力の温度バラツキが小さく、高信頼性である。   Furthermore, the heat-resistant self-bonding coating material according to the first embodiment has a small temperature variation in the bonding force of the heat-resistant self-bonding enameled wire 10 itself and is highly reliable.

次に、第2の実施形態を説明する。   Next, a second embodiment will be described.

第2の実施形態に係る耐熱自己融着性塗料は、第1の実施形態に係る耐熱自己融着性塗料の構成に加え、さらにスルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、滑剤を含有する。   The heat-resistant self-fusing paint according to the second embodiment includes a lubricant with respect to 100 parts by weight of the sulfone group-containing polyhydroxy polyether resin in addition to the configuration of the heat-resistant self-fusing paint according to the first embodiment. Containing.

滑剤は、特に限定されるものではないが、ポリエチレンワックス、シリコーン樹脂、フッ素樹脂などの合成系、蜜蝋、カルナウバ蝋、キャンデリラワックスなどの天然系があり、これらの単独または複数の組み合わせにより使用することができる。塗料への溶解性、皮膜(被膜)化してからのすべり性および入手性から蜜蝋の使用が好ましい。   The lubricant is not particularly limited, and there are synthetic systems such as polyethylene wax, silicone resin and fluororesin, and natural systems such as beeswax, carnauba wax and candelilla wax, and these are used alone or in combination. be able to. Use of beeswax is preferred from the viewpoint of solubility in paint, slipperiness after formation of a film (film), and availability.

また、滑剤の添加量は、スルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、1〜10重量部が好ましく、更に1〜5重量部が好適である。1重量部未満ではすべり性が所望の値に達しないこと、10重量部を超えると、ワニス中での滑剤の分散が大幅に悪化してしまう場合がある。   Further, the addition amount of the lubricant is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the sulfone group-containing polyhydroxy polyether resin. If it is less than 1 part by weight, the slipping property does not reach a desired value. If it exceeds 10 parts by weight, dispersion of the lubricant in the varnish may be greatly deteriorated.

第2の実施形態に係る耐熱自己融着性塗料を用いて、図1の耐熱自己融着性エナメル線10と同様のエナメル線を作製すれば、滑剤により融着皮膜にすべり性を付与できるため、静摩擦係数が0.10以下である耐熱自己融着性エナメル線が得られる。   If an enameled wire similar to the heat-resistant self-bonding enameled wire 10 in FIG. 1 is produced using the heat-resistant self-bonding coating material according to the second embodiment, the slipping property can be imparted to the melted film by the lubricant. A heat-resistant self-bonding enameled wire having a static friction coefficient of 0.10 or less is obtained.

上記実施形態では、導体1上に絶縁層2を介して融着層3を設けた2層構造の耐熱自己融着性エナメル線10を説明したが、上記各実施形態に係る耐熱自己融着性塗料は、導体上に直接融着層を設けた1層構造の耐熱自己融着性エナメル線にも応用できる。   In the above embodiment, the heat-resistant self-bonding enameled wire 10 having a two-layer structure in which the fusion layer 3 is provided on the conductor 1 via the insulating layer 2 has been described. The paint can also be applied to a heat-resistant self-bonding enameled wire having a single-layer structure in which a bonding layer is directly provided on a conductor.

次に、本発明に係る熱硬化型耐熱自己融着性エナメル線の実施例を比較例と共に説明する。   Next, examples of the thermosetting heat-resistant self-bonding enameled wire according to the present invention will be described together with comparative examples.

(ポリアミドイミドエナメル線の作製)
図1に示すように、導体径φ0.8mmの導体1上にポリアミドイミド塗料を塗布、焼き付けすることにより皮膜厚さ0.030mmの絶縁層2を有するポリアミドイミドエナメル線を得た。
(Production of polyamide-imide enamel wire)
As shown in FIG. 1, a polyamide-imide enamel wire having an insulating layer 2 with a film thickness of 0.030 mm was obtained by applying and baking a polyamide-imide paint on a conductor 1 having a conductor diameter of φ0.8 mm.

(実施例1)
分子骨格中に占めるスルホン基の含有率が40%のスルホン基含有ポリヒドロキシポリエーテル樹脂100重量部、4,4’−ジフェニルメタンビスマレイミド10重量部をそれぞれ採取した。これをシクロヘキサノンと高沸点アルキルベンゼンからなる混合溶剤に溶解することにより樹脂分濃度25%の耐熱自己融着性塗料を作製した。
Example 1
100 parts by weight of a sulfone group-containing polyhydroxy polyether resin having a sulfone group content of 40% in the molecular skeleton and 10 parts by weight of 4,4′-diphenylmethane bismaleimide were collected. This was dissolved in a mixed solvent composed of cyclohexanone and high-boiling alkylbenzene to prepare a heat-resistant self-fusing paint having a resin concentration of 25%.

次に、上記ポリアミドイミドエナメル線の上に、実施例1の耐熱自己融着性塗料を塗布、焼き付けすることにより、厚さ0.010mmの融着層3を有する図1の耐熱自己融着性エナメル線10を得た。   Next, the heat-resistant self-fusing property shown in FIG. 1 having the fusion layer 3 having a thickness of 0.010 mm is obtained by applying and baking the heat-resistant self-fusing coating material of Example 1 on the polyamideimide enameled wire. An enameled wire 10 was obtained.

(実施例2)
4,4’−ジフェニルメタンビスマレイミドを30重量部とした以外は実施例1と同様の手法により耐熱自己融着性エナメル線10を得た。
(Example 2)
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 1 except that 4,4′-diphenylmethane bismaleimide was changed to 30 parts by weight.

(実施例3)
4,4’−ジフェニルメタンビスマレイミドを50重量部とした以外は実施例1と同様の手法により耐熱自己融着性エナメル線10を得た。
(Example 3)
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 1 except that 50 parts by weight of 4,4′-diphenylmethane bismaleimide was used.

(実施例4)
4,4’−ジフェニルメタンビスマレイミドを75重量部とした以外は実施例1と同様の手法により耐熱自己融着性エナメル線10を得た。
Example 4
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 1 except that 75 parts by weight of 4,4′-diphenylmethane bismaleimide was used.

(実施例5)
4,4’−ジフェニルメタンビスマレイミドを100重量部とした以外は実施例1と同様の手法により耐熱自己融着性エナメル線10を得た。
(Example 5)
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 1 except that 100 parts by weight of 4,4′-diphenylmethane bismaleimide was used.

(実施例6)
4,4’−ジフェニルメタンビスマレイミドに代わりm−フェニレンビスマレイミド30重量部を用いた以外は実施例1と同様の手法により耐熱自己融着性エナメル線10を得た。
(Example 6)
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 1 except that 30 parts by weight of m-phenylene bismaleimide was used instead of 4,4′-diphenylmethane bismaleimide.

(実施例7)
分子骨格中に占めるスルホン基の含有率が40%のスルホン基含有ポリヒドロキシポリエーテル樹脂100重量部、4,4’−ジフェニルメタンビスマレイミド30重量部をそれぞれ採取した。これをシクロヘキサノンと高沸点アルキルベンゼンからなる混合溶剤に溶解することにより樹脂分濃度25%の実施例2の耐熱自己融着性塗料を作製した。
(Example 7)
100 parts by weight of sulfone group-containing polyhydroxy polyether resin having a sulfone group content of 40% in the molecular skeleton and 30 parts by weight of 4,4′-diphenylmethane bismaleimide were collected. This was dissolved in a mixed solvent composed of cyclohexanone and high-boiling alkylbenzene to prepare a heat-resistant self-fusing paint of Example 2 having a resin concentration of 25%.

これに蜜蝋1重量部を添加し溶解することにより実施例7の耐熱自己融着性塗料を得た。上記のポリアミドイミドエナメル線の上に、実施例7の融着塗料を塗布、焼き付けすることにより融着層厚さ0.010mmの耐熱自己融着性エナメル線10を得た。   1 part by weight of beeswax was added thereto and dissolved to obtain the heat-resistant self-fusing paint of Example 7. A heat-resistant self-bonding enameled wire 10 having a fusion layer thickness of 0.010 mm was obtained by applying and baking the coating material of Example 7 on the polyamideimide enameled wire.

(実施例8)
蜜蝋の添加量を2.5重量部とした以外は実施例7と同様の手法により耐熱自己融着性エナメル線10を得た。
(Example 8)
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 7 except that the amount of beeswax added was 2.5 parts by weight.

(実施例9)
蜜蝋の添加量を5.0重量部とした以外は実施例7と同様の手法により耐熱自己融着性エナメル線10を得た。
Example 9
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 7 except that the amount of beeswax added was 5.0 parts by weight.

(実施例10)
蜜蝋の添加量を10.0重量部とした以外は、実施例7と同様の手法により耐熱自己融着性エナメル線10を得た。
(Example 10)
A heat-resistant self-bonding enameled wire 10 was obtained in the same manner as in Example 7 except that the amount of beeswax added was 10.0 parts by weight.

(比較例1)
分子骨格中に占めるスルホン基の含有率が40%のスルホン基含有ポリヒドロキシポリエーテル樹脂をシクロヘキサノンと高沸点アルキルベンゼンからなる混合溶剤に溶解することにより樹脂分濃度25%の比較例1の融着塗料を作製した。
(Comparative Example 1)
The fusion coating composition of Comparative Example 1 having a resin content concentration of 25% by dissolving a sulfo group-containing polyhydroxy polyether resin having a sulfone group content of 40% in the molecular skeleton in a mixed solvent composed of cyclohexanone and high-boiling alkylbenzene. Was made.

上記のポリアミドイミドエナメル線の上に、比較例1の融着塗料を塗布、焼き付けすることにより融着層厚さ0.010mmの自己融着性エナメル線を得た。   A self-adhesive enameled wire having a fused layer thickness of 0.010 mm was obtained by applying and baking the fused paint of Comparative Example 1 on the polyamideimide enameled wire.

(比較例2)
4,4’−ジフェニルメタンビスマレイミドを7.5重量部とした以外は実施例1と同様の手法により耐熱自己融着性エナメル線を得た。
(Comparative Example 2)
A heat-resistant self-bonding enameled wire was obtained in the same manner as in Example 1 except that 7.5 parts by weight of 4,4′-diphenylmethane bismaleimide was used.

(比較例3)
4,4’−ジフェニルメタンビスマレイミドを110重量部とした以外は実施例1と同様の手法により耐熱自己融着性エナメル線を得た。
(Comparative Example 3)
A heat-resistant self-bonding enameled wire was obtained in the same manner as in Example 1 except that 4,4′-diphenylmethane bismaleimide was changed to 110 parts by weight.

(比較例4)
蜜蝋の添加量を0.5重量部とした以外は実施例7と同様の手法により耐熱自己融着性エナメル線を得た。
(Comparative Example 4)
A heat-resistant self-bonding enameled wire was obtained in the same manner as in Example 7 except that the amount of beeswax added was 0.5 parts by weight.

(比較例5)
蜜蝋の添加量を12.5重量部とした以外は実施例7と同様の手法により耐熱自己融着性エナメル線を得た。
(Comparative Example 5)
A heat-resistant self-bonding enameled wire was obtained in the same manner as in Example 7 except that the amount of beeswax added was 12.5 parts by weight.

(比較例6)
4,4’−ジフェニルメタンビスマレイミドの代わりにレゾール型フェノール樹脂H−2181(日立化成社製)を15重量部用いたこと以外は実施例1と同様の手法により耐熱自己融着性エナメル線を得た。
(Comparative Example 6)
A heat-resistant self-bonding enameled wire was obtained in the same manner as in Example 1 except that 15 parts by weight of resol type phenol resin H-2181 (manufactured by Hitachi Chemical Co., Ltd.) was used instead of 4,4′-diphenylmethane bismaleimide. It was.

(比較例7)
4,4’−ジフェニルメタンビスマレイミドの代わりに安定化イソシアネートAP−STABLEを5重量部用いたこと以外は実施例1と同様の手法により耐熱自己融着性エナメル線を得た。
(Comparative Example 7)
A heat resistant self-bonding enameled wire was obtained in the same manner as in Example 1 except that 5 parts by weight of stabilized isocyanate AP-STABLE was used instead of 4,4′-diphenylmethane bismaleimide.

(比較例8)
ポリスルホン樹脂をクレゾールとキシレンの混合剤に溶解することにより樹脂分濃度25%の比較例8の融着塗料を作製した。次に、上記ポリアミドイミドエナメル線の上に、比較例8の融着塗料を塗布、焼き付けすることにより融着層厚さ0.010mmの自己融着性エナメル線を得た。
(Comparative Example 8)
A fusion paint of Comparative Example 8 having a resin concentration of 25% was prepared by dissolving polysulfone resin in a mixture of cresol and xylene. Next, the fusion-bonding paint of Comparative Example 8 was applied onto the polyamide-imide enamel wire and baked to obtain a self-bonding enamel wire having a fusion layer thickness of 0.010 mm.

(自己融着性エナメル線の試験方法)
(1)熱融着性試験
熱融着性試験はNEMA規格に準拠し行った。供試用の耐熱自己融着性エナメル線を内径5.6mmの70ターンのヘリカルコイルとした。このヘリカルコイルを所定の温度で10分間加熱し隣接線間を熱融着させた。次に、その隣接線間を熱融着させたヘリカルコイルを室温(20℃)で座屈試験し、座屈強度を融着力とした。
(Test method for self-bonding enameled wire)
(1) Thermal fusibility test The thermal fusibility test was performed in accordance with NEMA standards. The heat resistant self-bonding enamel wire for the test was a 70-turn helical coil with an inner diameter of 5.6 mm. This helical coil was heated at a predetermined temperature for 10 minutes to heat-seal between adjacent wires. Next, the helical coil in which the adjacent lines were thermally fused was subjected to a buckling test at room temperature (20 ° C.), and the buckling strength was defined as the fusion force.

(2)高温下の接着力試験
熱融着性試験と同様にNEMA規格に準拠し行った。供試用の耐熱自己融着性エナメル線を内径5.6mmの70ターンのヘリカルコイルとし、220℃で10分間加熱して隣接線間を熱融着させた。尚、比較例8のみは240℃で10分間加熱し、熱融着させた。次に、隣接線間を熱融着させたヘリカルコイルを200℃中に10分間置き、200℃中で座屈試験を行い、座屈強度を接着力とした。
(2) Adhesive strength test at high temperature It was performed in conformity with the NEMA standard in the same manner as the thermal fusion test. The heat-resistant self-bonding enamel wire for the test was made into a 70-turn helical coil with an inner diameter of 5.6 mm and heated at 220 ° C. for 10 minutes to thermally bond the adjacent wires. Only Comparative Example 8 was heated at 240 ° C. for 10 minutes and thermally fused. Next, the helical coil in which the adjacent wires were heat-sealed was placed at 200 ° C. for 10 minutes, and a buckling test was performed at 200 ° C. to determine the buckling strength as the adhesive strength.

(3)熱硬化の確認
供試用の耐熱自己融着性エナメル線、自己融着性エナメル線10cmを各々2本採取し、マイクロメーターで外径を測定する。採取した2本のうちの1本をメチルエチルケトンに室温(20℃)で10分間浸漬した後、耐熱自己融着性エナメル線、自己融着性エナメル線の表面を脱脂綿でふき取り、マイクロメーターで外径を測定し融着層が剥離されたかどうかの確認を行った。もう1本を220℃で10分間加熱し、冷却した後同様にメチルエチルケトンに室温(20℃)で10分間浸漬し、ふき取り後の外径を測定して、熱硬化の有無を確認した。なお、比較例8はメチルエチルケトンに溶解しないことから除外した。
(3) Confirmation of thermosetting Take two heat-resistant self-bonding enameled wires and 10 cm of self-bonding enameled wires for testing, and measure the outer diameter with a micrometer. After one of the two samples was immersed in methyl ethyl ketone for 10 minutes at room temperature (20 ° C), the heat-resistant self-bonding enameled wire and the surface of the self-bonding enameled wire were wiped with absorbent cotton and the outer diameter was measured with a micrometer. Was measured, and it was confirmed whether or not the fused layer was peeled off. The other was heated at 220 ° C. for 10 minutes, cooled, and then similarly immersed in methyl ethyl ketone at room temperature (20 ° C.) for 10 minutes, and the outer diameter after wiping was measured to confirm the presence or absence of thermosetting. Comparative Example 8 was excluded because it did not dissolve in methyl ethyl ketone.

(4)静摩擦係数
図2に図1の耐熱自己融着性エナメル線の静摩擦係数の測定に用いた傾斜法静摩擦係数試験機の概要を示す。
(4) Static Friction Coefficient FIG. 2 shows an outline of the gradient method static friction coefficient tester used for measuring the static friction coefficient of the heat resistant self-bonding enameled wire of FIG.

この試験機を用いて、図2に示すように、長さ400mmの供試用の耐熱自己融着性エナメル線を3本採り、標点距離を350mmとし3%伸長後、2本を試料23として傾斜可能に設けたプレート21に、もう1本を半分に切りそれぞれ試料23としてプレート22に取り付ける。そして、プレート22を、線同士が直角になるようにプレート21上に重ねる。その場合、試料23が接触していることを確認する。次に、プレート21を傾斜速度1度/3秒に傾斜させ、プレート22が少しでも動き出す時のプレート21の傾斜角度θを求める。静摩擦係数(μ)はμ=tanθにより求める。なお、tanθはtanθ表示盤24に表示されており、指針25の位置から直読出来る様になっている。なお、傾斜角度θが0のときに水準器26が水平を示していないときは水平を示すように水平調節ネジ27で調整を行う。   Using this testing machine, as shown in FIG. 2, three heat-resistant self-bonding enamel wires with a length of 400 mm were taken, the gauge distance was 350 mm, and after 3% elongation, two were used as sample 23. Another plate is cut in half on the plate 21 provided so as to be inclined, and each is attached to the plate 22 as a sample 23. Then, the plate 22 is overlaid on the plate 21 so that the lines are at right angles. In that case, it is confirmed that the sample 23 is in contact. Next, the plate 21 is inclined at an inclination speed of 1 degree / 3 seconds, and the inclination angle θ of the plate 21 when the plate 22 starts to move even a little is obtained. The static friction coefficient (μ) is obtained by μ = tan θ. Note that tan θ is displayed on the tan θ display board 24 so that it can be read directly from the position of the pointer 25. If the level 26 is not level when the tilt angle θ is 0, the level adjustment screw 27 is used to adjust the level.

表1に、実施例1〜10の耐熱自己融着性塗料(エナメル線作製後は融着層3)の組成と耐熱自己融着性エナメル線の融着力及び静摩擦係数を示す。表2には、比較例1〜8について表1と同様に示す。   Table 1 shows the composition of the heat-resistant self-bonding paints of Examples 1 to 10 (the fusion layer 3 after the enamel wire is prepared), the fusing force and the static friction coefficient of the heat-resistant self-bonding enamel wire. In Table 2, it shows similarly to Table 1 about Comparative Examples 1-8.

Figure 0005080915
Figure 0005080915

Figure 0005080915
Figure 0005080915

表1に示すように、実施例1〜10は、240℃未満の温度で十分な熱融着力を発現しており、しかも200℃の高温雰囲気下において、十分な接着力を有していることがわかる。   As shown in Table 1, Examples 1 to 10 exhibit a sufficient heat-sealing force at a temperature of less than 240 ° C., and have a sufficient adhesive force in a high-temperature atmosphere of 200 ° C. I understand.

これに対し、ビスマレイミドを添加しないスルホン基含有ポリヒドロキシポリエーテル樹脂単独である比較例1は、高温下の接着力が実施例1〜10に比べ大幅に劣る。   On the other hand, Comparative Example 1, which is a sulfone group-containing polyhydroxy polyether resin alone without adding bismaleimide, is significantly inferior to Examples 1-10 in adhesive strength at high temperatures.

比較例2はビスマレイミドの添加量が7.5重量部であり、高温下の接着力が実施例の約半分である。   In Comparative Example 2, the amount of bismaleimide added is 7.5 parts by weight, and the adhesive strength at high temperature is about half that of the example.

比較例3はビスマレイミドの添加量が110重量部であり、高温下の接着力が実施例1〜10に比べ向上せず、またワニス中に析出物が発生する。   In Comparative Example 3, the amount of bismaleimide added is 110 parts by weight, the adhesive strength at high temperature is not improved as compared with Examples 1 to 10, and precipitates are generated in the varnish.

比較例4は滑剤を0.5重量部添加したものであるが、すべり性が滑剤を規定量(1〜5重量部)添加した実施例7〜10に比べ低下する。   In Comparative Example 4, 0.5 part by weight of the lubricant is added, but the slipping property is lowered as compared with Examples 7 to 10 in which the specified amount (1 to 5 parts by weight) of the lubricant is added.

比較例5は滑剤を12.5重量部添加したものであるが、1週間でワニス中の滑剤が一部析出し分散不良が発生した。   In Comparative Example 5, 12.5 parts by weight of a lubricant was added. In one week, a part of the lubricant in the varnish was precipitated and poor dispersion occurred.

比較例6はビスマレイミドに代えてレゾール型フェノール樹脂を硬化剤として用いたものであるが、高温下の接着力が実施例1〜9に及ばないと共に、40℃の雰囲気に1週間程度放置することにより熱融着力が低下する。これは経時変化により架橋が進み融着層の流れを阻害するものと考えられ実用上大きな問題である。   In Comparative Example 6, a resol type phenol resin was used as a curing agent instead of bismaleimide, but the adhesive strength under high temperature did not reach that of Examples 1 to 9 and was left in an atmosphere at 40 ° C. for about 1 week. As a result, the heat sealing force decreases. This is a big problem in practical use because it is considered that cross-linking progresses with time and the flow of the fusion layer is inhibited.

比較例7はビスマレイミドに代えて安定化イソシアネートを硬化剤として用いたものであるが、焼き付け時に硬化が進行し熱融着力が大幅に低目である。   In Comparative Example 7, stabilized isocyanate was used as a curing agent in place of bismaleimide, but curing progressed during baking and the thermal fusion power was significantly low.

比較例8はポリスルホン樹脂を用いたものであるが、220℃での熱融着力が低く、より高温(240℃以上)での条件を必要とする。また、高温下での接着力も実施例に及ばない。   Although the comparative example 8 uses a polysulfone resin, the heat-sealing force at 220 ° C. is low, and a condition at a higher temperature (240 ° C. or higher) is required. Also, the adhesive strength at high temperatures is not as good as in the examples.

特に、これら比較例1〜8に対し実施例1〜6はいずれも220℃の熱融着力及び高温下での接着力も良好である。また、比較例6の様な熱融着力の経時変化も生じない。   In particular, each of Examples 1 to 6 with respect to Comparative Examples 1 to 8 has good heat-sealing power at 220 ° C. and adhesive strength at high temperatures. Further, the time-dependent change of the heat sealing force as in Comparative Example 6 does not occur.

実施例7〜10は実施例2に滑剤として蜜蝋を添加したものであるが、すべり性は著しく向上し、巻線性の向上が見込まれる。また、熱融着力、高温下での接着力も実施例1〜6と同等の値を示す。   In Examples 7-10, beeswax was added as a lubricant to Example 2, but the slipperiness was remarkably improved and the winding property was expected to be improved. Moreover, the heat sealing | fusion force and the adhesive force under high temperature also show the value equivalent to Examples 1-6.

本発明の好適な第1の実施形態である耐熱自己融着性塗料を用いた耐熱自己融着性エナメル線の一例を示す横断面図である。It is a cross-sectional view showing an example of a heat-resistant self-bonding enameled wire using a heat-resistant self-bonding paint that is a preferred first embodiment of the present invention. 図2(a)は、実施例において、エナメル線の静摩擦係数の測定に用いる傾斜法静摩擦係数試験機の平面図、図2(b)はその正面図、図2(c)はその側面図である。2A is a plan view of a gradient method static friction coefficient tester used for measuring the static friction coefficient of an enamel wire in the embodiment, FIG. 2B is a front view thereof, and FIG. 2C is a side view thereof. is there.

符号の説明Explanation of symbols

1 導体
2 絶縁層
3 融着層
10 耐熱自己融着性エナメル線
DESCRIPTION OF SYMBOLS 1 Conductor 2 Insulating layer 3 Fusion layer 10 Heat resistant self-bonding enameled wire

Claims (6)

化学式(1)に示すスルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、ビスマレイミドを10〜50重量部含有してなることを特徴とする耐熱自己融着性塗料組成物。
Figure 0005080915
A heat-resistant self-fusing coating composition comprising 10 to 50 parts by weight of bismaleimide with respect to 100 parts by weight of a sulfone group-containing polyhydroxy polyether resin represented by chemical formula (1) .
Figure 0005080915
化学式(1)に示すスルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、ビスマレイミドを10〜50重量部含有し、さらに上記スルホン基含有ポリヒドロキシポリエーテル樹脂100重量部に対して、滑剤を1〜10重量部含有することを特徴とする耐熱自己融着性塗料組成物。 10 to 50 parts by weight of bismaleimide with respect to 100 parts by weight of the sulfone group-containing polyhydroxy polyether resin represented by the chemical formula (1), and further with respect to 100 parts by weight of the sulfone group-containing polyhydroxy polyether resin. 1 to 10 parts by weight of a heat-resistant self-fusing coating composition, 上記滑剤が、ポリエチレンワックス、シリコーン樹脂、フッ素樹脂などの合成系、蜜蝋、カルナウバ蝋、キャンデリラワックスなどの天然系のいずれか単独または複数の組み合わせからなる請求項2記載の耐熱自己融着性塗料組成物。   The heat-resistant self-bonding paint according to claim 2, wherein the lubricant is composed of one or a combination of synthetic systems such as polyethylene wax, silicone resin, fluororesin, and natural systems such as beeswax, carnauba wax, and candelilla wax. Composition. 上記スルホン基含有ポリヒドロキシポリエーテル樹脂は、分子骨格中にスルホン基が30〜50%含有されていると共に、上記ビスマレイミドと溶剤に溶解されている請求項1〜3いずれかに記載の耐熱自己融着性塗料組成物。   The heat-resistant self according to any one of claims 1 to 3, wherein the sulfone group-containing polyhydroxy polyether resin contains 30 to 50% of a sulfone group in a molecular skeleton and is dissolved in the bismaleimide and a solvent. A fusible coating composition. 上記溶剤が、飽和脂環式ケトン類、フェノール類、ジエチレングリコールモノアルキルエーテル類から選ばれる少なくとも1種以上からなる請求項4記載の耐熱自己融着性塗料組成物。   The heat-resistant self-bonding coating composition according to claim 4, wherein the solvent comprises at least one selected from saturated alicyclic ketones, phenols, and diethylene glycol monoalkyl ethers. 導体上に直接または他の絶縁物を介して、融着層を設けてなる耐熱自己融着性エナメル線において、請求項1〜5いずれかに記載の耐熱自己融着性塗料組成物を形成する塗料を塗布焼き付けし、上記融着層を形成してなることを特徴とする耐熱自己融着性エナメル線。   The heat-resistant self-bonding coating composition according to any one of claims 1 to 5 is formed in a heat-resistant self-bonding enameled wire in which a bonding layer is provided directly on the conductor or via another insulator. A heat-resistant self-bonding enameled wire formed by coating and baking a paint to form the above-mentioned fused layer.
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