JPH0245575A - Self-fusing insulating paint - Google Patents
Self-fusing insulating paintInfo
- Publication number
- JPH0245575A JPH0245575A JP19862688A JP19862688A JPH0245575A JP H0245575 A JPH0245575 A JP H0245575A JP 19862688 A JP19862688 A JP 19862688A JP 19862688 A JP19862688 A JP 19862688A JP H0245575 A JPH0245575 A JP H0245575A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- bisphenol
- formula
- reaction
- self
- 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.)
- Granted
Links
- 239000003973 paint Substances 0.000 title claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 125000001174 sulfone group Chemical group 0.000 claims abstract description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 24
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 150000007524 organic acids Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000003457 sulfones Chemical group 0.000 abstract description 3
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical group C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 abstract description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical group C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 24
- 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 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 150000007530 organic bases Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000013034 phenoxy resin Substances 0.000 description 4
- 229920006287 phenoxy resin Polymers 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- -1 alkylene ether modified ethylene terephthalate Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- IEEZXCFWEVKMQT-UHFFFAOYSA-N 4-(1-phenylpropyl)phenol Chemical compound C=1C=C(O)C=CC=1C(CC)C1=CC=CC=C1 IEEZXCFWEVKMQT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012374 esterification agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Insulating Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は優れた耐熱性を有するスルホン基含有ポリヒド
ロキシポリエーテル樹脂を含有する自己融着性絶縁塗料
に関する。DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a self-bonding insulating paint containing a sulfone group-containing polyhydroxy polyether resin having excellent heat resistance.
「従来技術」
自己融着性エナメル電線の融着層に用いられる融着被膜
材料は一般にポリビニルブチラール樹脂、ポリアミド系
樹脂、アルキレンエーテル変性エチレンテレフタレート
樹脂等の熱可塑性樹脂が使用されている。しかしこれら
の融着材料は熱変形温度が低く、機器の使用温度が高く
なったシ間欠的温度上昇により融着層の流動や熱変形を
起こしてしまい、耐熱寿命Ａ種あるいはＥ種程度の部品
にしか使用できない。"Prior Art" The adhesive coating material used for the adhesive layer of self-bonding enameled electric wires is generally a thermoplastic resin such as polyvinyl butyral resin, polyamide resin, or alkylene ether modified ethylene terephthalate resin. However, these adhesive materials have a low heat distortion temperature, and when the operating temperature of the equipment is high, intermittent temperature rises can cause the adhesive layer to flow and thermal deformation, resulting in parts with a heat-resistant life of class A or class E. Can only be used.
又接着力や耐熱変形等の改良のためにエポキシ樹脂、フ
ェノール樹脂、ポリイソシアネートブロック体等の熱硬
化性樹脂を混合して熱硬化型とし半硬化状態に塗布し焼
付けて、自己融着性絶縁電線を得る方法がある。しかし
この方法は焼付被膜の可撓性、作業性や熱硬化性樹脂の
配合に制限され大巾な向上は期待できない。一方耐熱性
の高いエンジニアリングプラスチック、例えばポリスル
ホン樹脂、ポリエーテルスルホン樹脂を用いる方法もあ
る。この方法の場合、耐熱性はすぐれているものの融着
成形するときに高温を必要とするため、絶縁電線の不良
を発生させたり形成被膜が可撓性に乏しい欠点があった
。In order to improve adhesion and heat deformation resistance, thermosetting resins such as epoxy resin, phenol resin, and polyisocyanate blocks are mixed to form a thermosetting type, applied to a semi-cured state, and baked to create self-bonding insulation. There is a way to get the wire. However, this method is limited by the flexibility of the baked film, workability, and the composition of the thermosetting resin, and no significant improvement can be expected. On the other hand, there is also a method of using engineering plastics with high heat resistance, such as polysulfone resin and polyethersulfone resin. Although this method has excellent heat resistance, it requires high temperatures during fusion molding, resulting in defects in the insulated wire and poor flexibility in the formed coating.
又実用上有効な方法としてフェノキン樹脂を用いる方法
がある。フェノキシ樹脂単独又はその分子中の２級水酸
基を利用しブロック化インシアネート類を架橋剤として
配合し熱硬化させることができる。フェノキシ樹脂は自
己融着性にすぐれているものの耐熱性が低く熱変形温度
８５〜１００℃であり使用用途が限定されている。この
耐熱性を改善するために特殊なフェノキシ樹脂が提案さ
れており、代表的には臭素化ポリヒドロキシポリエーテ
ル樹脂、スルホン基含有ポリヒドロキシポリエーテル樹
脂がある。臭素化ポリヒドロキシポリエーテル樹脂は臭
素含有量によυ耐熱性が変化するため臭素含有量を選択
し、自己融着性と耐熱性のバランスがとれた性能を得る
ことができ有効であった。しかし２００℃×２４０時間
の長期耐熱信頼テストによ＃）塗膜破壊が起り絶縁不良
となる欠点があった。Furthermore, there is a method using phenokine resin as a practically effective method. It is possible to thermally cure the phenoxy resin alone or by blending blocked incyanates as a crosslinking agent using the secondary hydroxyl group in the molecule. Although phenoxy resin has excellent self-fusion properties, it has low heat resistance, with a heat deformation temperature of 85 to 100°C, and its uses are limited. Special phenoxy resins have been proposed to improve this heat resistance, and representative examples include brominated polyhydroxy polyether resins and sulfone group-containing polyhydroxy polyether resins. Since the heat resistance of brominated polyhydroxypolyether resin changes depending on the bromine content, it was effective to select the bromine content and obtain performance with a well-balanced self-bonding property and heat resistance. However, a long-term heat resistance reliability test at 200° C. for 240 hours showed that the coating film was destroyed and the insulation was poor.
一方スルホン基含有ポリヒドロキシボリエーテ骨格を含
有することにより耐熱性を向上させることが知られてい
る。しかし加熱融着温度と耐熱性は相反する性質のだめ
、ビスフェノールＳの骨格の含有量や分子量及び還元比
粘度を選択しなければ実用性がなく、い壕だすぐれたも
のが見い出されてい々いのが現状である。On the other hand, it is known that heat resistance can be improved by containing a sulfone group-containing polyhydroxyboriate skeleton. However, heat fusion temperature and heat resistance are contradictory properties, and it is not practical unless the content of the bisphenol S skeleton, molecular weight, and reduced specific viscosity are selected. is the current situation.
「発明が解決しようとする課題」
近年の電子部品は高品質、高信頼性が要求され％にカラ
ーテレビ建おいては画面の色ずれ発生がないこと、さら
に鮮明度の高い高画質が要求されてきている。画面の色
ずれ等の原因については画面に映しだすだめの重要な役
割をもっている偏向コイルがテレビ受信中にコイル温度
４０〜９０℃に上昇するため熱変形したりコイル巻線の
捻じれ変形する為と考えられている。すなわち偏向コイ
ルの熱接着加工性と巻線加工後の被膜の耐熱性、耐捻じ
れ変形性を同時に解決された樹脂を見い出すのが必須で
あった。``Problem to be solved by the invention'' In recent years, electronic components are required to be of high quality and high reliability, and color TVs are required to have no color shift on the screen and high image quality with high clarity. It's coming. The cause of color shift on the screen is that the deflection coil, which plays an important role in projecting images on the screen, is thermally deformed due to the coil temperature rising to 40 to 90 degrees Celsius during TV reception, and the coil windings are twisted and deformed. It is believed that. In other words, it was essential to find a resin that can simultaneously solve the problems of heat bonding processability of the deflection coil, heat resistance of the coating after winding, and resistance to torsional deformation.
本発明者らはビスフェノールＳ類骨格を含有するポリヒ
ドロキシポリエーテル樹脂について着目し、その改良を
行ったものである。すなわち熱接着性を向上させＳため
には実用性のあるできるだけ低温にお（Ａで加熱碧着が
可能であることが必要であり、そのために本発明の樹脂
の還元比粘度を限定選択することにより優れた加工性が
得られることを見い出したものである。更に樹脂の熱変
形温度やガラス転移点を高めるにはビスフェノールＳ骨
格の含有量を増すことが非常て有効であった。The present inventors focused their attention on a polyhydroxy polyether resin containing a bisphenol S skeleton, and made improvements thereto. In other words, in order to improve thermal adhesion, it is necessary to be able to thermally bond the resin at a temperature as low as practical (A), and for this purpose, the reduced specific viscosity of the resin of the present invention must be selected in a limited manner. Furthermore, it was found that increasing the bisphenol S skeleton content was very effective in increasing the heat distortion temperature and glass transition point of the resin.
しかしながらビスフェノールＳ骨格を増すと兜、脂自身
の溶融粘度が上昇し、熱接着性がわるくなる重大な欠点
が新たに生じることに々る。発明者らは前述の問題を解
決するために次の事をみいだした。すなわちビスフェノ
ールＳ骨格の含有量を高めた樹脂においては、分子中の
水酸基の一部を低分子有機酸又はそのエステル及びカプ
ロラクトンでエステル化変性することにより耐熱性を実
用レベルに保持し、且つ熱接着性の優れた樹脂を見い出
した。However, when the bisphenol S skeleton is increased, the melt viscosity of the fat itself increases, resulting in a new serious drawback of poor thermal adhesion. The inventors discovered the following in order to solve the above-mentioned problem. In other words, in a resin with a high content of bisphenol S skeleton, a part of the hydroxyl groups in the molecule is esterified and modified with a low-molecular organic acid or its ester and caprolactone to maintain heat resistance at a practical level and to maintain thermal adhesive properties. We have discovered a resin with excellent properties.
又ビスフェノールＳ骨格の含有量とエステル化変性率は
互に対比した割合で選択する必要があり、ビスフェノー
ルＳ類の骨格を低減するとエステル化変性率を下げて耐
熱性と熱接着性のバランスをとることができる。In addition, the content of bisphenol S skeleton and the esterification modification rate must be selected in proportion to each other; reducing the bisphenol S skeleton reduces the esterification modification rate and balances heat resistance and thermal adhesiveness. be able to.
さらに有益であるものとしてビスフェノールＳの他に芳
香族にメチル基の置換したビスフェノールＳ類を選択す
るとより効果的である。かかるビスフェノールＳ類とし
て具体的には、３，３′−ジメチル４．４−ジヒドロキ
シジフェニルスルホン、３゜３’、５．５’−テトラメ
チル４，４−ジヒドロキシジフェニルスルホンがあげら
れ、これらを骨格に導入することにより耐熱性と熱接着
性のバランスをとることができたのである。ガラス転移
点が高く速比
元粘度が限定した範囲の物性をもつスルホン基台△
有ポリヒドロキシポリエーテル樹脂を含有する絶ａｍ料
は、従来技術の欠点を解消し且つコイル巻後の熱接着性
、耐熱変形性の優れた自己融着絶縁電線を提供すること
ができるのである。Furthermore, it is more effective to select, in addition to bisphenol S, bisphenol S having an aromatic substitution with a methyl group. Specific examples of such bisphenol S include 3,3'-dimethyl 4,4-dihydroxydiphenylsulfone and 3゜3',5.5'-tetramethyl 4,4-dihydroxydiphenylsulfone, which have a skeleton structure. By introducing it into the market, it was possible to achieve a good balance between heat resistance and thermal adhesion. The absolute AM material containing a sulfone-based polyhydroxy polyether resin with a high glass transition point and a limited range of specific viscosity eliminates the drawbacks of the conventional technology and has excellent thermal adhesion after coil winding. Therefore, it is possible to provide a self-bonding insulated wire with excellent heat deformation resistance.
「課題を解決するための手段及び作用」本発明は、
（１）下記の一形式ＣＩ〕で表されるスルホン基含有ポ
リヒドロキシポリエーテル樹脂を含有することを特徴と
する自己融着性絶縁塗料。"Means and Effects for Solving the Problems" The present invention provides: (1) A self-adhesive insulating paint characterized by containing a sulfone group-containing polyhydroxy polyether resin represented by one type CI below. .
〔式中Ｘはメチル基を、ＹばＳ０２又はＣ（ＣＨ３）２
を、Ｒは水素原子を示し、ｎはＯ〜２０の整数、ｍは２
０以上の整数、ｉはＯ〜４の整数を示す。[In the formula, X is a methyl group, Y is S02 or C(CH3)2
, R represents a hydrogen atom, n is an integer of O to 20, m is 2
An integer of 0 or more; i represents an integer of 0 to 4;
〜７０％の範囲にあシ且つシクロヘキサノン希釈溶液の
還元比粘度が０．３５〜０．６５の範囲である。〕
（Ｑ：） ＮＩＪ求項（１）に記載の化学式〔Ｉ〕に
おいてＸ、 Ｙ。-70%, and the reduced specific viscosity of the diluted cyclohexanone solution is in the range of 0.35 to 0.65. ] (Q:) In the chemical formula [I] described in NIJ requirement (1), X, Y.
ｎ、ｍ、ｉは請求項（１）と同一であるが、Ｒは水素原
子又は低分子有機酸残基又は
−ＣＣＨ２ＣＨ２ＣＨ２−ＯＨを示し
以上でありシクロヘキサノン希釈溶液の還元比粘度が０
．３５〜０．６５の範囲であわ、且つＯＲのエステル化
率が３〜１００％であるスルホン基含有ポリヒドロキシ
ポリエーテル樹脂を含有することを特徴とする自己融着
性絶縁塗料である。n, m, and i are the same as in claim (1), but R represents a hydrogen atom, a low-molecular-weight organic acid residue, or -CCH2CH2CH2-OH, and the reduced specific viscosity of the diluted cyclohexanone solution is 0.
．． This is a self-fusing insulating coating material characterized by containing a sulfone group-containing polyhydroxy polyether resin having a hardness in the range of 35 to 0.65 and an OR esterification rate of 3 to 100%.
本発明樹脂はビスフェノールＡ又はビスフェノールＳ類
のジェポキシ化合物とビスフェノールＡ又はビスフェノ
ールＳ類を有機塩基の存在下、不活性極性溶媒中で反応
さすことによって得られ、必要に応じて分子中のアルコ
ール性水醗基の一部をエステル化変性したもので、−形
式〔■〕をもつ自己融着性にすぐれた耐熱性スルホン基
含有ポリヒドロキシポリエーテル樹脂である。The resin of the present invention is obtained by reacting a jepoxy compound of bisphenol A or bisphenol S with bisphenol A or bisphenol S in the presence of an organic base in an inert polar solvent, and if necessary, alcoholic water in the molecule is added. It is a heat-resistant sulfone group-containing polyhydroxypolyether resin with excellent self-bonding properties, which has a part of the base group modified by esterification and has a - format [■].
原料であるジェポキシ化合物はビスフェノールＡのジェ
ポキシ化合物、又はビスフェノールＳ類のジェポキシ化
合物であり、ビスフェノールＡ又はビスフェノールＳ類
とエピクロルヒドリンの大過剰の範囲で得られるもので
公知の方法によって得ることができる。ビスフェノール
Ａは工業的に生産されているもので良く、より具体的に
は２゜２ビス（４−ヒドロキシジフェニル）プロパンが
望まシく、ビスフェノールＳ類については４．４′−ジ
ヒドロキシジフェニルスルホン、３．３−ジメチル４．
４−ジヒドロキシジフェニルスルホン、３゜３．５．５
−テトラメチル４．４−ジヒドロキシジフェニルスルホ
ンがあげられる。The jepoxy compound as a raw material is a jepoxy compound of bisphenol A or a jepoxy compound of bisphenol S, and can be obtained by a known method in a large excess of bisphenol A or bisphenol S and epichlorohydrin. Bisphenol A may be one that is industrially produced, and more specifically, 2゜2bis(4-hydroxydiphenyl)propane is preferable, and for bisphenol S, 4,4'-dihydroxydiphenylsulfone, 3. .3-dimethyl4.
4-dihydroxydiphenylsulfone, 3°3.5.5
-tetramethyl 4,4-dihydroxydiphenylsulfone.
本発明のスルホン基を有するポリヒドロキシポリエーテ
ル樹脂はビスフェノールＡ又はビスフエノールＳ類の合
計が１又はそれ以上と、前記したビスフェノールＡ又は
ビスフェノールＳ類のジェポキシ化合物の合計が１又は
それ以上とを、エポキシ基とビスフェノール類のＯＨ基
とが当量となる様に不活性極性溶媒中で有機塩基触媒の
存在下反応させて得られたもので、必要に応じて分子中
に存在する２級水酸基の３〜１００％に相当する当量の
低分子有機酸又はそのエステル又はカプロラクトンでエ
ステル化反応して得られるものである。The polyhydroxy polyether resin having a sulfone group of the present invention has a total of 1 or more bisphenol A or bisphenol S, and a total of 1 or more jepoxy compounds of bisphenol A or bisphenol S as described above. It is obtained by reacting the epoxy group and the OH group of bisphenols in equivalent amounts in an inert polar solvent in the presence of an organic base catalyst. It is obtained by an esterification reaction with an equivalent amount of a low molecular weight organic acid or its ester or caprolactone corresponding to ~100%.
本発明においてジェポキシ化合物のエポキシ基に対する
フェノール類のモル比は１．０５〜０．９５の範囲を含
むもので、好壕しくけ１．０３〜０．９７である。１．
０５以上又は０．９５以下では高分子量のものが得られ
ない。ビスフェノールＡとビスフェノールＳ類の比率は
生成樹脂の耐熱性に重大な影響を受けるため、ビスフェ
ノールＳ類成分〜７０％が好ましい。ビスフェノールｓ
ｍ成分の割合が大きくなると耐熱性が向上するが溶剤
に対する溶解性や流動性がわるくなるので、よシ好まし
くは０．２５〜０．６が最適である。ビスフェノールＡ
／ビスフェノールＳ類の比と生成するヒト四キシポリエ
ーテル樹脂の耐熱性は、参考例によって示すと表１の関
係が得られる。In the present invention, the molar ratio of the phenol to the epoxy group of the jepoxy compound is in the range of 1.05 to 0.95, preferably 1.03 to 0.97. 1.
If the molecular weight is 0.05 or more or 0.95 or less, a product with a high molecular weight cannot be obtained. Since the ratio of bisphenol A to bisphenol S is significantly affected by the heat resistance of the resulting resin, the bisphenol S component is preferably 70% to 70%. bisphenol s
As the ratio of the m component increases, heat resistance improves, but solubility and fluidity in solvents deteriorate, so the optimum ratio is preferably 0.25 to 0.6. Bisphenol A
The relationship between the ratio of /bisphenol S and the heat resistance of the human tetraxypolyether resin produced is shown in Table 1 using reference examples.
一方ビスフエノールＳ類の成分の割合が増加してもアル
コール性水醗基の３〜１００％をエステル化すること及
び／又はビスフェノールＳのベンゼン環にメチル基を導
入することにより、耐熱性、溶解性、流動性、耐熱変形
性のバランスを計ることができる。On the other hand, even if the proportion of bisphenol S components increases, heat resistance and solubility can be improved by esterifying 3 to 100% of the alcoholic water groups and/or introducing a methyl group into the benzene ring of bisphenol S. It is possible to balance properties, fluidity, and heat deformation resistance.
反応溶媒として好適なものの例はシクロヘキサノン、ア
セトフェノ／、ベンゾフェノン、Ｎ−メチルピロリドン
等のケトン類、フリ７ラール等のベンゼン、１−クロロ
２−ニトロベンゼン、１−クロロ３−ニトロベンゼン、
モノクロルベンゼン等の芳香族化合物、ジメチルスルホ
キシド等のスルホキシド類、ジメチルホルムアミド、環
状又は直鎖状エーテル化合物類のジオキサン、ジェトキ
シエタン等がある。あるいは上記の混合溶媒を用いるこ
とができる。Examples of suitable reaction solvents include cyclohexanone, acetophenone, benzophenone, ketones such as N-methylpyrrolidone, benzenes such as fur7ral, 1-chloro2-nitrobenzene, 1-chloro3-nitrobenzene,
Examples include aromatic compounds such as monochlorobenzene, sulfoxides such as dimethyl sulfoxide, dimethylformamide, and cyclic or linear ether compounds such as dioxane and jetoxyethane. Alternatively, the above mixed solvents can be used.
触媒としては公知の触媒で良く有機塩基が効果的である
。有機塩基の代表的なものとしてはトリエチルアミン、
ｎ−ブチルアミン、メチルアミン誘導体、エチルアミン
誘導体、ピペリジン、ピペリジン誘導体ピロリジン、Ｎ
−メチルピロリジン、モルホリン、トリエチレンジアミ
ン、ヘキサメチレンジアミン、ピリジン、イミダゾール
類、１，８シアサビシクロ（５，４，０）ウンデセ／−
７等の有機塩基類等を挙げることができる。触媒はビス
フェノール類に対して０．５ないし４モル係の範囲で使
用される。特に触媒量は製品の還元比粘度に影響をおよ
ぼすので特に重要であり、本発明においてより好ましく
は１．０〜３モル係が最適である。As the catalyst, any known catalyst may be used, and organic bases are effective. Typical organic bases include triethylamine,
n-butylamine, methylamine derivative, ethylamine derivative, piperidine, piperidine derivative pyrrolidine, N
-Methylpyrrolidine, morpholine, triethylenediamine, hexamethylenediamine, pyridine, imidazoles, 1,8cyasabicyclo(5,4,0)undece/-
Examples include organic bases such as No. 7 and the like. The catalyst is used in an amount of 0.5 to 4 molar based on the bisphenol. In particular, the amount of catalyst is particularly important since it affects the reduced specific viscosity of the product, and in the present invention, the optimum amount is more preferably 1.0 to 3 molar ratio.
触媒量が４モル係以上の場合は反応速度が早く制御がむ
ずかしく、生成物のゲル化や分子内分枝反応が進んで好
ましくない。触媒が０．５モル係以下の場合は反応時間
が長時間にわたシ、所望の分子量に到達せずに低分子化
合物が多く残存してしまう。When the amount of catalyst is 4 molar or more, the reaction rate is fast and difficult to control, and gelation of the product and intramolecular branching reaction progress, which is undesirable. If the catalyst has a molar ratio of less than 0.5, the reaction time will be long, and the desired molecular weight will not be reached and many low-molecular compounds will remain.
反応温度は８０〜２００℃の間が好ましく特に不活性極
性溶媒の沸点に左右されるが、好ましくは１００〜１８
０℃が有効である。又反応が進行するに従い反応物の粘
度が上昇するため適時、不活性種性溶媒を追加して均一
化を計ることが必要である。反応時間は２〜８時間を要
する。増粘がなくなったら必要に応じて低分子有機酸又
はそのエステル、カプロラクトンを、分子内２級水酸基
の３〜１００％相当する量を仕込み、さらに同温度で継
続して４時間反応させる。The reaction temperature is preferably between 80 and 200°C, depending on the boiling point of the inert polar solvent, but preferably between 100 and 18°C.
0°C is effective. Furthermore, as the reaction progresses, the viscosity of the reactant increases, so it is necessary to add an inert seed solvent from time to time to ensure uniformity. The reaction time requires 2 to 8 hours. When the viscosity disappears, a low molecular weight organic acid or its ester, caprolactone, is charged in an amount corresponding to 3 to 100% of the secondary hydroxyl groups in the molecule, and the reaction is continued at the same temperature for 4 hours.
エステル化剤としてはカプロラクトンが挙げられ、ラク
トンを開環し１級水酸基を側鎖に生成することができる
。又低分子有機酸及びそのエステルとしては以下のもの
があげられる。代表的にはギ酸、酢酸、安息香酸、プロ
ピオン醗、ステアリン酸、パラトルエンスルホン醗、メ
ルカプト酸、及びそのメチルエステル又はエチルエステ
ル類、さらにはクロロアセチル等のハロゲン化アセチル
化合物があげられる。２級水酸基へのカプロラクトンの
開環重合及びエステル化反応は１００〜２００℃の反応
温度で行なう。この反応では新たに触媒を添加しなくて
もよく、必要により触媒を用いても良く、かかる触媒と
してテトラブチルチタネート、テトラエチルチタネート
、テトラエチルチタネート等のチタン化合物、さらには
塩化第一スズ、臭化第一スズ、ヨウ化第−スズ等があげ
られる。使用量は反応温度によって異なるが一般には１
１０００ｐｐから０．ｌｐｐｍで好ましくは５００ ｐ
ｐｐｍ−０−２ｐｐを用いる。Examples of the esterification agent include caprolactone, which can open the ring of lactone and generate a primary hydroxyl group in the side chain. Examples of low molecular weight organic acids and esters thereof include the following. Representative examples include formic acid, acetic acid, benzoic acid, propionic acid, stearic acid, para-toluenesulfonic acid, mercaptoic acid, methyl esters or ethyl esters thereof, and halogenated acetyl compounds such as chloroacetyl. The ring-opening polymerization and esterification reaction of caprolactone to a secondary hydroxyl group are carried out at a reaction temperature of 100 to 200°C. In this reaction, it is not necessary to add a new catalyst, and a catalyst may be used if necessary. Such catalysts include titanium compounds such as tetrabutyl titanate, tetraethyl titanate, and tetraethyl titanate, as well as stannous chloride and stannous bromide. Examples include tin and stannous iodide. The amount used varies depending on the reaction temperature, but generally 1
1000pp to 0. preferably 500 p in lppm
Use ppm-0-2pp.
反応の終点は酸価あるいはガスクロマトグラフィーによ
り決定する。還元比粘度は熱接着性に重大な影響を与え
る物性である。本発明において還元比粘度とは樹脂（１
００チ） ０．２ ｙを１００Ｍ１のシクロヘキサノン
溶液に調整し恒温水槽（２５℃）中、キャノンフェンス
ケ桑７５粘度計にテ測定した値である。The end point of the reaction is determined by acid value or gas chromatography. Reduced specific viscosity is a physical property that has a significant effect on thermal adhesiveness. In the present invention, reduced specific viscosity refers to resin (1
This is the value obtained by adjusting 0.2y to a 100M1 cyclohexanone solution and measuring it with a Canon Fenske Kuwa 75 viscometer in a constant temperature water bath (25°C).
以下実施例を比較例とともに説明する。Examples will be described below along with comparative examples.
「実施例、比較例」
実施例１
エポキシ当量１８６．５１／ｅｑのビスフェノールＡ（
以下ＢＰＡという）型エポキシ樹脂（東部化成（株）製
ＹＤ−１２８、以下ＹＤ−１２８と略す）１８６．５９
ト４．４−ジヒドロキシジフェニルスルホン（以下Ｂ
ＰＳと略す＞１２２．１ｙ（０，４８８モル）とシクロ
ヘキサノン３０８．６９とを１１丸底フラスコに仕込み
、窒素パージしながら昇温し完全に溶解後、トリエチル
アミン０．７７ｙ（０，００７６モル）を加え１５０℃
、４時間で反応をさせた。"Examples, Comparative Examples" Example 1 Bisphenol A (with an epoxy equivalent of 186.51/eq)
186.59
4,4-dihydroxydiphenylsulfone (hereinafter referred to as B
122.1y (abbreviated as PS) (0,488 mol) and 308.69 cyclohexanone were placed in a 11 round bottom flask, heated while purging with nitrogen to completely dissolve, and then 0.77y (0,0076 mol) of triethylamine was added. Add 150℃
, the reaction was allowed to take place for 4 hours.
反応終了後は渦紋使用の不活性溶蝶もしくはその他の溶
媒で３０チに希釈し溶液を精密涙過する。After the reaction is completed, the solution is diluted to 30% with an inert molten liquid or other solvent, and the solution is passed through a precision sieve.
得られたスルホン基含有ポリヒドロキシポリエーテル樹
脂溶液をバーコーターにてポリエステルフィルムに塗布
し、１６０℃、３０分熱風循環乾燥機で揮発分を除去し
２０μの樹脂フィルムを得た。The obtained sulfone group-containing polyhydroxypolyether resin solution was applied to a polyester film using a bar coater, and volatile components were removed using a hot air circulation dryer at 160° C. for 30 minutes to obtain a 20 μm resin film.
上記樹脂フィルムを集めて還元比粘度、ガラス転移点（
ＴＭＡ法）等を測定した。以下の各実施例、各比較例と
も反応後に同様の処理をした。得られた樹脂の物性を表
１に示す。Collect the above resin films and check the reduced specific viscosity and glass transition point (
TMA method) etc. were measured. In each of the following Examples and Comparative Examples, the same treatment was performed after the reaction. Table 1 shows the physical properties of the obtained resin.
実施例２
実施例１と同様に仕込み、触媒を添加する前にトルエン
による還流脱水を行い、トルエンを溜去したのち、触媒
Ｎ−メチルモルホリンを０．７７ｙ添加し、実施例１と
同様に１５０℃、４時間で反応をさせた後、ε−カプロ
ラクトンを１５．４ ｙ（５ｐｈｒ ）加え、さらに４
時間反応をさせた。得られた樹脂の物性を表１に示す。Example 2 Prepared in the same manner as in Example 1, reflux dehydration with toluene was performed before adding the catalyst, and after distilling off the toluene, 0.77y of N-methylmorpholine was added as the catalyst, and 150 y was added as in Example 1. After reacting at ℃ for 4 hours, 15.4 y (5 phr) of ε-caprolactone was added, and then 4
A time reaction was allowed. Table 1 shows the physical properties of the obtained resin.
実施例３
エポキシ当ｉ ２４１．４ ｙ／ ｅｑのＢＰＳ型エポ
キシ樹脂２４１．４７とＢＰＳ １２２．１ｙ（０，４
８８モル）とシクロヘキサノン３６３．５９とを仕込み
、実施例２と同様に還流脱水後、Ｎ−メチルモルホリン
０．７７ ’；！ （０，００７６モル）を加え、１５
０°Ｃ１４時間で反応をさせたのちにε−カプロラクト
ン１３６．６ｙ（３７，６ｐｈｒ ）を加え、さらに４
時間反応をさせた。樹脂の物性を表１に示す。Example 3 BPS type epoxy resin 241.47 with i 241.4 y/eq and BPS 122.1 y (0,4
88 mol) and 363.59 cyclohexanone, and after dehydration under reflux in the same manner as in Example 2, N-methylmorpholine 0.77';! (0,0076 mol) and 15
After reacting at 0°C for 14 hours, 136.6y (37.6 phr) of ε-caprolactone was added, and then 4
A time reaction was allowed. Table 1 shows the physical properties of the resin.
実施例４
ＹＤ−１２８（エポキシ当量１８６．５ ｙ／ ｅｑ
）１８６．５ ｙとビス（３，５−ジメチル−４−ヒド
ロキシフェニル）スルホン（以下ＴＭＳと略す）１４９
．５１ （０，４８８モル）とシクロヘキサノン３３６
ｙとを仕込み、窒素パージしながら昇温溶解後、２−エ
チル−４メチルイミダゾール６．７２ｐｈｒを添加し、
１５０℃、７時間で反応をさせた。Example 4 YD-128 (epoxy equivalent weight 186.5 y/eq
) 186.5 y and bis(3,5-dimethyl-4-hydroxyphenyl)sulfone (hereinafter abbreviated as TMS) 149
．． 51 (0,488 mol) and cyclohexanone 336
After dissolving at elevated temperature while purging with nitrogen, 6.72 phr of 2-ethyl-4 methylimidazole was added,
The reaction was carried out at 150°C for 7 hours.
得られた樹脂の物性を表１に示す。Table 1 shows the physical properties of the obtained resin.
実施例５
実施例４ど同様に仕込み、還流脱水後、ピリジン０．６
９ （０，００７６モル）を加え、１５０℃、４時間で
反応をさせたのち、ε−カプロラクトン１０．１ｙ（３
ｐｈｒ ）を加え、さらに４時間反応をした。Example 5 Prepared in the same manner as Example 4, and after reflux dehydration, pyridine 0.6
9 (0,0076 mol) and reacted at 150°C for 4 hours, ε-caprolactone 10.1y (3
phr) was added, and the reaction was further continued for 4 hours.
実施例６
ＹＤ−１２８（エポキシ当量１８６．５１？／ ｅｑ
）１８６．５ ｙとビス（３２３−メチル−４−ヒドロ
キシフェニル）スルホン１３５．８ｙとシクロヘキサノ
ン３２２．３７とを仕込み、窒素パージし々がら昇温溶
解後、トリエチルアミン０．７７９を加え、１５０℃、
４時間で反応を行なった。Example 6 YD-128 (epoxy equivalent weight 186.51?/eq
) 186.5 y, bis(323-methyl-4-hydroxyphenyl)sulfone 135.8 y, and cyclohexanone 322.37 y, and after dissolving at elevated temperature while purging with nitrogen, 0.779 y of triethylamine was added, and 150°C.
The reaction was carried out for 4 hours.
比較例Ｉ
ＹＤ−１２８（エポキシ当量１８６．５ ｙ／ｅｑ）１
８６．５ ｙとＢＰＳ １２２．７ｙ（０，４９モル）
とシクロヘキサノン３０９．２ ｙとを仕込み、窒素ノ
（−ジしながら昇温溶解し、トリエチルアミン２．４８
．７（０，０２４５モル）を加え、１５０℃、４時間反
応を行なった。Comparative Example I YD-128 (Epoxy equivalent weight 186.5 y/eq) 1
86.5 y and BPS 122.7 y (0,49 mol)
and 309.2 y of cyclohexanone, and dissolved at elevated temperature while blowing with nitrogen, to dissolve 2.48 y of triethylamine.
．． 7 (0,0245 mol) was added thereto, and the reaction was carried out at 150°C for 4 hours.
比較例２
ＹＤ−１２８（エポキシ当ｆ１１８６．５ ｙ／ ｅ（
１）１８６．５ ｙとＢＰＳ １２０．３ Ｐ （０，
４８モル）とシクロヘキサノン３０６．８９とを仕込み
、触媒としてはピリジンｌ、９ｙ（０−０２４モル）を
用い、比較例１と同様に反応を行なった。Comparative Example 2 YD-128 (epoxy f1186.5 y/e(
1) 186.5 y and BPS 120.3 P (0,
A reaction was carried out in the same manner as in Comparative Example 1, using pyridine 1,9y (0-024 mol) as a catalyst.
比較例３
ＹＤ−１２８（エポキシ当量１８６．５９’／ｅｑ）１
８６．５９とＢＰＡ ８４ ｙ（０，３６８４モル）と
ＢＰＳ ３０．４ｙ（０，１２１５モル）とシクロヘキ
サノン３０３．８１とを仕込み、ピリジン０−９７ｙ（
０，０２４３モル）を用い、反応を行なった。Comparative example 3 YD-128 (epoxy equivalent 186.59'/eq) 1
Pyridine 0-97y (
0,0243 mol) was used to carry out the reaction.
比較例４
ＢＰＳ屋エポキシ樹脂（エポキシ当量２４１．４ｙ／ｅ
ｑ）２４１．４ｙとＢＰＳ １２２．７？ （０，４９
モル）とシクロヘキサノン３６４．１９とを仕込み、比
較例１と同様に反応を行なった。Comparative example 4 BPS shop epoxy resin (epoxy equivalent 241.4y/e
q) 241.4y and BPS 122.7? (0,49
A reaction was carried out in the same manner as in Comparative Example 1.
表 １
１、 ｎ／ （ｍ＋ ｎ ） ：式〔ＤによるＢＰＳ類
の含有量（ｗｔチ）。Table 1 1, n/(m+n): Content of BPS (wt) according to the formula [D].
２、エステル化率：ε−カプロラクトンのモル数／フェ
ノキシ樹脂中水酸基のモル数。2. Esterification rate: number of moles of ε-caprolactone/number of moles of hydroxyl groups in the phenoxy resin.
３、還元比粘度：固形樹脂０．２ ｙをシクロヘキサノ
ンで１００ ｔｎｌの溶液に調製し、牟７５キャノンフ
ェンスケ動粘度計を用い、２５℃で測定した値。3. Reduced specific viscosity: Value measured at 25° C. by preparing a 100 tnl solution of 0.2 y of solid resin with cyclohexanone and using a 75 Cannon Fenske kinematic viscometer.
４、Ｔｇ：高車ＤＴ−３０を用いてＴＭＡの測定値。4. Tg: TMA measurement value using Takashisha DT-30.
５、融着性： ＪＩＳ−Ｋ ６８５０を準する、融着条
件２００℃×１０分セン断接着強度が、室温で１２０Ｋ
ｙ／σ２以上では○、１２０ ｈ／口口取以下は×。5. Fusion property: Based on JIS-K 6850, fusion conditions: 200°C x 10 minutes, shear adhesive strength is 120K at room temperature.
○ for y/σ2 or more, × for 120 h/kuchitori or less.
６、耐熱変形性：１００℃に於ける融着性の判定。6. Heat deformation resistance: Judgment of fusion properties at 100°C.
「発明の効果」
本発明で使用するスルホン基含有ポリヒドロキシポリエ
ーテル樹脂は樹脂そのものの還元比粘度を０．３５〜０
．６５の範囲にしたにもかかわらず、ガラス転移点が高
い事が特徴であり、従来技術では考えられなかったこと
である。この樹脂を使用した自己融着性絶縁塗料は電線
に塗布した場合にすぐれた熱接着性、耐熱変形性を与え
るという予期されなかった効果を示すものである。"Effects of the Invention" The sulfone group-containing polyhydroxypolyether resin used in the present invention has a reduced specific viscosity of 0.35 to 0.
．． Although it is in the range of 65, it is characterized by a high glass transition point, which was inconceivable with the prior art. A self-adhesive insulating paint using this resin exhibits unexpected effects in that it provides excellent thermal adhesion and heat deformation resistance when applied to electric wires.
Claims (2)
ポリヒドロキシポリエーテル樹脂を含有することを特徴
とする自己融着性絶縁塗料。 ▲数式、化学式、表等があります▼ 〔 I 〕 〔式中Ｘはメチル基を、ＹはＳＯ＿２又は Ｃ（ＣＨ＿３）＿２を、Ｒは水素原子を示し、ｎは０〜
２０の整数、ｍは２０以上の整数、ｉは０〜４の整数を
示す。更に ▲数式、化学式、表等があります▼が全体の１５〜 ７０％の範囲にあり且つシクロヘキサノン希釈溶液の還
元比粘度が０．３５〜０．６５の範囲である。〕(1) A self-adhesive insulating paint characterized by containing a sulfone group-containing polyhydroxy polyether resin represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, X is a methyl group, Y is SO_2 or C(CH_3)_2, R is a hydrogen atom, and n is 0 to
An integer of 20, m is an integer of 20 or more, and i is an integer of 0 to 4. Furthermore, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is in the range of 15 to 70% of the total, and the reduced specific viscosity of the diluted cyclohexanone solution is in the range of 0.35 to 0.65. ]
、Ｙ、ｎ、ｍ、ｉは請求項（１）と同一であるが、Ｒは
水素原子又は低分子有機酸残基又は ▲数式、化学式、表等があります▼を示し ▲数式、化学式、表等があります▼が全体の３５％ 以上でありシクロヘキサノン希釈溶液の還元比粘度が０
．３５〜０．６５の範囲であり、且つＯＲのエステル化
率が３〜１００％であるスルホン基含有ポリヒドロキシ
ポリエーテル樹脂を含有することを特徴とする自己融着
性絶縁塗料。(2) In the chemical formula [I] according to claim (1),
, Y, n, m, and i are the same as in claim (1), but R represents a hydrogen atom, a low-molecular organic acid residue, or ▲a mathematical formula, a chemical formula, a table, etc. etc. ▼ is more than 35% of the total and the reduced specific viscosity of the diluted cyclohexanone solution is 0.
．． 35 to 0.65, and a sulfone group-containing polyhydroxy polyether resin having an esterification rate of 3 to 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63198626A JP2663353B2 (en) | 1988-08-08 | 1988-08-08 | Self-fusing insulating paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63198626A JP2663353B2 (en) | 1988-08-08 | 1988-08-08 | Self-fusing insulating paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0245575A true JPH0245575A (en) | 1990-02-15 |
| JP2663353B2 JP2663353B2 (en) | 1997-10-15 |
Family
ID=16394326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63198626A Expired - Fee Related JP2663353B2 (en) | 1988-08-08 | 1988-08-08 | Self-fusing insulating paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2663353B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006321879A (en) * | 2005-05-18 | 2006-11-30 | Nippon Steel Chem Co Ltd | Polymer having aromatic ether sulfone skeleton, method for producing the same and composition of the same |
| JP2009067934A (en) * | 2007-09-14 | 2009-04-02 | Hitachi Magnet Wire Corp | Heat-resistant self-fusing paint and heat-resistant self-fusing enamel wire |
| JP2009099557A (en) * | 2007-09-27 | 2009-05-07 | Sumitomo Electric Wintec Inc | Self-fusion insulated wire and motor for driving compressor |
| US8816038B2 (en) | 2006-01-12 | 2014-08-26 | Nippon Steel & Sumikin Chemical Co., Ltd. | Aromatic ether polymer, method for producing the same, and polymer composition |
| JP2017115055A (en) * | 2015-12-25 | 2017-06-29 | 日立化成株式会社 | Phenoxy resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS604523A (en) * | 1983-06-23 | 1985-01-11 | Sumitomo Bakelite Co Ltd | Electrical insulating resin paste |
-
1988
- 1988-08-08 JP JP63198626A patent/JP2663353B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS604523A (en) * | 1983-06-23 | 1985-01-11 | Sumitomo Bakelite Co Ltd | Electrical insulating resin paste |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006321879A (en) * | 2005-05-18 | 2006-11-30 | Nippon Steel Chem Co Ltd | Polymer having aromatic ether sulfone skeleton, method for producing the same and composition of the same |
| US8816038B2 (en) | 2006-01-12 | 2014-08-26 | Nippon Steel & Sumikin Chemical Co., Ltd. | Aromatic ether polymer, method for producing the same, and polymer composition |
| JP2009067934A (en) * | 2007-09-14 | 2009-04-02 | Hitachi Magnet Wire Corp | Heat-resistant self-fusing paint and heat-resistant self-fusing enamel wire |
| JP2009099557A (en) * | 2007-09-27 | 2009-05-07 | Sumitomo Electric Wintec Inc | Self-fusion insulated wire and motor for driving compressor |
| JP2017115055A (en) * | 2015-12-25 | 2017-06-29 | 日立化成株式会社 | Phenoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2663353B2 (en) | 1997-10-15 |
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