JP7593539B2 - Method for producing polyamide-imide resin solution useful for electrical insulating paint and electrical insulating coated wire - Google Patents
Method for producing polyamide-imide resin solution useful for electrical insulating paint and electrical insulating coated wire Download PDFInfo
- Publication number
- JP7593539B2 JP7593539B2 JP2020153432A JP2020153432A JP7593539B2 JP 7593539 B2 JP7593539 B2 JP 7593539B2 JP 2020153432 A JP2020153432 A JP 2020153432A JP 2020153432 A JP2020153432 A JP 2020153432A JP 7593539 B2 JP7593539 B2 JP 7593539B2
- Authority
- JP
- Japan
- Prior art keywords
- dimethylpropanamide
- methoxy
- solvent
- mdmpa
- varnish
- 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.)
- Active
Links
- 239000004962 Polyamide-imide Substances 0.000 title claims description 133
- 229920002312 polyamide-imide Polymers 0.000 title claims description 133
- 239000011347 resin Substances 0.000 title claims description 129
- 229920005989 resin Polymers 0.000 title claims description 129
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000003973 paint Substances 0.000 title description 22
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 claims description 205
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- 239000007810 chemical reaction solvent Substances 0.000 claims description 84
- 239000002904 solvent Substances 0.000 claims description 82
- 239000000243 solution Substances 0.000 claims description 77
- 238000010790 dilution Methods 0.000 claims description 61
- 239000012895 dilution Substances 0.000 claims description 61
- 239000012948 isocyanate Substances 0.000 claims description 52
- 150000002513 isocyanates Chemical class 0.000 claims description 52
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 6
- 239000002966 varnish Substances 0.000 description 79
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 60
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 53
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 44
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 13
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- 238000001879 gelation Methods 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 210000003298 dental enamel Anatomy 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000009719 polyimide resin Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 3
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- -1 phenoxyphenyl Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000004135 Bone phosphate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- PMTMAFAPLCGXGK-JMTMCXQRSA-N (15Z)-12-oxophyto-10,15-dienoic acid Chemical compound CC\C=C/C[C@H]1[C@@H](CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-JMTMCXQRSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- YLFRRPUBVUAHSR-UHFFFAOYSA-N 16-dehydro-pregnenolone Natural products C1C=C2CC(O)CCC2(C)C2C1C1CC=C(C(=O)C)C1(C)CC2 YLFRRPUBVUAHSR-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- UCPOEBHXOCKECV-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CCC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O UCPOEBHXOCKECV-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- DDVYLSFEKWFRFS-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CCC1=CC=C(C(O)=O)C(C(O)=O)=C1 DDVYLSFEKWFRFS-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AXCSBFRIHQXBSG-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 AXCSBFRIHQXBSG-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- PMTMAFAPLCGXGK-UHFFFAOYSA-N OPDA Natural products CCC=CCC1C(CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-UHFFFAOYSA-N 0.000 description 1
- 101100028078 Oryza sativa subsp. japonica OPR1 gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical group OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- HVNWRBWNOPYOER-UHFFFAOYSA-N pentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)C(C(O)=O)CC(O)=O HVNWRBWNOPYOER-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Insulated Conductors (AREA)
Description
本発明は、電気絶縁塗料及び電気絶縁被覆電線に有用なポリアミドイミド樹脂溶液の製法に関するものである。 The present invention relates to a method for producing a polyamide-imide resin solution useful for electrical insulating paints and electrical insulating coated wires .
ポリアミドイミド樹脂は、耐熱性、耐薬品性及び耐溶剤性等に優れている為 各種の基材のコ－ト剤等として広く用いられている。例えば、電気絶縁塗料や当該塗料を用いた電気絶縁電線等として使用されている。
当該ポリアミドイミド樹脂の重合や溶解希釈等の用途として、その優れた溶解性等から、従来、Ｎ－メチル－２－ピロリドン（ＮＭＰ）等が用いられてきたが、近年、環境保全面、安全衛生面、経済性などから、それに代わる各種の反応溶剤や希釈溶剤が検討されてきて、又、有機溶媒に代わって媒体に水を使用する水系樹脂溶液も注目されてきたりしている。
当該代替え溶剤として、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）やガンマブチロラクトン（ＧＢＬ）等が注目されていて、又、水を含む水系ポリアミドイミド樹脂組成物等も提案されているが、反応溶剤の使用量やその水分量の大きさや希釈溶剤の種類等如何により、ポリアミドイミド樹脂生成の際や電気絶縁塗料（ワニス）生成の際に、ゲル化してしまったり、ワニスの外観に濁りを生じたりし、又、ワニスを電線（コイル）に被覆してなる電気絶縁電線において、耐軟化性の低下等が見られたりする。
又、ポリアミドイミド樹脂の合成において、最終の到達温度如何により、ワニスの外観に濁りを生じたりする。
本発明は、こうした背景で、ポリアミドイミド樹脂を酸成分とイソシアネ－ト成分とを用いた方法で製造する所謂イソシアネ－ト法によるポリアミドイミド樹脂について、上記した問題の解明をなして、ゲル化、ワニス外観の濁り、及び、電気絶縁電線における耐軟化性の低下等の改善を意図したものである。
Polyamide-imide resins are widely used as coating agents for various substrates due to their excellent heat resistance, chemical resistance, and solvent resistance, etc. For example, they are used as electrical insulating paints and electrical insulating wires using said paints.
Conventionally, N-methyl-2-pyrrolidone (NMP) and the like have been used for applications such as polymerization, dissolution, and dilution of the polyamide-imide resin because of its excellent solubility. However, in recent years, various alternative reaction solvents and dilution solvents have been studied from the standpoints of environmental conservation, safety and hygiene, and economy, and also aqueous resin solutions that use water as a medium instead of organic solvents have been attracting attention.
As such alternative solvents, 3-methoxy-N,N-dimethylpropanamide (MDMPA), gamma-butyrolactone (GBL), and the like have attracted attention, and aqueous polyamideimide resin compositions containing water have also been proposed. However, depending on the amount of reaction solvent used, the amount of water contained therein, the type of dilution solvent, and the like, gelation may occur during the production of polyamideimide resin or electrical insulating paint (varnish), or the appearance of the varnish may become cloudy. Furthermore, in an electrically insulated electric wire in which the varnish is coated on an electric wire (coil), a decrease in softening resistance may be observed.
Furthermore, in the synthesis of polyamide-imide resin, depending on the final temperature reached, the appearance of the varnish may become cloudy.
In view of the above background, the present invention is intended to solve the above-mentioned problems with polyamide-imide resins produced by the so-called isocyanate method, in which a polyamide-imide resin is produced by a method using an acid component and an isocyanate component, and to improve gelation, cloudy appearance of varnish, and reduced softening resistance in insulated wires.
こうした背景の従来例として、特開２０１９－１０４９３９号公報には、ポリアミドイミド樹脂の製造方法において、溶剤中の水分量をｗ（ｐｐｍ）とし、加熱時間をｔ（分）として、ｗおよびｔが特定の式を満たすことを求めているが、当該ポリアミドイミド樹脂の製造方法は、ジアミン、ジカルボン酸、および、テトラカルボン酸二無水物を溶剤中で共重合しポリアミドイミド樹脂前駆体を得る工程における当該工程を開始する際の溶剤中の水分量を規定したもので、ポリアミドイミド樹脂をアミン成分を用いた方法で製造するもので、ポリアミドイミド樹脂をイソシアネ－ト成分を用いた方法で製造するイソシアネ－ト法によるものではない。 As a conventional example of this background, JP 2019-104939 A describes a method for producing polyamide-imide resin, in which the amount of water in the solvent is w (ppm) and the heating time is t (minutes), and requires that w and t satisfy a specific formula. However, this method for producing polyamide-imide resin specifies the amount of water in the solvent at the start of a step in which a diamine, a dicarboxylic acid, and a tetracarboxylic dianhydride are copolymerized in the solvent to obtain a polyamide-imide resin precursor, and produces polyamide-imide resin by a method using an amine component, not by an isocyanate method in which polyamide-imide resin is produced by a method using an isocyanate component.
特許６１７９７９５（特開２０１４－１８１３３２号公報）には、ポリアミドイミド樹脂と水とを含有するポリアミドイミド樹脂溶液が開示され、水が樹脂溶液に特定量存在することが規定されているが、当該特許では、イソシアネ－ト基にアミノ基（ポリアミン）が結合してできる樹脂中のウレア結合が、アミド結合やイミド結合に対して特定量含有するように、ポリアミン成分を使用している。 Patent 6179795 (JP 2014-181332 A) discloses a polyamideimide resin solution containing polyamideimide resin and water, and specifies that a specific amount of water is present in the resin solution, but in this patent, a polyamine component is used so that a specific amount of urea bonds in the resin, which are formed when amino groups (polyamines) are bonded to isocyanate groups, are contained relative to amide bonds and imide bonds.
特開２０１４－２６９７９０号公報には、溶媒中の水分含有量について触れる記載があるが、ポリイミドの前駆体のポリアミック酸を含む溶液をイミド化してポリイミド樹脂を含む溶液を得、該溶液からポリイミド樹脂の粉体を抽出するポリイミド樹脂粉体の製造方法で、ポリアミドイミド樹脂の製法に関するものではない。 JP 2014-269790 A mentions the water content in the solvent, but it is a method for producing polyimide resin powder in which a solution containing polyamic acid, a precursor of polyimide, is imidized to obtain a solution containing polyimide resin, and polyimide resin powder is extracted from the solution; it is not related to a method for producing polyamide-imide resin.
特許６０１５５５１（特開２０１４－６２２２３号公報）には、ポリアミドイミド樹脂を含み、且つ、溶剤としてガンマブチロラクトンを含むことを特徴とする潤滑塗料用ポリアミドイミド樹脂組成物、それを含む塗料、及びその塗料を塗布された摺動部材についての記載があり、そのポリアミドイミド樹脂にあっては、ベンゼン環にメチル基の置換基を有するイソシアナ－ト成分を使用して、当該イソシアネ－ト成分に基づく特定の式の繰り返し単位が５０ｍｏｌ％以上含有するようにすることが記載されているだけで、ポリアミドイミド樹脂生成の際や塗料生成の際のゲル化の問題や塗料外観の濁りや電気絶縁電線における耐軟化性の低下等の問題に触れる記載はない。 Patent 6015551 (JP Patent Publication 2014-62223 A) describes a polyamideimide resin composition for lubricating paints, which contains polyamideimide resin and gamma-butyrolactone as a solvent, a paint containing the same, and a sliding member coated with the paint. The only description is that the polyamideimide resin uses an isocyanate component having a methyl group substituent on the benzene ring, and contains 50 mol% or more of repeating units of a specific formula based on the isocyanate component. There is no description of problems such as gelation during polyamideimide resin production or paint production, cloudiness of the paint's appearance, or reduced softening resistance in insulated electric wires.
ＷＯ２０１８／１５０５６６公報には、ポリアミドイミド樹脂と３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドと水を含むポリアミドイミド樹脂組成物が記載されていて、当該ポリアミドイミド樹脂組成物には、当該３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの他の溶剤として、ガンマブチロラクトンや１，３－ジメチル－２－イミダゾリジンを用いることができることが記載されているが、当該特許は、水を溶媒として使用する水性ポリアミドイミド樹脂組成物の特許である。 WO2018/150566 describes a polyamideimide resin composition containing polyamideimide resin, 3-methoxy-N,N-dimethylpropanamide, and water, and describes that the polyamideimide resin composition can use gamma-butyrolactone or 1,3-dimethyl-2-imidazolidine as a solvent other than the 3-methoxy-N,N-dimethylpropanamide, but the patent is for an aqueous polyamideimide resin composition that uses water as a solvent.
特表２０１７－５１７５８２号公報には、ポリアミド－イミドおよび／またはポリイミド用の溶媒としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの使用、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドとポリアミド－イミドおよび／またはポリイミドとを含む組成物、ならびに３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドを用いる前記組成物の製造方法が記載されていて、前記組成物がワイヤエナメルであることも記載されている。又、単独の３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの使用、又は、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドおよび希釈剤の混合使用で少なくとも６０ｗｔ％の３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドおよび４０ｗｔ％以下の希釈剤を含有する混合物の使用も記載されている。更には、当該特許では、溶媒としてのＮ－メチル－２－ピロリドン（ＮＭＰ）なしで製造することができる組成物、より具体的にはワイヤエナメル、ならびに、それらの製造方法に付いての記載もある。
然し乍ら、当該公報の発明において用いられる希釈剤としては、キシレン、ソルベントナフサ、トルエン、エチルベンゼン、クメン、重ベンゼン等が記載されているだけで、又、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、ジメチルアセトアミド及び芳香族炭化水素（キシレンおよびソルベントナフサの１：１混合物）が記載されているだけで、ガンマブチロラクトンについて触れる記載はない。更には、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの使用により、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド含有エナメルは、今までの従来技術のＮＭＰ含有エナメルと同じ特性レベルを示すとなっているだけで、ポリアミドイミド樹脂生成の際や塗料生成の際のゲル化の問題や塗料外観の濁りや電気絶縁電線における耐軟化性の低下等の問題に触れる記載はない。
JP 2017-517582 A describes the use of 3-methoxy-N,N-dimethylpropanamide as a solvent for polyamide-imide and/or polyimide, a composition containing 3-methoxy-N,N-dimethylpropanamide and polyamide-imide and/or polyimide, and a method for producing the composition using 3-methoxy-N,N-dimethylpropanamide, and also describes that the composition is a wire enamel. It also describes the use of 3-methoxy-N,N-dimethylpropanamide alone, or a mixture of 3-methoxy-N,N-dimethylpropanamide and a diluent, containing at least 60 wt % of 3-methoxy-N,N-dimethylpropanamide and 40 wt % or less of a diluent. Furthermore, the patent also describes compositions, more specifically wire enamels, that can be produced without N-methyl-2-pyrrolidone (NMP) as a solvent, and methods for producing the same.
However, the publication only describes xylene, solvent naphtha, toluene, ethylbenzene, cumene, heavy benzene, etc. as diluents used in the invention, and also describes 3-methoxy-N,N-dimethylpropanamide, dimethylacetamide, and aromatic hydrocarbons (a 1:1 mixture of xylene and solvent naphtha), without mentioning gamma-butyrolactone. Furthermore, it only states that the use of 3-methoxy-N,N-dimethylpropanamide makes enamel containing 3-methoxy-N,N-dimethylpropanamide exhibit the same property level as the NMP-containing enamel of the conventional prior art, but makes no mention of problems such as gelation during polyamideimide resin production or paint production, cloudiness of the paint appearance, or reduced softening resistance in insulated electric wires.
特開２０１０－１８０２６２号公報には、少なくとも（ａ）水分率２．０重量％以下のポリイミド系樹脂を溶剤に溶解する工程および（ｂ）溶剤もしくはポリイミド系樹脂の溶液または混合液に水を添加する工程を含む樹脂組成物の製造方法が記載され、又、前記（ｂ）の工程において、水分量を樹脂組成物中１．０重量％以上８．０重量％以下に調整する上記記載の樹脂組成物の製造方法が記載されていて、溶剤ではなく、ポリイミド系樹脂及び樹脂組成物中の水分量を規定している。 JP 2010-180262 A describes a method for producing a resin composition that includes at least (a) a step of dissolving a polyimide resin having a moisture content of 2.0% or less by weight in a solvent, and (b) a step of adding water to the solvent or a solution or mixture of the polyimide resin. It also describes a method for producing the above-mentioned resin composition in which the moisture content in the resin composition is adjusted to 1.0% or more by weight and 8.0% or less by weight in the step (b), and specifies the moisture content in the polyimide resin and the resin composition, not the solvent.
本発明は、上記従来技術の有する欠点を解消し、又、前記要請に答えることの出来る技術を提供することを目的としたものである。
特に、本発明は、ポリアミドイミド樹脂生成の際や塗料生成の際のゲル化の問題や塗料外観の濁り等の問題や電気絶縁電線における耐軟化性の低下等の問題解決を意図した新規の技術の提供を目的としたものである。
本発明の他の目的や新規な特徴については本件明細書及び図面の記載からも明らかになるであろう。
SUMMARY OF THE PRESENT EMBODIMENT An object of the present invention is to provide a technique that can eliminate the drawbacks of the prior art and meet the above-mentioned demands.
In particular, the present invention aims to provide a novel technology intended to solve problems such as gelation during the production of polyamide-imide resins or coating materials, problems such as cloudy appearance of coating materials, and reduced softening resistance in insulated wires.
Other objects and novel features of the present invention will become apparent from the description of the present specification and the drawings.
本発明は、次の要旨に係る。
反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドを用い、酸成分とイソシアネ－ト成分とを共重合させてポリアミドイミド樹脂を得、得られたポリアミドイミド樹脂を希釈溶剤としてのγ－ブチロラクトンに溶解させてポリアミドイミド樹脂溶液を得るポリアミドイミド樹脂溶液の製法であって、且、
前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド中の含水量を２０００ｐｐｍ未満の範囲に調整し、前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの前記希釈溶剤としてのγ－ブチロラクトンに対しての比率を前者７０～３０重量％：後者３０～７０重量％とし、前記イソシアネ－ト成分としてベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分を単独使用するか、又は、当該ベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分とベンゼン環にメチル基の置換基を有するイソシアネ－ト成分とを混合使用する場合には、前者のベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分を５０ｍｏｌ％を超えた範囲で使用し、前記共重合反応によりポリアミドイミド樹脂を製造する際の最終到達温度を１１７℃以下としてなるポリアミドイミド樹脂溶液の製法であって、当該共重合反応時には水を添加していてもポリアミドイミド樹脂を希釈溶剤に溶解させて得られたポリアミドイミド樹脂溶液中には添加した水を含まないようにすることを特徴とする電気絶縁塗料及び電気絶縁被覆電線に有用なポリアミドイミド樹脂溶液の製法。
The present invention relates to the following gist.
A method for producing a polyamideimide resin solution, comprising the steps of: using 3-methoxy-N,N-dimethylpropanamide as a reaction solvent, copolymerizing an acid component with an isocyanate component to obtain a polyamideimide resin; and dissolving the obtained polyamideimide resin in γ-butyrolactone as a dilution solvent to obtain a polyamideimide resin solution,
The water content in 3-methoxy-N,N-dimethylpropanamide as the reaction solvent is adjusted to a range of less than 2000 ppm, the ratio of 3-methoxy-N,N-dimethylpropanamide as the reaction solvent to γ-butyrolactone as the dilution solvent is set to 70 to 30% by weight for the former and 30 to 70% by weight for the latter, and as the isocyanate component, an isocyanate component having no methyl group substituent on the benzene ring is used alone, or an isocyanate component having no methyl group substituent on the benzene ring and an isocyanate component having a methyl group substituent on the benzene ring are used alone. In the case where a mixture of an isocyanate component and an isocyanate component not having a methyl group substituent on the benzene ring is used in an amount exceeding 50 mol %, and the final temperature achieved in producing a polyamide-imide resin by the copolymerization reaction is set to 117°C or lower , the method for producing a polyamide-imide resin solution useful for an electric insulating coating material and an electric insulating coated electric wire is characterized in that even if water is added during the copolymerization reaction, the polyamide-imide resin solution obtained by dissolving the polyamide-imide resin in a dilution solvent does not contain the added water.
本発明によれば、次のような利点がある。
本発明によれば、前記１に記載のように、反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドを用い、酸成分とイソシアネ－ト成分とを共重合させてポリアミドイミド樹脂を得、得られたポリアミドイミド樹脂を希釈溶剤としてのγ－ブチロラクトンに溶解させてポリアミドイミド樹脂溶液を得るポリアミドイミド樹脂溶液の製法であって、且、前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド中の含水量を２０００ｐｐｍ未満の範囲に調整し、前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの前記希釈溶剤としてのγ－ブチロラクトンに対しての比率を前者７０～３０重量％：後者３０～７０重量％とし、前記イソシアネ－ト成分としてベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分を単独使用するか、又は、当該ベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分とベンゼン環にメチル基の置換基を有するイソシアネ－ト成分とを混合使用する場合には、前者のベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分を５０ｍｏｌ％を超えた範囲で使用し、前記共重合反応によりポリアミドイミド樹脂を製造する際の最終到達温度を１１７℃以下としてなるポリアミドイミド樹脂溶液の製法であって、当該共重合反応時には水を添加していてもポリアミドイミド樹脂を希釈溶剤に溶解させて得られたポリアミドイミド樹脂溶液中には添加した水を含まないようにすることにより、ポリアミドイミド樹脂生成の際や電気絶縁塗料（ワニス）生成の際に、ゲル化してしまったり、ワニスの外観に濁りを生じたりすることが解消され、又、ワニスを電線（コイル）に被覆した電気絶縁電線において、耐軟化性の低下を阻止でき、従来、Ｎ－メチル－２－ピロリドン（ＮＭＰ）等が用いられてきた分野において、環境保全面、安全衛生面、経済性などの面からも、それに代わる代替技術を達成できるようになった。
The present invention has the following advantages.
According to the present invention, as described in 1 above, there is provided a method for producing a polyamideimide resin solution, comprising using 3-methoxy-N,N-dimethylpropanamide as a reaction solvent, copolymerizing an acid component and an isocyanate component to obtain a polyamideimide resin, and dissolving the obtained polyamideimide resin in γ-butyrolactone as a diluent solvent to obtain a polyamideimide resin solution, wherein the water content in the 3-methoxy-N,N-dimethylpropanamide as the reaction solvent is adjusted to a range of less than 2000 ppm, the ratio of the 3-methoxy-N,N-dimethylpropanamide as the reaction solvent to the γ-butyrolactone as the diluent solvent is set to 70 to 30% by weight for the former and 30 to 70% by weight for the latter, and an isocyanate component having no methyl group substituent on the benzene ring is used alone as the isocyanate component, or a mixture of an isocyanate component having no methyl group substituent on the benzene ring and an isocyanate component having a methyl group substituent on the benzene ring is used alone as the isocyanate component. In the case where a cyanate component is used in combination, the isocyanate component having no methyl group substituent on the benzene ring of the former isocyanate component is used in an amount exceeding 50 mol %, and the final temperature reached during the production of polyamideimide resin by the copolymerization reaction is set to 117°C or lower . Even if water is added during the copolymerization reaction, the polyamideimide resin solution obtained by dissolving the polyamideimide resin in a dilution solvent does not contain the added water. This eliminates gelation during the production of polyamideimide resin or electrical insulating paint (varnish) and the occurrence of turbidity in the appearance of the varnish. Furthermore, it is possible to prevent a decrease in softening resistance in an electrical insulated wire in which varnish is coated on the wire (coil). In fields in which N-methyl-2-pyrrolidone (NMP) and the like have conventionally been used, it has become possible to achieve an alternative technology from the standpoints of environmental conservation, safety and hygiene, and economy.
本発明によるポリアミドイミド樹脂溶液は、電気絶縁塗料及び電気絶縁被覆電線に有用で、前記ポリアミドイミド樹脂溶液を用いて電気絶縁塗料とし、又、当該電気絶縁塗料を用いて電気絶縁被覆電線することにより、ワニスの外観に濁りを生じたりすることが解消され、又、ワニスを電線（コイル）に被覆した電気絶縁電線において、耐軟化性の低下を阻止でき、従来、Ｎ－メチル－２－ピロリドン（ＮＭＰ）等が用いられてきた分野において、環境保全面、安全衛生面、経済性などの面からも、それに代わる代替え技術を達成できるようになる。 The polyamide-imide resin solution according to the present invention is useful for electrical insulating paints and electrical insulating coated electric wires. By using the polyamide-imide resin solution to prepare an electrical insulating paint or to prepare an electrical insulating coated electric wire using the electrical insulating paint, the occurrence of turbidity in the appearance of the varnish is eliminated, and in an electrical insulated electric wire in which the varnish is coated on an electric wire (coil), a decrease in softening resistance can be prevented. In fields in which N-methyl-2-pyrrolidone (NMP) and the like have conventionally been used, an alternative technology can be achieved in terms of environmental conservation, safety and hygiene, economy, and the like.
本発明は、反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用いる。
反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用いることにより、従来、Ｎ－メチル－２－ピロリドン（ＮＭＰ）を重合の際の反応溶剤（重合溶剤）として用いて製造されてきた汎用のポリアミドイミド樹脂とほぼ同等の特性を有するポリアミドイミド樹脂を得ることができる。
一方、反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）及びγ－ブチロラクトン（ＧＢＬ）を用いた場合、それにより得られた電気絶縁塗料を導体上に塗布、焼付けて電気絶縁電線としたところ、前記汎用のポリアミドイミド樹脂よりも、耐軟化性の低下が見られた。
The present invention uses 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent.
By using 3-methoxy-N,N-dimethylpropanamide (MDMPA) as a reaction solvent, it is possible to obtain a polyamide-imide resin having properties almost equivalent to those of general-purpose polyamide-imide resins that have conventionally been produced using N-methyl-2-pyrrolidone (NMP) as a reaction solvent (polymerization solvent) during polymerization.
On the other hand, when 3-methoxy-N,N-dimethylpropanamide (MDMPA) and γ-butyrolactone (GBL) were used as the reaction solvent, the obtained electrical insulating paint was applied to a conductor and baked to form an electrically insulated electric wire, and a decrease in softening resistance was observed compared to the general-purpose polyamideimide resin.
前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）は、当該３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）中の含水量の如何が重要であることが判った。
反応開始時に反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の水分量を測定し、又、既定の水分量になるように、精製水を添加し、当該反応溶剤中の水分量を調整する。
その調整の一例を示すと、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の水分量を１０００ｐｐｍと規定し、反応溶剤中の水分量が５００ｐｐｍの場合、精製水を添加して反応溶剤中の水分量が１０００ｐｐｍとなるように水分量を調整する。
仮に、反応溶剤の水分量が１０００ｐｐｍの場合は精製水は添加しない。
本発明では、当該反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の水分量は、２０００ｐｐｍ未満に調整することが必要である。
当該反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）中の含水量が、２０００ｐｐｍ以上の場合には、ポリアミドイミド樹脂溶液に濁りが生じる。
反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）及びγ－ブチロラクトン（ＧＢＬ）からなる混合溶剤を用いた場合、ワニスを電線（コイル）に被覆した電気絶縁電線において、耐軟化性の低下が見られるので、反応溶剤としては、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）単独使用がよいことが判った、
It has been found that the water content in 3-methoxy-N,N-dimethylpropanamide (MDMPA) used as the reaction solvent is important.
At the start of the reaction, the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent is measured, and purified water is added to adjust the water content in the reaction solvent to a predetermined value.
As an example of such adjustment, if the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as a reaction solvent is specified as 1000 ppm, and the water content in the reaction solvent is 500 ppm, purified water is added to adjust the water content so that the water content in the reaction solvent becomes 1000 ppm.
If the water content of the reaction solvent is 1000 ppm, purified water is not added.
In the present invention, it is necessary to adjust the water content of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA), to less than 2000 ppm.
When the water content in the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) is 2000 ppm or more, the polyamide-imide resin solution becomes turbid.
When a mixed solvent of 3-methoxy-N,N-dimethylpropanamide (MDMPA) and γ-butyrolactone (GBL) was used as a reaction solvent, a decrease in softening resistance was observed in an insulated electric wire in which a varnish was coated on the electric wire (coil). Therefore, it was found that it is better to use 3-methoxy-N,N-dimethylpropanamide (MDMPA) alone as a reaction solvent.
本発明では、上記のように、反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、酸成分とイソシアネ－ト成分とを共重合させてポリアミドイミド樹脂を得、得られたポリアミドイミド樹脂を希釈溶剤に溶解させてポリアミドイミド樹脂溶液を得る。
当該希釈溶剤としては、γ－ブチロラクトン（ＧＢＬ）の他に、反応溶剤と同じ３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用いることも検討され、又、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）とγ－ブチロラクトン（ＧＢＬ）からなる混合溶剤を用いることも検討されたが、ワニスを電線（コイル）に被覆した電気絶縁電線において、耐軟化性の低下が見られ、反応溶剤の３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）とは別個のγ－ブチロラクトン（ＧＢＬ）の使用が好ましいことが判った。
希釈溶剤は、ポリアミドイミド樹脂の溶解の機能の他に、ポリアミドイミド樹脂溶液の冷却機能も果たす。
In the present invention, as described above, 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as a reaction solvent, an acid component and an isocyanate component are copolymerized to obtain a polyamide-imide resin, and the obtained polyamide-imide resin is dissolved in a diluent solvent to obtain a polyamide-imide resin solution.
As the dilution solvent, in addition to γ-butyrolactone (GBL), the use of 3-methoxy-N,N-dimethylpropanamide (MDMPA), which is the same as the reaction solvent, was also considered. Also, the use of a mixed solvent consisting of 3-methoxy-N,N-dimethylpropanamide (MDMPA) and γ-butyrolactone (GBL) was considered. However, a decrease in softening resistance was observed in an insulated electric wire in which the varnish was coated on the electric wire (coil), and it was found that the use of γ-butyrolactone (GBL), which is separate from the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA), is preferable.
The dilution solvent not only dissolves the polyamide-imide resin, but also cools the polyamide-imide resin solution.
ポリアミドイミド樹脂溶液の製法において、前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）中の含水量を２０００ｐｐｍ未満に調整すると共に、前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の前記希釈溶剤のγ－ブチロラクトン（ＧＢＬ）に対しての比率を３０重量％以上とする。
反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドと当該希釈溶剤としてのγ－ブチロラクトンとの比率が、前者７０～３０重量％：後者３０～７０重量％とすることが好ましいことも判った。
当該比率を脱れると、ポリアミドイミド樹脂（溶液）のゲル化を招いたりする。
In a method for producing a polyamide-imide resin solution, the water content in 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent is adjusted to less than 2000 ppm, and the ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent to γ-butyrolactone (GBL) as the dilution solvent is set to 30% by weight or more.
It was also found that the ratio of 3-methoxy-N,N-dimethylpropanamide as the reaction solvent to γ-butyrolactone as the dilution solvent is preferably 70 to 30% by weight for the former: 30 to 70% by weight for the latter.
If the ratio is outside this range, gelation of the polyamideimide resin (solution) may occur.
本発明では、前記共重合反応によりポリアミドイミド樹脂を製造する際に、末端封止剤を添加するとよい。
共重合反応によりポリアミドイミド樹脂を製造する際に、末端封止剤を添加してなることにより、ワニスの外観に濁りを生じたりすることが解消され、又、ワニスを電線（コイル）に被覆した電気絶縁電線において、耐軟化性の低下を阻止でき、従来、Ｎ－メチル－２－ピロリドン（ＮＭＰ）等が用いられてきた分野において、環境保全面、安全衛生面、経済性などの面からも、それに代わる代替技術を達成できるようになる。
ポリアミドイミド樹脂は、分子量が増大するにつれ、伸張率、弾性率が増大して柔軟性、耐熱性などが向上するが、一方では溶剤への溶解性が低下したり、溶液が高粘度化するなどの不利がある。
カルボキシル基および／または酸無水物基を分子末端に有するポリアミドイミド樹脂の当該分子末端基を末端封止剤で封止されているとよい。
当該末端封止剤として、一価アルコ－ルが好ましく、エタノ－ル、メタノ－ル等が使用できる。
In the present invention, when the polyamide-imide resin is produced by the copolymerization reaction, an end-capping agent may be added.
By adding an end-capping agent when producing a polyamide-imide resin by a copolymerization reaction, the occurrence of turbidity in the appearance of the varnish can be eliminated, and a decrease in softening resistance can be prevented in an insulated electric wire in which the varnish is coated on the electric wire (coil). In addition, in fields in which N-methyl-2-pyrrolidone (NMP) and the like have conventionally been used, an alternative technology can be achieved that is also advantageous in terms of environmental conservation, safety and hygiene, and economy.
As the molecular weight of polyamide-imide resin increases, the elongation rate and elastic modulus increase, improving flexibility and heat resistance, etc., but on the other hand, there are disadvantages such as a decrease in solubility in solvents and an increase in the viscosity of the solution.
It is preferable that the molecular end groups of the polyamide-imide resin having a carboxyl group and/or an acid anhydride group at the molecular end are blocked with a terminal blocking agent.
The end-capping agent is preferably a monohydric alcohol, such as ethanol or methanol.
本発明において、当該共重合（縮合反応）によりポリアミドイミド樹脂を得るのにイソシアネ－ト法により、酸成分とイソシアネ－ト成分とを共重合させて行う。
酸成分としては、例えば、芳香族三塩基酸無水物が使用される。
当該芳香族三塩基酸無水物としては、トリメリット酸無水物が好適である。
トリメリット酸無水物の例としては、ベンゼン－１，２，４－トリカルボン酸１，２無水物（ＴＭＡ）が挙げられる。
トリメリット酸無水物に加えて、他の多塩基酸、例えば、芳香族テトラカルボン酸二無水物が挙げられる。
In the present invention, the polyamide-imide resin is obtained by the copolymerization (condensation reaction) by copolymerizing an acid component and an isocyanate component by the isocyanate method.
As the acid component, for example, an aromatic tribasic acid anhydride is used.
As the aromatic tribasic acid anhydride, trimellitic anhydride is preferable.
An example of a trimellitic anhydride is benzene-1,2,4-tricarboxylic acid 1,2 anhydride (TMA).
In addition to trimellitic anhydride, other polybasic acids, such as aromatic tetracarboxylic dianhydrides, are included.
芳香族テトラカルボン酸二無水物の具体例としては、非縮合多環式の芳香族テトラカルボン酸二無水物、単環式の芳香族テトラカルボン酸二無水物及び縮合多環式の芳香族テトラカルボン酸二無水物が挙げられる。
非縮合多環式の芳香族テトラカルボン酸二無水物としては、４，４’－オキシジフタル酸二無水物（ＯＰＤＡ）、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、２，２’，３，３’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、２，２’，３，３’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェノキシフェニル）プロパン二無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物、１，２－ビス（２，３－ジカルボキシフェニル）エタン二無水物、１，１－ビス（２，３－ジカルボキシフェニル）エタン二無水物、１，２－ビス（３，４－ジカルボキシフェニル）エタン二無水物、１，１－ビス（３，４－ジカルボキシフェニル）エタン二無水物、ビス（３，４－ジカルボキシフェニル）メタン二無水物、ビス（２，３－ジカルボキシフェニル）メタン二無水物、４，４’－（ｐ－フェニレンジオキシ）ジフタル酸二無水物、４，４’－（ｍ－フェニレンジオキシ）ジフタル酸二無水物が挙げられる。
又、単環式の芳香族テトラカルボン酸二無水物としては、１，２，４，５－ベンゼンテトラカルボン酸二無水物が挙げられる。
縮合多環式の芳香族テトラカルボン酸二無水物としては、２，３，６，７－ナフタレンテトラカルボン酸二無水物が挙げられる。
これらは単独でまたは２種以上を組み合わせて用いることができる。
Specific examples of the aromatic tetracarboxylic acid dianhydride include non-condensed polycyclic aromatic tetracarboxylic acid dianhydrides, monocyclic aromatic tetracarboxylic acid dianhydrides, and condensed polycyclic aromatic tetracarboxylic acid dianhydrides.
Examples of non-condensed polycyclic aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic dianhydride (OPDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. phenoxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalic dianhydride, and 4,4'-(m-phenylenedioxy)diphthalic dianhydride.
Furthermore, an example of the monocyclic aromatic tetracarboxylic dianhydride is 1,2,4,5-benzenetetracarboxylic dianhydride.
An example of the condensed polycyclic aromatic tetracarboxylic dianhydride is 2,3,6,7-naphthalenetetracarboxylic dianhydride.
These may be used alone or in combination of two or more.
当該酸成分としては、脂肪族テトラカルボン酸二無水物でもよい。
脂肪族テトラカルボン酸二無水物としては、環式または非環式の脂肪族テトラカルボン酸二無水物が挙げられる。
環式脂肪族テトラカルボン酸二無水物とは、脂環式炭化水素構造を有するテトラカルボン酸二無水物であり、その具体例としては、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物等のシクロアルカンテトラカルボン酸二無水物、ビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸二無水物、ジシクロヘキシル３，３’－４，４’－テトラカルボン酸二無水物およびこれらの位置異性体が挙げられる。これらは単独でまたは２種以上を組み合わせて用いることができる。
非環式脂肪族テトラカルボン酸二無水物の具体例としては、１，２，３，４－ブタンテトラカルボン酸二無水物、および１，２，３，４－ペンタンテトラカルボン酸二無水物等が挙げられ、これらは単独でまたは２種以上を組み合わせて用いることができる。また、環式脂肪族テトラカルボン酸二無水物および非環式脂肪
族テトラカルボン酸二無水物を組み合わせて用いてもよい。
The acid component may be an aliphatic tetracarboxylic dianhydride.
The aliphatic tetracarboxylic dianhydride may be a cyclic or acyclic aliphatic tetracarboxylic dianhydride.
The cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include cycloalkane tetracarboxylic dianhydrides such as 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and 1,2,3,4-cyclopentane tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl 3,3'-4,4'-tetracarboxylic dianhydride, and positional isomers thereof. These can be used alone or in combination of two or more kinds.
Specific examples of the acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-pentanetetracarboxylic dianhydride, which may be used alone or in combination of two or more. Also, a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.
本発明のポリアミドイミド樹脂の共重合には、イソシアネ－ト成分が使用される。
当該イソシアネ－ト成分としては、例えば、ジイソシアネ－ト成分が使用される。当該ジイソシアネ－ト成分としては、代表的な例として、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）が挙げられる。
４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）以外のジイソシアネ－ト類としては、例えば、ヘキサメチレンジイソシアネ－ト（ＨＤＩ）、イソホロンジイソシアネ－ト（ＩＰＤＩ）、ジシクロヘキシルメタンジイソシアネ－ト（Ｈ－ＭＤＩ）、キシレンジイソシアネ－ト（ＸＤＩ）、水添ＸＤＩなどの脂肪族ジイソシアネ－ト類も挙げられる。４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）に、、ジフェニルスルホンジイソシアネ－ト（ＳＤＩ）などの芳香族ジイソシアネ－ト類などを併用することもできる。
本発明では、イソシアネ－ト成分として、例えば、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）のような、ベンゼン環にメチル基の置換基を有しないイソシアネ－ト（Ａ）を使用することが好ましい。本発明では、イソシアネ－ト成分として、上記のようなベンゼン環にメチル基の置換基を有しない、例えば、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）のようなイソシアネ－ト（Ａ）を単独使用することがより好ましい。
本発明では、イソシアネ－ト成分として、ベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分（Ａ）、例えば、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を単独使用せずに、当該ベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分（Ａ）とベンゼン環にメチル基の置換基を有するイソシアネ－ト成分（Ｂ）例えばトリレンジイソシアネ－ト（ＴＤＩ）とを混合使用する場合、全イソシアネ－ト成分を１００ｍｏｌ％とすると、前者のベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分（Ａ）を５０ｍｏｌ％を超えた範囲で使用する。
本発明では、イソシアネ－ト成分として、他に、トリフェニルメタントリイソシアネ－トなどの多官能イソシアネ－トやポリメリックイソシアネ－ト、又、ＭＤＩの異性体を含むもの等でも使用できる。
イソシアネ－ト成分として、経日変化を避けるために、適宜ブロック剤でイソシアネ－ト基を安定化したものを使用してもよい。ブロック剤としてはアルコ－ル、フェノ－ル、オキシム等があるが、ポリアミドイミド樹脂（溶液）のゲル化を招かないようにする必要がある。
An isocyanate component is used in the copolymerization of the polyamide-imide resin of the present invention.
As the isocyanate component, for example, a diisocyanate component is used. A representative example of the diisocyanate component is 4,4'-diphenylmethane diisocyanate (MDI).
Examples of diisocyanates other than 4,4'-diphenylmethane diisocyanate (MDI) include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H-MDI), xylene diisocyanate (XDI), hydrogenated XDI, etc. Aromatic diisocyanates such as diphenylsulfone diisocyanate (SDI) can also be used in combination with 4,4'-diphenylmethane diisocyanate (MDI).
In the present invention, it is preferable to use, as the isocyanate component, an isocyanate (A) that does not have a methyl group substituent on the benzene ring, such as 4,4'-diphenylmethane diisocyanate (MDI). In the present invention, it is more preferable to use, as the isocyanate component, an isocyanate (A) that does not have a methyl group substituent on the benzene ring, such as 4,4'-diphenylmethane diisocyanate (MDI), alone.
In the present invention, when an isocyanate component (A) having no methyl group substituents on its benzene ring, for example, 4,4'-diphenylmethane diisocyanate (MDI) is not used alone as the isocyanate component, but a mixture of the isocyanate component (A) having no methyl group substituents on its benzene ring and an isocyanate component (B) having a methyl group substituent on its benzene ring, for example, tolylene diisocyanate (TDI), is used, the former isocyanate component (A) having no methyl group substituents on its benzene ring is used in an amount exceeding 50 mol % when the total isocyanate components are taken as 100 mol %.
In the present invention, other isocyanate components that can be used include polyfunctional isocyanates such as triphenylmethane triisocyanate, polymeric isocyanates, and isocyanates containing isomers of MDI.
In order to prevent deterioration over time, the isocyanate component may be used with an appropriate blocking agent to stabilize the isocyanate group. Blocking agents include alcohol, phenol, oxime, etc., but it is necessary to avoid gelling of the polyamide-imide resin (solution).
本発明では、前記のように、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）中の含水量の如何が重要で、反応開始時に反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の水分量を測定し、又、既定の水分量になるように、精製水を添加し、当該反応溶剤中の水分量を調整したりして、当該反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の水分量（含水量）を、２０００ｐｐｍ未満の範囲に調整するが、得られたポリアミドイミド樹脂及び希釈溶剤に溶解されたポリアミドイミド樹脂溶液中には殆ど水を含まないようにする。
本発明では、反応溶剤として３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、前記酸成分と前記イソシアネ－ト成分とを共重合させてポリアミドイミド樹脂を得る際に、イソシアネ－ト成分を投入する前に、酸成分の例えばベンゼン－１，２，４－トリカルボン酸１，２無水物（ＴＭＡ）と水を適宜温度で反応させることで、当該酸成分の酸無水物の開環量を調節し、製造安定性の向上を狙ってもよい。
本発明における反応後のポリアミドイミド樹脂溶液（ワニス）の水分量についてであるが、反応溶液中の水分は反応時にすべて消費され、反応後の水分量は、存在するとしても、極く微量である
本発明では、共重合反応時には水を添加していても、ポリアミドイミド樹脂を希釈溶剤に溶解させて得られたポリアミドイミド樹脂溶液中には水を含まないようにする。ポリアミドイミド樹脂と水とを含有するポリアミドイミド樹脂溶液よりなる水系ポリアミドイミド樹脂組成物も存在するが、上記のように、本発明とは異なっている。
In the present invention, as described above, the water content in 3-methoxy-N,N-dimethylpropanamide (MDMPA) as a reaction solvent is important, and the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as a reaction solvent is measured at the start of the reaction, and purified water is added to adjust the water content in the reaction solvent so that the water content becomes a predetermined value, thereby adjusting the water content (water content) of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as a reaction solvent to a range of less than 2000 ppm, while the obtained polyamideimide resin and the polyamideimide resin solution dissolved in a dilution solvent contain almost no water.
In the present invention, when 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as a reaction solvent and the acid component and the isocyanate component are copolymerized to obtain a polyamide-imide resin, the amount of ring-opening of the acid anhydride of the acid component can be adjusted by reacting the acid component, for example, benzene-1,2,4-tricarboxylic acid 1,2 anhydride (TMA), with water at an appropriate temperature before adding the isocyanate component, thereby aiming to improve production stability.
Regarding the water content of the polyamideimide resin solution (varnish) after the reaction in the present invention, all water in the reaction solution is consumed during the reaction, and the amount of water after the reaction is very small, if any. In the present invention, even if water is added during the copolymerization reaction, the polyamideimide resin solution obtained by dissolving the polyamideimide resin in a diluent solvent does not contain water. There are also aqueous polyamideimide resin compositions consisting of polyamideimide resin solutions containing polyamideimide resin and water, but as mentioned above, they are different from the present invention.
本発明では、酸成分とイソシアネ－ト成分とを共重合させてポリアミドイミド樹脂を得るイソシアネ－ト法によるので、ジアミン等のアミノ基を有するポリアミンのようなアミン成分は使用しない。これにより、イソシアネ－ト基にアミノ基（ポリアミン）が結合してできる樹脂中のウレア結合が、アミド結合やイミド結合の他に生成されることを回避している。 In the present invention, the isocyanate method is used to obtain polyamide-imide resin by copolymerizing an acid component and an isocyanate component, so amine components such as polyamines having amino groups such as diamines are not used. This prevents the formation of urea bonds in the resin, which are formed when an amino group (polyamine) bonds with an isocyanate group, in addition to amide bonds and imide bonds.
本発明では、共重合反応によりポリアミドイミド樹脂を製造する際の最終到達温度を１１７℃以下とする。当該最終到達温度が１２０℃を超えると、ポリアミドイミド樹脂（溶液）のゲル化を招いたりする。 In the present invention, the final temperature reached when producing a polyamide-imide resin by a copolymerization reaction is set to not more than 117° C. If the final temperature reached exceeds 120° C., gelation of the polyamide-imide resin (solution) may occur.
本発明のポリアミドイミド樹脂溶液により電気絶縁塗料を構成できる。
当該電気絶縁塗料には、各種添加剤を添加することができる。
当該添加剤には、架橋剤、滑剤などが挙げられる。当該架橋剤の例としては、Ｔｉ触媒などが挙げられる。 又、当該滑剤としては、脂肪酸エステル、低分子ポリエチレン、ワックスなどが例示できる。
当該添加剤としては、他に必要に応じて、着色剤やフェノ－ル系酸化防止剤等の酸化防止剤（耐候剤）や難燃剤や反応触媒などを添加してもよい。
The polyamide-imide resin solution of the present invention can be used to form an electrical insulating coating material.
Various additives can be added to the electrical insulating paint.
The additives include crosslinking agents, lubricants, etc. Examples of the crosslinking agents include Ti catalysts, etc. Examples of the lubricants include fatty acid esters, low molecular weight polyethylene, wax, etc.
Other additives that may be added, if necessary, include colorants, antioxidants (weather resistance agents) such as phenolic antioxidants, flame retardants, and reaction catalysts.
本発明では、上記の電気絶縁塗料を導体上に塗布、焼付けして電気絶縁電線を構成することができる。
当該電気絶縁電線（マグネットワイヤ－）は、銅線などの導体（導線）に、電気絶縁塗料を塗布し、焼付炉で焼付けすればよい。
In the present invention, an electrically insulated wire can be produced by applying the above-mentioned electrically insulating paint onto a conductor and baking it.
The electrically insulated wire (magnet wire) can be produced by coating an electrically insulating paint on a conductor (conductor wire) such as a copper wire, and baking the paint in a baking oven.
以下に実施例を挙げ本発明のより詳細な理解に供する。当然のことながら本発明は以下の実施例のみに限定されるものではない。 The following examples are provided to provide a more detailed understanding of the present invention. Naturally, the present invention is not limited to the following examples.
２リットル容量のセパラブルフラスコに含水量が１５００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を１７００ｇ（１２．９モル）、ベンゼン－１，２，４－トリカルボン酸１，２無水物（ＴＭＡ）を７６０ｇ（４．１１モル）を仕込み、６５℃で１時間反応させた。
その後、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を１０００ｇ（４モル）投入し、１１２℃昇温し合成反応させた。１１２℃に到達後、希釈溶剤であるγ－ブチロラクトン（ＧＢＬ）を１６００ｇ、末端封止剤であるメタノ－ル（０．３ｍｏｌ）を１０ｇ加え、冷却を行い、目的とするポリアミドイミド樹脂溶液を得た。
反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率は次の通りであった。
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝５１．５ｗｔ％：４８．５ｗｔ％
ポリアミドイミド樹脂の分子量（Ｍｗ）は、４７０５３、ポリアミドイミド樹脂溶液の不揮発分は、３３ｗｔ％、粘度は、５２．６ｄＰａ・ｓであった。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
後述のように、当該ワニスを使用して電気絶縁電線を形成した。
A 2-liter separable flask was charged with 1700 g (12.9 mol) of 3-methoxy-N,N-dimethylpropanamide (MDMPA) having a water content of 1500 ppm and 760 g (4.11 mol) of benzene-1,2,4-tricarboxylic acid 1,2 anhydride (TMA), and the mixture was reacted at 65° C. for 1 hour.
Then, 1000 g (4 moles) of 4,4'-diphenylmethane diisocyanate (MDI) was added, and the temperature was raised to 112°C to carry out a synthesis reaction. After the temperature reached 112°C, 1600 g of γ-butyrolactone (GBL) as a dilution solvent and 10 g of methanol (0.3 mol) as an end-capping agent were added, and the mixture was cooled to obtain a target polyamideimide resin solution.
The ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was as follows:
3-Methoxy-N,N-dimethylpropanamide (MDMPA): γ-butyrolactone (GBL) = 51.5 wt%: 48.5 wt%
The molecular weight (Mw) of the polyamideimide resin was 47053, the non-volatile content of the polyamideimide resin solution was 33 wt %, and the viscosity was 52.6 dPa·s.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
The varnish was used to form an electrically insulated wire, as described below.
２リットル容量のセパラブルフラスコに３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を１７００ｇ（１２．９モル）、ベンゼン－１，２，４－トリカルボン酸１，２無水物（ＴＭＡ）を７６０ｇ（４．１１モル）、精製水を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量が１０００ｐｐｍになるように仕込み、６５℃で１時間反応させた。
その後、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を１０００ｇ（４モル）投入し、１１５℃まで昇温し合成反応させた。１１５℃に到達後、希釈溶剤であるγ－ブチロラクトン（ＧＢＬ）を１６００ｇ、末端封止剤であるメタノ－ル（０．３ｍｏｌ）を１０ｇ加え、冷却を行い、目的とするポリアミドイミド樹脂溶液を得た。
反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率は次の通りであった。
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝５１．５ｗｔ％：４８．５ｗｔ％
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A 2-liter separable flask was charged with 1700 g (12.9 mol) of 3-methoxy-N,N-dimethylpropanamide (MDMPA), 760 g (4.11 mol) of benzene-1,2,4-tricarboxylic acid 1,2 anhydride (TMA), and purified water such that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 1000 ppm, and the mixture was reacted at 65° C. for 1 hour.
Thereafter, 1000 g (4 moles) of 4,4'-diphenylmethane diisocyanate (MDI) was added, and the temperature was raised to 115°C to carry out a synthesis reaction. After the temperature reached 115°C, 1600 g of γ-butyrolactone (GBL) as a dilution solvent and 10 g of methanol (0.3 mol) as an end-capping agent were added, and the mixture was cooled to obtain a target polyamideimide resin solution.
The ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was as follows:
3-Methoxy-N,N-dimethylpropanamide (MDMPA): γ-butyrolactone (GBL) = 51.5 wt%: 48.5 wt%
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を５５３ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝３０ｗｔ％：７０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１０４℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 553 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 30 wt %:γ-butyrolactone (GBL) = 30 wt %: 70 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 104°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を１０００ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝４０ｗｔ％：６０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１７℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 1000 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 3-methoxy-N,N-dimethylpropanamide (MDMPA):γ-butyrolactone (GBL) = 40 wt %:60 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 117°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を１０００ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝５０ｗｔ％：５０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１５℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 1000 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 3-methoxy-N,N-dimethylpropanamide (MDMPA):γ-butyrolactone (GBL) = 50 wt %:50 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 115°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を１０００ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝６０ｗｔ％：４０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１２℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 1000 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 3-methoxy-N,N-dimethylpropanamide (MDMPA):γ-butyrolactone (GBL) = 60 wt %:40 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 112°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を４３４ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝５０ｗｔ％：５０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１４℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 434 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 3-methoxy-N,N-dimethylpropanamide (MDMPA):γ-butyrolactone (GBL) = 50 wt %:50 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 114°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を１５００ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝４０ｗｔ％：６０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１７℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 1500 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 3-methoxy-N,N-dimethylpropanamide (MDMPA):γ-butyrolactone (GBL) = 40 wt %:60 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 117°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を１０００ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝５０ｗｔ％：５０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１５℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 1000 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 3-methoxy-N,N-dimethylpropanamide (MDMPA):γ-butyrolactone (GBL) = 50 wt %:50 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 115°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量を１０００ｐｐｍとし、反応溶剤３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤γ－ブチロラクトン（ＧＢＬ）との比率を、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）：γ－ブチロラクトン（ＧＢＬ）＝５０ｗｔ％：５０ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１２℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
比較例１
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) was 1000 ppm, the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) was 3-methoxy-N,N-dimethylpropanamide (MDMPA):γ-butyrolactone (GBL) = 50 wt %:50 wt %, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 112°C to carry out the synthesis reaction.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
Comparative Example 1
反応溶剤として、含水量が３０００ｐｐｍのＮ－メチル－２－ピロリドン（ＮＭＰ）を用い、希釈溶剤としてジメチルアセトアミド（ＤＭＡｃ）を用い、
反応溶剤Ｎ－メチル－２－ピロリドン（ＮＭＰ）と希釈溶剤ジメチルアセトアミド（ＤＭＡｃ）との比率を、Ｎ－メチル－２－ピロリドン（ＮＭＰ）：ジメチルアセトアミド（ＤＭＡｃ）＝５１．５ｗｔ％：４８．５ｗｔ％とし、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１３０℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ポリアミドイミド樹脂の分子量（Ｍｗ）は、４０８０４、ポリアミドイミド樹脂溶液の不揮発分は、３３．０％、粘度は、１６ｄＰａ・ｓであった。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
当該ポリアミドイミド樹脂溶液（ワニス）は、従来例の汎用ワニスで、Ｎ－メチル－２－ピロリドン（ＮＭＰ）は、近年その毒性が懸念され、健康被害および環境への悪影響に鑑み、ヨーロッパ地域では「制限対象物質」に指定され、使用の届け出等の負担が必要となる見通しで、ＮＭＰなしのワイヤエナメルが求められている。
比較例２
As the reaction solvent, N-methyl-2-pyrrolidone (NMP) with a water content of 3000 ppm was used, and as the dilution solvent, dimethylacetamide (DMAc) was used.
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that the ratio of the reaction solvent N-methyl-2-pyrrolidone (NMP) to the dilution solvent dimethylacetamide (DMAc) was N-methyl-2-pyrrolidone (NMP):dimethylacetamide (DMAc) = 51.5 wt%:48.5 wt%, and after 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 130°C to carry out the synthesis reaction.
The molecular weight (Mw) of the polyamideimide resin was 40,804, the non-volatile content of the polyamideimide resin solution was 33.0%, and the viscosity was 16 dPa·s.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
The polyamide-imide resin solution (varnish) in question is a conventional general-purpose varnish, and N-methyl-2-pyrrolidone (NMP) has recently come under scrutiny due to its toxicity. In light of its health hazards and adverse effects on the environment, it has been designated a "restricted substance" in Europe, and it is expected that users will be required to pay for notification of its use, etc., and so there is a demand for wire enamels without NMP.
Comparative Example 2
反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としても３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１５℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
ポリアミドイミド樹脂の分子量（Ｍｗ）は、４７０５３、ポリアミドイミド樹脂溶液の不揮発分は、３３％、粘度は、５１．４ｄＰａ・ｓであった。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
然し乍ら、後述のように、反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としても３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用いてなる当該ポリアミドイミド樹脂溶液（ワニス）は、ワイヤエナメルとしてこれを電線に被覆して電気絶縁電線とした時に、耐軟化性の低下が見られる。
この結果、希釈溶剤としては、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用いず、γ－ブチロラクトン（ＧＢＬ）の使用が良い。
比較例３
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm was used as the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) was also used as the dilution solvent, 4,4'-diphenylmethane diisocyanate (MDI) was added, and the temperature was raised to 115°C to carry out the synthesis reaction.
The molecular weight (Mw) of the polyamideimide resin was 47053, the non-volatile content of the polyamideimide resin solution was 33%, and the viscosity was 51.4 dPa·s.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
However, as described below, when the polyamideimide resin solution (varnish) using 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm as the reaction solvent and also using 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the dilution solvent is used as wire enamel to coat an electric wire to produce an electrically insulated electric wire, a decrease in softening resistance is observed.
As a result, it is preferable to use γ-butyrolactone (GBL) as the dilution solvent rather than 3-methoxy-N,N-dimethylpropanamide (MDMPA).
Comparative Example 3
反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）及びγ－ブチロラクトン（ＧＢＬ）を用い、希釈溶剤としても３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）及びγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１５℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）とγ－ブチロラクトン（ＧＢＬ）との比は、前者：後者＝５２．９：４７．１で、希釈溶剤の３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）とγ－ブチロラクトン（ＧＢＬ）との比率は、前者：後者＝５１．５：４８．５であった。
得られたポリアミドイミド樹脂の分子量（Ｍｗ）は、７８６３８、ポリアミドイミド樹脂溶液の不揮発分は、３３ｗｔ％、粘度は、７９．４ｄＰａ・ｓであった。
ワニスはゲル化せず、ワニスの外観に濁りを生じたりすることはなかった。
然し乍ら、後述のように、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）１００％の当該ポリアミドイミド樹脂溶液（ワニス）は、ワイヤエナメルとしてこれを電線に被覆して電気絶縁電線とした時に、耐軟化性の低下が見られる。
この結果、反応溶剤は、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）単独が良いことが判った。
比較例４
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) and γ-butyrolactone (GBL) having a water content of 1000 ppm were used as the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) and γ-butyrolactone (GBL) were also used as the dilution solvent, 4,4'-diphenylmethane diisocyanate (MDI) was added, and the temperature was raised to 115°C to carry out the synthesis reaction.
The ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) having a water content of 1000 ppm to γ-butyrolactone (GBL) in the reaction solvent was the former:latter=52.9:47.1, and the ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) to γ-butyrolactone (GBL) in the dilution solvent was the former:latter=51.5:48.5.
The molecular weight (Mw) of the obtained polyamideimide resin was 78,638, the non-volatile content of the polyamideimide resin solution was 33 wt %, and the viscosity was 79.4 dPa·s.
The varnish did not gel, and the appearance of the varnish did not become cloudy.
However, as described below, when the polyamideimide resin solution (varnish) containing 100% 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as wire enamel to coat an electric wire to produce an electrically insulated electric wire, a decrease in softening resistance is observed.
As a result, it was found that 3-methoxy-N,N-dimethylpropanamide (MDMPA) alone was a good reaction solvent.
Comparative Example 4
反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１２２℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比は、前者：後者＝１０：９０とした。
得られたポリアミドイミド樹脂溶液（ワニス）は、合成翌日にゲル化してしまった。
希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用いてもよいが、反応溶剤としての水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）との比率が問題である。
比較例５
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm was used as the reaction solvent, γ-butyrolactone (GBL) was used as the dilution solvent, and 4,4'-diphenylmethane diisocyanate (MDI) was added and then the temperature was raised to 122°C to carry out the synthesis reaction.
The ratio of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm, to the dilution solvent, γ-butyrolactone (GBL), was set to 10:90.
The resulting polyamideimide resin solution (varnish) gelled the next day after synthesis.
Although γ-butyrolactone (GBL) may be used as a dilution solvent, the ratio of GBL to 3-methoxy-N,N-dimethylpropanamide (MDMPA) having a water content of 1000 ppm as a reaction solvent is problematic.
Comparative Example 5
反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１２℃まで昇温し合成反応させた以外は、比較例４と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比は、前者：後者＝２０：８０とした。
得られたポリアミドイミド樹脂溶液（ワニス）は、合成翌日にゲル化してしまった。
希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用いてもよいが、反応溶剤としての水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）との比（率）が問題である。
比較例６
A polyamideimide resin solution (varnish) was obtained in the same manner as in Comparative Example 4, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm was used as the reaction solvent, γ-butyrolactone (GBL) was used as the dilution solvent, and 4,4'-diphenylmethane diisocyanate (MDI) was added and then the temperature was raised to 112°C to carry out the synthesis reaction.
The ratio of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm, to the dilution solvent, γ-butyrolactone (GBL), was set to 20:80.
The resulting polyamideimide resin solution (varnish) gelled the next day after synthesis.
Although γ-butyrolactone (GBL) may be used as a dilution solvent, the ratio of water to 1000 ppm of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as a reaction solvent is problematic.
Comparative Example 6
反応溶剤として、含水量が３３００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１３０℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が３３００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比は、前者：後者＝５０：５０とした。
得られたポリアミドイミド樹脂溶液（ワニス）は、濁りを生じてしまった。
反応溶剤として、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、又、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、又、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤としてのγ－ブチロラクトン（ＧＢＬ）との比率が適切であっても、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量が問題であり、含水量が３３００ｐｐｍの場合では、ポリアミドイミド樹脂溶液（ワニス）に濁りを生じてしまう。
比較例７
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 3,300 ppm was used as the reaction solvent, γ-butyrolactone (GBL) was used as the dilution solvent, and 4,4'-diphenylmethane diisocyanate (MDI) was added and then the temperature was raised to 130°C to carry out the synthesis reaction.
The ratio of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 3,300 ppm, to the dilution solvent, γ-butyrolactone (GBL), was set to 50:50.
The resulting polyamideimide resin solution (varnish) became cloudy.
Even if 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as the reaction solvent and γ-butyrolactone (GBL) is used as the dilution solvent, and the ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent to γ-butyrolactone (GBL) as the dilution solvent is appropriate, the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent is a problem, and when the water content is 3300 ppm, the polyamideimide resin solution (varnish) becomes cloudy.
Comparative Example 7
反応溶剤として、含水量が２０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１１７℃まで昇温し合成反応させた以外は、比較例６と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が２０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比率は、前者：後者＝６０：４０とした。
得られたポリアミドイミド樹脂溶液（ワニス）は、濁りを生じてしまった。
反応溶剤として、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、又、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用いていても、又、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤としてのγ－ブチロラクトン（ＧＢＬ）との比率が適切であっても、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量が問題であり、含水量が２０００ｐｐｍの場合では、ポリアミドイミド樹脂溶液（ワニス）に濁りを生じてしまう。
比較例８
A polyamideimide resin solution (varnish) was obtained in the same manner as in Comparative Example 6, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 2000 ppm was used as the reaction solvent, γ-butyrolactone (GBL) was used as the dilution solvent, and 4,4'-diphenylmethane diisocyanate (MDI) was added and then the temperature was raised to 117°C to carry out the synthesis reaction.
The ratio of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 2000 ppm, to the dilution solvent, γ-butyrolactone (GBL), was set to 60:40.
The resulting polyamideimide resin solution (varnish) became cloudy.
Even if 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as the reaction solvent and γ-butyrolactone (GBL) is used as the dilution solvent, and even if the ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent to γ-butyrolactone (GBL) as the dilution solvent is appropriate, the water content of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent is a problem, and when the water content is 2000 ppm, the polyamideimide resin solution (varnish) becomes cloudy.
Comparative Example 8
反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１２５℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比率は、前者：後者＝４０：６０とした。
得られたポリアミドイミド樹脂溶液（ワニス）は、濁りを生じてしまった。
反応溶剤として、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、又、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用いていても、又、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤としてのγ－ブチロラクトン（ＧＢＬ）との比率が適切であっても、最終到達温度が問題であり、最終到達温度（℃）が、１２５℃では、ポリアミドイミド樹脂溶液（ワニス）に濁りを生じてしまう。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm was used as the reaction solvent, γ-butyrolactone (GBL) was used as the dilution solvent, and 4,4'-diphenylmethane diisocyanate (MDI) was added and then the temperature was raised to 125°C to carry out the synthesis reaction.
The ratio of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm, to the dilution solvent, γ-butyrolactone (GBL), was set to 40:60.
The resulting polyamideimide resin solution (varnish) became cloudy.
Even if 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as the reaction solvent and γ-butyrolactone (GBL) is used as the dilution solvent, and even if the ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent and γ-butyrolactone (GBL) as the dilution solvent is appropriate, the final reached temperature is a problem, and if the final reached temperature (°C) is 125°C, the polyamideimide resin solution (varnish) becomes cloudy.
反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１２０℃まで昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比は、前者：後者＝４０：６０とした。
得られたポリアミドイミド樹脂溶液（ワニス）は、濁りを生じてしまった。
反応溶剤として、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、又、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用いていても、又、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤としてのγ－ブチロラクトン（ＧＢＬ）との比率が適切であっても、最終到達温度が問題であり、最終到達温度（℃）が１２０℃では、ポリアミドイミド樹脂溶液（ワニス）に濁りを生じてしまう。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm was used as the reaction solvent, γ-butyrolactone (GBL) was used as the dilution solvent, and 4,4'-diphenylmethane diisocyanate (MDI) was added and then the temperature was raised to 120°C to carry out the synthesis reaction.
The ratio of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) having a water content of 1000 ppm, to the dilution solvent, γ-butyrolactone (GBL), was set to 40:60.
The resulting polyamideimide resin solution (varnish) became cloudy.
Even if 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as the reaction solvent and γ-butyrolactone (GBL) is used as the dilution solvent, and even if the ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent and γ-butyrolactone (GBL) as the dilution solvent is appropriate, the final reached temperature is a problem, and if the final reached temperature (°C) is 120°C , the polyamideimide resin solution (varnish) becomes cloudy.
反応溶剤として、含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用い、４，４’－ジフェニルメタンジイソシアネ－ト（ＭＤＩ）を投入後、１２４℃で昇温し合成反応させた以外は、実施例１と同様にして、ポリアミドイミド樹脂溶液（ワニス）を得た。
反応溶剤の含水量が１０００ｐｐｍの３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比は、前者：後者＝４０：６０とした。
得られたポリアミドイミド樹脂溶液（ワニス）は、濁りを生じてしまった。
反応溶剤として、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）を用い、又、希釈溶剤としてγ－ブチロラクトン（ＧＢＬ）を用いていても、又、反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤としてのγ－ブチロラクトン（ＧＢＬ）との比率が適切であっても、最終到達温度が問題であり、最終到達温度（℃）が、１２４℃では、ポリアミドイミド樹脂溶液（ワニス）に濁りを生じてしまう。
A polyamideimide resin solution (varnish) was obtained in the same manner as in Example 1, except that 3-methoxy-N,N-dimethylpropanamide (MDMPA) with a water content of 1000 ppm was used as the reaction solvent, γ-butyrolactone (GBL) was used as the dilution solvent, and 4,4'-diphenylmethane diisocyanate (MDI) was added and then the temperature was raised to 124°C to carry out the synthesis reaction.
The ratio of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA) having a water content of 1000 ppm, to the dilution solvent, γ-butyrolactone (GBL), was set to 40:60.
The resulting polyamideimide resin solution (varnish) became cloudy.
Even if 3-methoxy-N,N-dimethylpropanamide (MDMPA) is used as the reaction solvent and γ-butyrolactone (GBL) is used as the dilution solvent, and even if the ratio of 3-methoxy-N,N-dimethylpropanamide (MDMPA) as the reaction solvent and γ-butyrolactone (GBL) as the dilution solvent is appropriate, the final reached temperature is a problem, and if the final reached temperature (°C) is 124°C , the polyamideimide resin solution (varnish) becomes cloudy.
含水量の測定：
含水量の測定は、三菱ケミカルアナリテック（現：日東精工アナリテック）社製の水分測定装置ＣＡ－３１０を使用。
Moisture content determination:
The moisture content was measured using a moisture measuring device CA-310 manufactured by Mitsubishi Chemical Analytech (now Nitto Seiko Analytech).
上記で得られたポリアミドイミド樹脂塗料を使用して電気絶縁電線を形成した。
絶縁電線の構造及び仕様
（Ｉ）焼付炉（竪型熱風循環炉使用）
（ＩＩ）絞り方法；
ダイス６回（１．０５、１．０７、１．０９、１．１１、１．１３，１．１４）
（ＩＩＩ）焼付温度 炉温：下３７０℃－中４５０℃－上５００℃
アニ－ラ：５５０－５８０℃
（ＩＶ）線速； ２０ｍ／ｍｉｎ、２２ｍ／ｍｉｎ、２４ｍ／ｍｉｎ、
（Ｖ）導体径；１．０００ｍｍ
（ＶＩ）仕上げ寸法；表１及び表２に記載の通り。
（ＶＩＩ）皮膜厚；表１及び表２に記載の通り。
The polyamideimide resin coating material obtained above was used to form an insulated electric wire.
Structure and specifications of insulated electric wire (I) Baking oven (vertical hot air circulation oven)
(II) squeezing method;
6 rolls of the dice (1.05, 1.07, 1.09, 1.11, 1.13, 1.14)
(III) Baking temperature Furnace temperature: lower 370°C - middle 450°C - upper 500°C
Annealer: 550-580℃
(IV) Linear speed; 20m/min, 22m/min, 24m/min,
(V) Conductor diameter: 1.000 mm
(VI) Finished dimensions: as shown in Tables 1 and 2.
(VII) Coating thickness; as shown in Tables 1 and 2.
得られた 絶縁電線についてその特性の評価を行った。
電線特性の評価：
次の電線特性の評価方法にて電線特性の測定を行った。
（ａ）破壊電圧；
ＪＩＳ Ｃ ３２１６－４に準拠して、絶縁破壊電圧（ｋＶ）を測定した。
（ｂ）ｔａｎ（ヒ－タ－）；
誘電正接（ｔａｎδ）温度特性を測定。
（ｃ）耐軟化試験；
荷重７００ｇで測定。平均値（℃）を算出。
（ｄ）耐熱衝撃性 （ＪＩＳ法）；
２６０℃Ｘ１．０ｈｒ加熱処理後のキレツ数を測定。
（ｅ）耐熱衝撃性（ＮＥＭＡ法）；
ＮＥＭＡ法により、２４０℃Ｘ０．５ｈｒ加熱処理後のキレツ数を測定。
（ｆ）可とう性；
３０％伸張時巻付時の発生キレツ数を測定。１ｄ（自己径）、２ｄ（２倍径）及び３ｄ（３倍径）で測定。
（ｇ）一方向摩耗試験：
スクレ－プテスタ（自動車用電線摩耗試験機〕を使用して一方向摩耗試験を行い、ＪＩＳ Ｃ３００３－１９８４の耐摩耗性試験方法により耐摩耗性の評価を行った。
（ｈ）密着性：
作製した絶縁電線の絶縁皮膜に、その長手方向に沿って長さ２ｃｍほどの２本の切れ込みを０．５ｍｍ間隔で入れ、２本の切れ込みの間の絶縁皮膜の一端をピンセットでめくって、熱機械試験機（ＴＭＡ：サ－マルメカニカルアナルシス、セイコ－電子製）を用いて絶縁皮膜と銅線の１８０°剥離試験を行い、皮膜の密着力（ｍｍ）を測定した。露出（ｍｍ）と浮き（ｍｍ）を測定。
上記の結果を表１及び表２に示す。
表３に、反応溶剤の３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）と希釈溶剤のγ－ブチロラクトン（ＧＢＬ）との比率による得られたポリアミドイミド樹脂溶液（ワニス）への影響結果を示す。
表４に、反応溶剤の３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド（ＭＤＭＰＡ）の含水量による得られたポリアミドイミド樹脂溶液（ワニス）への影響結果を示す。
表５に、最終到達温度如何により得られたポリアミドイミド樹脂溶液（ワニス）への影響結果を示す。
The properties of the obtained insulated wire were evaluated.
Wire property evaluation:
The wire characteristics were measured using the following wire characteristic evaluation method.
(a) Breakdown voltage;
The dielectric breakdown voltage (kV) was measured in accordance with JIS C 3216-4.
(b) tan (heater);
Measure the dielectric tangent (tan δ) temperature characteristics.
(c) softening resistance test;
Measure with a load of 700g. Calculate the average value (℃).
(d) Thermal shock resistance (JIS method);
The number of cracks was measured after heat treatment at 260℃ for 1.0 hr.
(e) Thermal shock resistance (NEMA method);
The number of cracks after heat treatment at 240°C for 0.5 hours was measured using the NEMA method.
(f) flexibility;
The number of cracks that occurred during winding at 30% elongation was measured. Measurements were taken at 1d (original diameter), 2d (2x diameter), and 3d (3x diameter).
(g) Unidirectional abrasion test:
A unidirectional abrasion test was carried out using a scrape tester (abrasion tester for automotive electric wires), and the abrasion resistance was evaluated according to the abrasion resistance test method of JIS C3003-1984.
(h) Adhesion:
Two slits, each about 2 cm long, were made in the insulating coating of the prepared insulated electric wire along its length, spaced 0.5 mm apart, and one end of the insulating coating between the two slits was peeled back with tweezers to perform a 180° peel test between the insulating coating and the copper wire using a thermomechanical tester (TMA: Thermal Mechanical Analysis, manufactured by Seiko Electronics Co., Ltd.), and the adhesion strength (mm) of the coating was measured. The exposure (mm) and lift (mm) were also measured.
The above results are shown in Tables 1 and 2.
Table 3 shows the effect of the ratio of the reaction solvent 3-methoxy-N,N-dimethylpropanamide (MDMPA) to the dilution solvent γ-butyrolactone (GBL) on the resulting polyamideimide resin solution (varnish).
Table 4 shows the effect of the water content of the reaction solvent, 3-methoxy-N,N-dimethylpropanamide (MDMPA), on the resulting polyamideimide resin solution (varnish).
Table 5 shows the effect of the final temperature reached on the resulting polyamideimide resin solution (varnish).
本発明は、電気絶縁塗料又は電気絶縁電線の他、電気絶縁性を必要とする接着剤等の各種電気絶縁材料にも適用できる。 The present invention can be applied to various electrically insulating materials such as adhesives that require electrical insulation, in addition to electrically insulating paints and electrically insulated wires.
Claims (1)
前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド中の含水量を２０００ｐｐｍ未満の範囲に調整し、前記反応溶剤としての３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの前記希釈溶剤としてのγ－ブチロラクトンに対しての比率を前者７０～３０重量％：後者３０～７０重量％とし、前記イソシアネ－ト成分としてベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分を単独使用するか、又は、当該ベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分とベンゼン環にメチル基の置換基を有するイソシアネ－ト成分とを混合使用する場合には、前者のベンゼン環にメチル基の置換基を有しないイソシアネ－ト成分を５０ｍｏｌ％を超えた範囲で使用し、前記共重合反応によりポリアミドイミド樹脂を製造する際の最終到達温度を１１７℃以下としてなるポリアミドイミド樹脂溶液の製法であって、当該共重合反応時には水を添加していてもポリアミドイミド樹脂を希釈溶剤に溶解させて得られたポリアミドイミド樹脂溶液中には添加した水を含まないようにすることを特徴とする電気絶縁塗料及び電気絶縁被覆電線に有用なポリアミドイミド樹脂溶液の製法。 A method for producing a polyamideimide resin solution, comprising the steps of: using 3-methoxy-N,N-dimethylpropanamide as a reaction solvent, copolymerizing an acid component with an isocyanate component to obtain a polyamideimide resin; and dissolving the obtained polyamideimide resin in γ-butyrolactone as a dilution solvent to obtain a polyamideimide resin solution,
The water content in 3-methoxy-N,N-dimethylpropanamide as the reaction solvent is adjusted to a range of less than 2000 ppm, the ratio of 3-methoxy-N,N-dimethylpropanamide as the reaction solvent to γ-butyrolactone as the dilution solvent is set to 70 to 30% by weight for the former and 30 to 70% by weight for the latter, and as the isocyanate component, an isocyanate component having no methyl group substituent on the benzene ring is used alone, or an isocyanate component having no methyl group substituent on the benzene ring and an isocyanate component having a methyl group substituent on the benzene ring are used alone. When a mixture of an isocyanate component and an isocyanate component not having a methyl group substituent on the benzene ring is used in an amount exceeding 50 mol %, and the final temperature achieved in producing a polyamide-imide resin by the copolymerization reaction is set to 117°C or lower , and a method for producing a polyamide-imide resin solution useful for an electric insulating coating material and an electric insulating coated electric wire is characterized in that even if water is added during the copolymerization reaction, the polyamide-imide resin solution obtained by dissolving the polyamide-imide resin in a dilution solvent does not contain the added water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020153432A JP7593539B2 (en) | 2020-09-14 | 2020-09-14 | Method for producing polyamide-imide resin solution useful for electrical insulating paint and electrical insulating coated wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020153432A JP7593539B2 (en) | 2020-09-14 | 2020-09-14 | Method for producing polyamide-imide resin solution useful for electrical insulating paint and electrical insulating coated wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2022047576A JP2022047576A (en) | 2022-03-25 |
| JP7593539B2 true JP7593539B2 (en) | 2024-12-03 |
Family
ID=80781128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020153432A Active JP7593539B2 (en) | 2020-09-14 | 2020-09-14 | Method for producing polyamide-imide resin solution useful for electrical insulating paint and electrical insulating coated wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7593539B2 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009149757A (en) | 2007-12-20 | 2009-07-09 | Sumitomo Electric Wintec Inc | Polyamide imide and production method thereof, polyamide imide-based insulating coating, and insulated wire |
| JP2012219107A (en) | 2011-04-04 | 2012-11-12 | Hitachi Chemical Co Ltd | Polyamideimide resin composition, production method therefor, curable resin composition using the same and coating |
| JP2014062223A (en) | 2012-08-30 | 2014-04-10 | Toyobo Co Ltd | Polyamide-imide resin composition for lubricating coating material |
| JP2017517582A (en) | 2014-03-26 | 2017-06-29 | エランタス イタリア エス．アール．エル．Ｅｌａｎｔａｓ Ｉｔａｌｉａ Ｓ．Ｒ．Ｌ． | New solvents for polyamide-imide and polyimide |
| JP2019528368A (en) | 2016-08-23 | 2019-10-10 | デリム コーポレイション カンパニー リミテッド | Polyimide precursor resin composition having improved resin stability and heat resistance and transparency, method for producing polyimide film using the same, and polyimide film produced thereby |
| JP2020015880A (en) | 2018-07-27 | 2020-01-30 | 日立化成株式会社 | Heat resistant resin composition |
-
2020
- 2020-09-14 JP JP2020153432A patent/JP7593539B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009149757A (en) | 2007-12-20 | 2009-07-09 | Sumitomo Electric Wintec Inc | Polyamide imide and production method thereof, polyamide imide-based insulating coating, and insulated wire |
| JP2012219107A (en) | 2011-04-04 | 2012-11-12 | Hitachi Chemical Co Ltd | Polyamideimide resin composition, production method therefor, curable resin composition using the same and coating |
| JP2014062223A (en) | 2012-08-30 | 2014-04-10 | Toyobo Co Ltd | Polyamide-imide resin composition for lubricating coating material |
| JP2017517582A (en) | 2014-03-26 | 2017-06-29 | エランタス イタリア エス．アール．エル．Ｅｌａｎｔａｓ Ｉｔａｌｉａ Ｓ．Ｒ．Ｌ． | New solvents for polyamide-imide and polyimide |
| JP2019528368A (en) | 2016-08-23 | 2019-10-10 | デリム コーポレイション カンパニー リミテッド | Polyimide precursor resin composition having improved resin stability and heat resistance and transparency, method for producing polyimide film using the same, and polyimide film produced thereby |
| JP2020015880A (en) | 2018-07-27 | 2020-01-30 | 日立化成株式会社 | Heat resistant resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022047576A (en) | 2022-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8685536B2 (en) | Polyamide-imide resin insulating coating material, insulated wire and method of making the same | |
| JP5365899B2 (en) | Polyamideimide resin insulating paint and insulated wire using the same | |
| JP4473916B2 (en) | Polyamideimide resin insulating paint and insulated wire using the same | |
| CN102690596B (en) | Insulation compound and use the insulated line of this insulation compound | |
| US20120318555A1 (en) | Polyamide-imide resin insulating coating material, insulated wire and coil | |
| US20080160304A1 (en) | Polyamideimide compositions having multifunctional core structures | |
| CN102911594A (en) | Polyamide-imide resin insulating varnish and method of manufacturing the same, insulated wire and coil | |
| TWI682978B (en) | Water-dispersible electrodeposition solution for forming insulation coating | |
| CA2261770A1 (en) | Wire enamels, comprising polyesterimides and/or polyamideimides with polyoxyalkylenediamines as molecular building blocks | |
| JP5477327B2 (en) | Method for producing polyimide resin | |
| JP5109374B2 (en) | Polyamideimide resin solution and production method thereof, resin composition and coating composition | |
| JP7593539B2 (en) | Method for producing polyamide-imide resin solution useful for electrical insulating paint and electrical insulating coated wire | |
| JP2012234625A (en) | Insulated wire and electric coil and motor using the same | |
| JP2012164424A (en) | Polyester imide resin based varnish for low dielectric constant coating film | |
| JP5316857B2 (en) | Electrical insulating coating composition and insulated wire | |
| JP2016017085A (en) | Material for electrical insulation, electrically insulated product, electrical insulation coating, and electrically insulated wire | |
| CN109935392B (en) | Varnish for insulated wire, and motor | |
| JP2012243614A (en) | Insulated wire, and electric coil and motor using the same | |
| JP2011225741A (en) | Polyamideimide resin solution and method for producing the same, resin composition, and coating composition | |
| JP2013155281A (en) | Insulating coating, insulated wire using the insulating coating, and coil using the insulated wire | |
| JP5712661B2 (en) | Polyamideimide resin insulating paint and insulated wire using the same | |
| JPH09137118A (en) | Polyimide resin paint and insulated wire | |
| JP2010215785A (en) | Heat-resistant polyamideimide resin and seamless tubular body, coating film, coating film plate, and heat-resistant coating material using the same | |
| JP2012171979A (en) | Resin composition for electric insulation, and enamel wire | |
| JP2006316135A (en) | Polyimide resin composition, resin paint and insulated wire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230522 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240117 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240213 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240227 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20240528 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240611 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20240823 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20241022 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20241105 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7593539 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |