JPH0750105A - Electric insulating resin composition and enameled wire - Google Patents
Electric insulating resin composition and enameled wireInfo
- Publication number
- JPH0750105A JPH0750105A JP5194585A JP19458593A JPH0750105A JP H0750105 A JPH0750105 A JP H0750105A JP 5194585 A JP5194585 A JP 5194585A JP 19458593 A JP19458593 A JP 19458593A JP H0750105 A JPH0750105 A JP H0750105A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polyester
- enameled wire
- insulating resin
- electric insulating
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 7
- 239000004020 conductor Substances 0.000 claims abstract description 7
- 238000010292 electrical insulation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- -1 alkyl terephthalate Chemical compound 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 210000003298 dental enamel Anatomy 0.000 description 9
- 150000007519 polyprotic acids Polymers 0.000 description 9
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 8
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229930003836 cresol Natural products 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000004072 triols Chemical class 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- REIDAMBAPLIATC-UHFFFAOYSA-M 4-methoxycarbonylbenzoate Chemical compound COC(=O)C1=CC=C(C([O-])=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電気絶縁用樹脂組成物お
よびエナメル線に関する。TECHNICAL FIELD The present invention relates to a resin composition for electrical insulation and an enamel wire.
【従来の技術】従来から電気絶縁用樹脂組成物、特にエ
ナメル線用樹脂組成物としては、比較的機械特性、電気
特性、耐熱性などのバランスがとれているため、ポリエ
ステルワニスが多く使用されている。しかし、近年のエ
ナメル線製造メーカーの製造工程の合理化や生産性向上
の観点から、高速焼付け性を有し、かつ特性低下のない
ポリエステルワニスが要求されている。従来のポリエス
テルワニスは、適正焼付け速度以上で焼付けを行うとそ
の特性が著しく劣る。この主な理由は、ポリエステルワ
ニスの硬化速度が遅く、適正焼付け速度以上で焼付けた
場合、ポリエステル樹脂が充分に高分子量化せず、塗膜
が充分な強靱性や耐熱性を示さないためである。したが
って、焼付け速度をさらに増加させるためには、ポリエ
ステルワニスの硬化速度を向上させる必要がある。2. Description of the Related Art Conventionally, polyester varnish is often used as a resin composition for electrical insulation, particularly a resin composition for enameled wire, because it has a relatively good balance of mechanical properties, electrical properties and heat resistance. There is. However, from the viewpoint of streamlining the manufacturing process and improving productivity of enameled wire manufacturers in recent years, there has been a demand for a polyester varnish having a high-speed baking property and having no property deterioration. The properties of conventional polyester varnish are remarkably inferior when baked at an appropriate baking speed or higher. The main reason for this is that the curing speed of the polyester varnish is slow, and when baked at an appropriate baking speed or higher, the polyester resin does not have a sufficiently high molecular weight and the coating film does not exhibit sufficient toughness and heat resistance. . Therefore, in order to further increase the baking speed, it is necessary to improve the hardening speed of the polyester varnish.
【０００２】[0002]
【発明が解決しようとする課題】本発明は、上記の従来
技術の問題を解決し、従来よりも高速で導体に焼付けて
エナメル線とした場合でも特性が低下しない電機絶縁用
樹脂組成物およびこれを用いたエナメル線を提供するも
のである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and a resin composition for electric machine insulation, which does not deteriorate in characteristics even when baked on a conductor to form an enamel wire at a higher speed than conventional ones, and the same. To provide an enamel wire using.
【０００３】[0003]
【課題を解決するための手段】本発明者らは、上記課題
に鑑み鋭意研究した結果、末端カルボキシル基または鎖
中単位として遊離のカルボキシル基を有するカルボキシ
ル化ポリエステルにエポキシ樹脂を特定割合で配合した
電気絶縁用樹脂組成物が硬化速度が速く、従来よりも高
速で導体に焼付けてエナメル線とした場合でも、諸特性
が良好であることを見出し、本発明に到った。Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have blended a carboxylated polyester having a terminal carboxyl group or a free carboxyl group as a unit in the chain with an epoxy resin in a specific ratio. The present inventors have found that the electrical insulating resin composition has a high curing speed, and that even when it is baked on a conductor at a higher speed than in the conventional case to form an enamel wire, various characteristics are good, and the present invention has been completed.
【０００４】すなわち、本発明は、水酸基含有ポリエス
テルに酸無水物を反応させて得られる末端カルボキシル
基または鎖中単位として遊離のカルボキシル基を有する
カルボキシル化ポリエステル１００重量部に対し、エポ
キシ樹脂３〜２０重量部を配合してなる電気絶縁用樹脂
組成物およびこの電気絶縁用樹脂組成物を導体上に塗
布、焼付けてなるエナメル線に関する。That is, the present invention is based on 100 parts by weight of a carboxylated polyester having a terminal carboxyl group obtained by reacting a hydroxyl group-containing polyester with an acid anhydride or a free carboxyl group as a unit in the chain, and an epoxy resin 3 to 20. TECHNICAL FIELD The present invention relates to a resin composition for electrical insulation in which parts by weight are mixed, and an enamel wire obtained by applying and baking the resin composition for electrical insulation on a conductor.
【０００５】本発明に用いられる水酸基含有ポリエステ
ルは、多価アルコール成分とテレフタル酸またはテレフ
タル酸アルキルを含む多塩基酸成分とを公知の方法によ
り反応させて得られる。多価アルコール成分としては、
例えば、エチレングリコール、ジエチレングリコール、
プロピレングリコール、ネオペンチルグリコール、１，
４−ブタンジオール、１，６−ヘキサンジオール等のジ
オール類、グリセリン、トリス−２−ヒドロキシエチル
イソシアヌレート、トリメチロールプロパン、ヘキサン
トリオール等のトリオール類などが用いられるが、トリ
オール類を多価アルコール成分の３０〜８０当量％の範
囲とするのが好ましく、より好ましくは４０〜６０当量
％の範囲にされる。トリオール類の配合割合が少ないと
硬化性および耐熱性が劣り、また多すぎると密着性およ
び可撓性が低下する場合がある。The hydroxyl group-containing polyester used in the present invention is obtained by reacting a polyhydric alcohol component with a terephthalic acid or a polybasic acid component containing an alkyl terephthalate by a known method. As a polyhydric alcohol component,
For example, ethylene glycol, diethylene glycol,
Propylene glycol, neopentyl glycol, 1,
Diols such as 4-butanediol and 1,6-hexanediol, triols such as glycerin, tris-2-hydroxyethyl isocyanurate, trimethylolpropane and hexanetriol are used, and triols are polyhydric alcohol components. Is preferably in the range of 30 to 80 equivalent%, and more preferably in the range of 40 to 60 equivalent%. If the blending ratio of triols is small, the curability and heat resistance may be poor, and if it is too large, the adhesion and flexibility may be poor.
【０００６】多塩基酸成分としてはテレフタル酸または
テレフタル酸アルキルが必須成分として用いられる。テ
レフタル酸そのものを用いてもよいが、エステル交換反
応により得られるテレフタル酸アルキル、例えばテレフ
タル酸ジメチル、テレフタル酸モノメチル、テレフタル
酸ジエチル等を用いてもよい。テレフタル酸またはテレ
フタル酸アルキルの使用量は、多塩基酸成分に対して４
０〜１００当量％の範囲が好ましい。また耐熱性向上た
め、一般式（１）As the polybasic acid component, terephthalic acid or alkyl terephthalate is used as an essential component. Although terephthalic acid itself may be used, an alkyl terephthalate obtained by a transesterification reaction, such as dimethyl terephthalate, monomethyl terephthalate, and diethyl terephthalate may be used. The amount of terephthalic acid or alkyl terephthalate used is 4 with respect to the polybasic acid component.
The range of 0 to 100 equivalent% is preferable. In order to improve heat resistance, the general formula (1)
【化１】 （式中のＲ1は３価の有機基、Ｒ2は４価の有機基を意味
する）に示されるイミド酸を併用することが好ましい。
このイミド酸としては、例えばジアミン１モルに対して
無水トリメリット酸２モルを反応させることにより得ら
れるイミドジカルボン酸（特公昭５１−４０１１３号公
報参照）が挙げられる。ジアミンと無水トリメリット酸
とは前もってイミドジカルボン酸としないで水酸基含有
ポリエステルの製造時に加えてもよい。[Chemical 1] (In the formula, R 1 represents a trivalent organic group and R 2 represents a tetravalent organic group) is preferably used in combination.
Examples of the imide acid include imide dicarboxylic acid obtained by reacting 2 mol of trimellitic anhydride with 1 mol of diamine (see Japanese Patent Publication No. 51-40113). The diamine and trimellitic anhydride may be added at the time of producing the hydroxyl group-containing polyester without being converted to imidodicarboxylic acid in advance.
【０００７】イミド酸の使用量は多塩基酸成分の３〜６
０当量％の範囲が好ましく、より好ましくは５〜４０当
量％の範囲とされる。イミド酸の使用量が少なすぎると
耐熱性が劣る傾向にあり、多すぎるとエナメル線の外観
が低下する場合がある。また多塩基酸成分として、エナ
メル銅線用ポリエステルワニスに常用される例えばイソ
フタル酸、アジピン酸、セバシン酸等を併用してもよ
い。多価アルコール成分と多塩基酸成分との配合割合に
は特に制限はないが、可撓性および耐熱性の点から、カ
ルボキシル基に対する水酸基の当量比を１．２〜２．４
にすることが好ましく、１．４〜１．８とすることがよ
り好ましい。The amount of imide acid used is 3 to 6 of the polybasic acid component.
The range of 0 equivalent% is preferable, and the range of 5 to 40 equivalent% is more preferable. If the amount of imidic acid used is too small, the heat resistance tends to be poor, and if it is too large, the appearance of the enameled wire may deteriorate. Further, as the polybasic acid component, for example, isophthalic acid, adipic acid, sebacic acid or the like which is commonly used for polyester varnish for enamel copper wire may be used in combination. The mixing ratio of the polyhydric alcohol component and the polybasic acid component is not particularly limited, but from the viewpoint of flexibility and heat resistance, the equivalent ratio of the hydroxyl group to the carboxyl group is 1.2 to 2.4.
It is preferable to set it to 1.4, and it is more preferable to set it to 1.4 to 1.8.
【０００８】本発明に用いられる末端カルボキシル基ま
たは鎖中単位として遊離のカルボキシル基を有するカル
ボキシル化ポリエステルは、上記で得られた水酸基含有
ポリエステルに酸無水物を付加反応させて得られる。酸
無水物としては、カルボキシル形成基を２個以上有する
ものであれば特に制限はなく、例えば、無水トリメリッ
ト酸、無水フタル酸、無水コハク酸等が用いられる。The carboxylated polyester having a terminal carboxyl group or a free carboxyl group as a unit in the chain used in the present invention can be obtained by addition-reacting an acid anhydride with the hydroxyl group-containing polyester obtained above. The acid anhydride is not particularly limited as long as it has two or more carboxyl forming groups, and, for example, trimellitic anhydride, phthalic anhydride, succinic anhydride and the like are used.
【０００９】カルボキシル化ポリエステルの合成法には
特に制限はなく、例えば、多価アルコール成分とテレフ
タル酸またはテレフタル酸アルキルを含む多塩基酸成分
とを上記の割合で、エステル化触媒の存在下に１７０〜
２５０℃の温度で加熱反応した後、１５０〜１８０℃に
降温し、酸無水物を付加させることにより行うことがで
きる。エステル化触媒としては、例えばテトラブトキシ
チタネート、酢酸鉛、ジブチルスズラウレート、ナフテ
ン酸亜鉛等を用いることができる。また合成時の粘度が
高いため、例えばフェノール、クレゾール、キシレノー
ル等のクレゾール系溶媒の共存下で合成を行うことが好
ましい。本発明において、カルボキシル化ポリエステル
の酸価は、耐熱性と耐溶剤性の点から、３〜５０とする
ことが好ましく、５〜５０とすることがより好ましい。
酸価は酸無水物の使用量によって調節され、反応中に酸
価を測定してこの範囲とされる。The method for synthesizing the carboxylated polyester is not particularly limited, and for example, the polyhydric alcohol component and the polybasic acid component containing terephthalic acid or alkyl terephthalate are added in the above proportions in the presence of an esterification catalyst to give 170 ~
It can be carried out by heating the reaction at a temperature of 250 ° C., then lowering the temperature to 150 to 180 ° C., and adding an acid anhydride. As the esterification catalyst, for example, tetrabutoxy titanate, lead acetate, dibutyl tin laurate, zinc naphthenate or the like can be used. Further, since the viscosity at the time of synthesis is high, it is preferable to perform the synthesis in the coexistence of a cresol-based solvent such as phenol, cresol, or xylenol. In the present invention, the acid value of the carboxylated polyester is preferably 3 to 50, more preferably 5 to 50 from the viewpoint of heat resistance and solvent resistance.
The acid value is adjusted by the amount of the acid anhydride used, and the acid value is measured during the reaction to be within this range.
【００１０】本発明に用いられるエポキシ樹脂には制限
はなく、通常２〜４価のエポキシ樹脂が用いられ、例え
ばエピコート８２８、エピコート１００４、エピコート
１００７（ビスフェノール型エポキシ樹脂、油化シェル
エポキシ社製商品名）、エポン１０３１Ｓ（多官能エポ
キシ樹脂、油化シェルエポキシ社製商品名）、ＥＲＬ４
２２１（脂環式エポキシ樹脂、ユニオンカーバイド社製
商品名）、ＤＮ４３８（クレゾールノボラック型エポキ
シ樹脂、チバガイギー社製商品名）等が用いられる。There is no limitation on the epoxy resin used in the present invention, and a divalent to tetravalent epoxy resin is usually used. For example, Epicoat 828, Epicoat 1004, Epicoat 1007 (bisphenol type epoxy resin, a product manufactured by Yuka Shell Epoxy Co., Ltd. Name), Epon 1031S (multifunctional epoxy resin, trade name manufactured by Yuka Shell Epoxy Co., Ltd.), ERL4
221 (alicyclic epoxy resin, trade name manufactured by Union Carbide Co., Ltd.), DN438 (cresol novolac type epoxy resin, trade name manufactured by Ciba Geigy Co., Ltd.) and the like are used.
【００１１】本発明の電気絶縁用樹脂組成物は、上記の
カルボキシル化ポリエステル１００重量部に対してエポ
キシ樹脂３〜２０重量部を配合して得られる。エポキシ
樹脂の配合量が３重量部未満では高速焼付け時の特性向
上に効果がなく、２０重量部を超えると可撓性が低下す
る。本発明の電気絶縁用樹脂組成物には、必要に応じて
テトラブトキシチタネートなどの硬化剤を添加してもよ
く、また芳香族カルボン酸の亜鉛、鉛、マンガン等の金
属塩を外観改良剤として添加してもよい。本発明の電気
絶縁用樹脂組成物は、導体上に焼付けて可撓性、耐熱性
等の諸特性に優れたエナメル線とされるが、該組成物が
優れた硬化性を有するため、従来より高速で焼付けた場
合にもエナメル線特性が低下することはない。The resin composition for electrical insulation of the present invention can be obtained by mixing 3 to 20 parts by weight of an epoxy resin with 100 parts by weight of the above-mentioned carboxylated polyester. If the amount of the epoxy resin compounded is less than 3 parts by weight, there is no effect in improving the characteristics during high-speed baking, and if it exceeds 20 parts by weight, flexibility decreases. The resin composition for electrical insulation of the present invention may be added with a curing agent such as tetrabutoxy titanate, if necessary, and zinc, lead or manganese of an aromatic carboxylic acid as an appearance improver. You may add. The resin composition for electrical insulation of the present invention is baked on a conductor to be an enameled wire excellent in various properties such as flexibility and heat resistance, but since the composition has excellent curability, Enamel wire characteristics do not deteriorate even when baked at high speed.
【００１２】[0012]
【実施例】以下、本発明を実施例によりさらに詳しく説
明するが、本発明はこれらに限定されるものではない。
なお、例中の％は特に記載がないかぎり重量％を意味す
る。 （１）カルボキシル化ポリエステル樹脂液の調製 温度計、攪拌機およびコンデンサ付き４つ口フラスコ
に、４，４′−ジアミノジフェニルメタン１９．８ｇ
（０．２当量）、無水トリメリット酸３８．４ｇ（０．
４当量）、テレフタル酸ジメチル３４９．２ｇ（３．６
当量）、グリセリン９８．１ｇ（３．２０当量）、エチ
レングリコール９９．２ｇ（３．２０当量）、クレゾー
ル１１７ｇおよびテトラブトキシチタネート１．３３ｇ
を入れ、窒素気流中で１７０℃に昇温して２時間反応さ
せた。次いで、得られた溶液を２１５℃に昇温して４時
間反応させて水酸基含有ポリエステルを合成した後、１
７０℃に降温して無水トリメリット酸２８．８ｇ（０．
３当量）を反応させて酸価を測定し、酸価２５の時点で
反応を止めてカルボキシル化ポリエステルを得た。得ら
れた樹脂溶液にクレゾール５６６ｇ、テトラブトキシチ
タネート４２．２ｇおよびオクテン酸亜鉛（金属分６
％）１３．３ｇを添加して不揮発分４０％のカルボキシ
ル化ポリエステル樹脂液を得た。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In addition,% in the examples means% by weight unless otherwise specified. (1) Preparation of carboxylated polyester resin liquid 4,4′-diaminodiphenylmethane (19.8 g) was placed in a four-necked flask equipped with a thermometer, a stirrer and a condenser.
(0.2 equivalent), trimellitic anhydride 38.4 g (0.
4 equivalents), dimethyl terephthalate 349.2 g (3.6
Equivalent), glycerin 98.1 g (3.20 equivalent), ethylene glycol 99.2 g (3.20 equivalent), cresol 117 g and tetrabutoxy titanate 1.33 g.
Was charged, and the temperature was raised to 170 ° C. in a nitrogen stream to react for 2 hours. Then, the obtained solution was heated to 215 ° C. and reacted for 4 hours to synthesize a hydroxyl group-containing polyester, and then 1
The temperature was lowered to 70 ° C. and 28.8 g of trimellitic anhydride (0.
3 equivalents) were reacted to measure the acid value, and when the acid value was 25, the reaction was stopped to obtain a carboxylated polyester. Cresol 566 g, tetrabutoxy titanate 42.2 g and zinc octenoate (metal content 6
%) 13.3 g was added to obtain a carboxylated polyester resin liquid having a nonvolatile content of 40%.
【００１３】（２）ポリエステル樹脂液の調製 温度計、攪拌機およびコンデンサ付き４つ口フラスコ
に、４，４′−ジアミノジフェニルメタン３９．６ｇ
（０．４当量）、無水トリメリット酸７６．８ｇ（０．
８当量）、テレフタル酸ジメチル３４９．２ｇ（３．６
当量）、グリセリン７３．０ｇ（２．３８当量）、エチ
レングリコール９９．８ｇ（３．２２当量）、クレゾー
ル１１４ｇおよびテトラブトキシチタネート１．２８ｇ
を入れ、窒素気流中で１７０℃に昇温して３時間反応さ
せた。次いで、得られた溶液を２１５℃に昇温して６時
間反応させポリエステルを合成した。得られた樹脂溶液
にクレゾール５８３ｇを加え、テトラブトキシチタネー
ト２６．４ｇおよびナフテン酸亜鉛（金属分６％）２
５．３ｇを添加して不揮発分４０％のポリエステル樹脂
液を得た。(2) Preparation of polyester resin liquid In a four-necked flask equipped with a thermometer, a stirrer and a condenser, 3,4 g of 4,4'-diaminodiphenylmethane was added.
(0.4 equivalent), 76.8 g of trimellitic anhydride (0.
8 equivalents), 349.2 g of dimethyl terephthalate (3.6
Equivalent), glycerin 73.0 g (2.38 equivalent), ethylene glycol 99.8 g (3.22 equivalent), cresol 114 g and tetrabutoxy titanate 1.28 g.
Was charged, the temperature was raised to 170 ° C. in a nitrogen stream, and the reaction was performed for 3 hours. Next, the obtained solution was heated to 215 ° C. and reacted for 6 hours to synthesize polyester. 583 g of cresol was added to the obtained resin solution, and 26.4 g of tetrabutoxy titanate and zinc naphthenate (metal content 6%) 2
5.3 g was added to obtain a polyester resin liquid having a nonvolatile content of 40%.
【００１４】実施例１、２および比較例１、２ （１）で得られたカルボキシル化ポリエステル樹脂液１
００ｇに、エピコート８２８（ビスフェノール型エポキ
シ樹脂、油化シェルエポキシ社製商品名）およびエピコ
ート１００７（ビスフェノール型エポキシ樹脂、油化シ
ェルエポキシ社製）をそれぞれ４ｇ（１０重量％）添加
して電気絶縁用樹脂組成物（実施例１はエポコート８２
８、実施例２はエピコート１００７を添加）を得た。こ
れらの電気絶縁用樹脂組成物を下記に示す焼付け条件に
従って直径１．０mmの銅線に塗布し、線速１６ｍ／分で
焼付けを行い、エナメル線を作製した。Examples 1 and 2 and Comparative Examples 1 and 2 Carboxylated polyester resin liquid 1 obtained in (1)
4 g (10 wt%) of Epicoat 828 (bisphenol type epoxy resin, trade name of Yuka Shell Epoxy Co., Ltd.) and Epicoat 1007 (bisphenol type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) were added to 00 g for electrical insulation. Resin composition (Epocoat 82 in Example 1)
8 and Example 2 added Epicoat 1007). The resin composition for electrical insulation was applied to a copper wire having a diameter of 1.0 mm according to the baking conditions shown below and baked at a linear speed of 16 m / min to prepare an enamel wire.
【００１５】また比較のため（１）で得られたカルボキ
シル化ポリエステル樹脂液（比較例１）および（２）で
得られたポリエステル樹脂液（比較例２）を同様にして
塗布し、比較例１では線速１４ｍ／分および１６ｍ／分
で焼付けを行い、比較例２では線速１２ｍ／分および１
３ｍ／分で焼付けを行い、エナメル線を作製した。 〔焼付け条件〕 焼付け炉：熱風式堅炉（炉長５．５ｍ） 炉温：入口／出口＝３２０℃／４３０℃ 得られたエナメル線の一般特性をＪＩＳ Ｃ ３００３
に準じて測定し、結果を表１に示した。For comparison, the carboxylated polyester resin liquid obtained in (1) (Comparative Example 1) and the polyester resin liquid obtained in (2) (Comparative Example 2) were applied in the same manner, and Comparative Example 1 Baking was performed at linear velocities of 14 m / min and 16 m / min, and in Comparative Example 2, linear velocities of 12 m / min and 1
Baking was performed at 3 m / min to produce an enamel wire. [Baking conditions] Baking furnace: Hot air furnace (furnace length 5.5 m) Furnace temperature: Inlet / outlet = 320 ° C / 430 ° C The general characteristics of the obtained enameled wire are JIS C 3003.
The results are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１から、実施例１、２の電気絶縁用樹脂
組成物を用いて得られたエナメル線は、従来より高速
（線速１６ｍ／分）で焼付けを行っても優れた耐クレー
ジング性および耐軟化性に優れることが示される。これ
に対し、比較例１および比較例２では、線速をそれぞれ
１４ｍ／分から１６ｍ／分（約１４％）、１２ｍ／分か
ら１３ｍ／分（約８％）上げると、耐クレージング性お
よび耐軟化性に劣ることが示される。From Table 1, the enameled wires obtained by using the resin compositions for electrical insulation of Examples 1 and 2 have excellent crazing resistance even when baked at a higher speed (linear speed of 16 m / min) than before. And that it is excellent in softening resistance. On the other hand, in Comparative Example 1 and Comparative Example 2, when the linear velocity was increased from 14 m / min to 16 m / min (about 14%) and from 12 m / min to 13 m / min (about 8%), respectively, crazing resistance and softening resistance Is shown to be inferior to.
【００１８】[0018]
【発明の効果】本発明の電気絶縁用樹脂組成物によれ
ば、従来よりもはるかに高速で焼付けた場合でも、耐ク
レージング性および耐熱性等の諸特性に優れたエナメル
線を製造することができ、工業的にきわめて有用であ
る。According to the resin composition for electric insulation of the present invention, it is possible to produce an enameled wire excellent in various properties such as crazing resistance and heat resistance even when baked at a much higher speed than before. It is possible and industrially very useful.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年１月３１日[Submission date] January 31, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】多塩基酸成分としてはテレフタル酸または
テレフタル酸アルキルが必須成分として用いられる。テ
レフタル酸そのものを用いてもよいが、エステル交換反
応により得られるテレフタル酸アルキル、例えばテレフ
タル酸ジメチル、テレフタル酸モノメチル、テレフタル
酸ジエチル等を用いてもよい。テレフタル酸またはテレ
フタル酸アルキルの使用量は、多塩基酸成分に対して４
０〜１００当量％の範囲が好ましい。また耐熱性向上た
め、一般式（１）As the polybasic acid component, terephthalic acid or alkyl terephthalate is used as an essential component. Although terephthalic acid itself may be used, an alkyl terephthalate obtained by a transesterification reaction, such as dimethyl terephthalate, monomethyl terephthalate, and diethyl terephthalate may be used. The amount of terephthalic acid or alkyl terephthalate used is 4 with respect to the polybasic acid component.
The range of 0 to 100 equivalent% is preferable. In order to improve heat resistance, the general formula (1)
【化１】 （式中のＲ1は３価の有機基、Ｒ2は２価の有機基を意味
する）に示されるイミド酸を併用することが好ましい。
このイミド酸としては、例えばジアミン１モルに対して
無水トリメリット酸２モルを反応させることにより得ら
れるイミドジカルボン酸（特公昭５１−４０１１３号公
報参照）が挙げられる。ジアミンと無水トリメリット酸
とは前もってイミドジカルボン酸としないで水酸基含有
ポリエステルの製造時に加えてもよい。[Chemical 1] (R 1 is a trivalent organic group in the formula, R 2 denotes a divalent organic group) may be used together imide acid represented preferred.
Examples of the imide acid include imide dicarboxylic acid obtained by reacting 2 mol of trimellitic anhydride with 1 mol of diamine (see Japanese Patent Publication No. 51-40113). The diamine and trimellitic anhydride may be added at the time of producing the hydroxyl group-containing polyester without being converted to imidodicarboxylic acid in advance.
Claims (2)
応させて得られる末端カルボキシル基または鎖中単位と
して遊離のカルボキシル基を有するカルボキシル化ポリ
エステル１００重量部に対し、エポキシ樹脂３〜２０重
量部を配合してなる電気絶縁用樹脂組成物。1. An epoxy resin in an amount of 3 to 20 parts by weight is added to 100 parts by weight of a carboxylated polyester having a terminal carboxyl group obtained by reacting a hydroxyl group-containing polyester with an acid anhydride or a free carboxyl group as a unit in the chain. A resin composition for electrical insulation obtained by the method.
導体上に塗布、焼付けてなるエナメル線。2. An enameled wire obtained by applying and baking the resin composition for electrical insulation according to claim 1 on a conductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5194585A JPH0750105A (en) | 1993-08-05 | 1993-08-05 | Electric insulating resin composition and enameled wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5194585A JPH0750105A (en) | 1993-08-05 | 1993-08-05 | Electric insulating resin composition and enameled wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0750105A true JPH0750105A (en) | 1995-02-21 |
Family
ID=16326994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5194585A Pending JPH0750105A (en) | 1993-08-05 | 1993-08-05 | Electric insulating resin composition and enameled wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0750105A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010077283A (en) * | 2008-09-26 | 2010-04-08 | Japan U-Pica Co Ltd | Multibranched polyester(meth)acrylate compound |
-
1993
- 1993-08-05 JP JP5194585A patent/JPH0750105A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010077283A (en) * | 2008-09-26 | 2010-04-08 | Japan U-Pica Co Ltd | Multibranched polyester(meth)acrylate compound |
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