JP2007146101A - Aromatic resin composition, heat-resistant coating material containing the aromatic resin composition as coating component and coating binder for sliding part - Google Patents
Aromatic resin composition, heat-resistant coating material containing the aromatic resin composition as coating component and coating binder for sliding part Download PDFInfo
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- JP2007146101A JP2007146101A JP2006036711A JP2006036711A JP2007146101A JP 2007146101 A JP2007146101 A JP 2007146101A JP 2006036711 A JP2006036711 A JP 2006036711A JP 2006036711 A JP2006036711 A JP 2006036711A JP 2007146101 A JP2007146101 A JP 2007146101A
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- aromatic
- resin composition
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- aromatic resin
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 40
- 239000011342 resin composition Substances 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 239000011230 binding agent Substances 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 title claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 39
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 39
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 21
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000003368 amide group Chemical group 0.000 claims abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005462 imide group Chemical group 0.000 claims abstract description 5
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000005056 polyisocyanate Chemical class 0.000 claims description 5
- 229920001228 polyisocyanate Chemical class 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 2
- 150000007974 melamines Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 22
- 239000003973 paint Substances 0.000 description 17
- -1 melamine compound Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 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 9
- 239000002253 acid Substances 0.000 description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 5
- 229920003270 Cymel® Polymers 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- UOFDVLCOMURSTA-UHFFFAOYSA-N 2-(2-carboxyphenoxy)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(O)=O UOFDVLCOMURSTA-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- XZOQPRNOAGCWNT-UHFFFAOYSA-N 4-[[(3,4-dicarboxyphenyl)-dimethylsilyl]oxy-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 XZOQPRNOAGCWNT-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
- 229920003275 CYMEL® 325 Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 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
- 150000002576 ketones Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 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 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、芳香族系樹脂組成物、該芳香族系樹脂組成物を塗料成分としてなる耐熱性塗料及び摺動部コーティング塗料に関する。 The present invention relates to an aromatic resin composition, a heat resistant paint and a sliding part coating paint comprising the aromatic resin composition as a paint component.
従来、ポリアミドイミド樹脂組成物を用いた耐熱性塗料が知られている(例えば、特許文献1を参照。)。
ポリアミドイミド樹脂は、耐熱性、耐薬品性及び耐溶剤性に優れているため、各種の基材のコート剤として広く使用され、例えば、エナメル線用ワニス、耐熱塗料などとして使用されている。
Conventionally, a heat-resistant paint using a polyamideimide resin composition is known (for example, see Patent Document 1).
Polyamideimide resins are excellent in heat resistance, chemical resistance and solvent resistance, and are therefore widely used as coating agents for various substrates, for example, enameled wire varnishes and heat resistant paints.
しかし、この優れた特性を得るためには、通常250℃以上で硬化を行わなければならない。
また、近年の技術の進歩により、強い耐磨耗性が要求され従来のトリメリット酸無水物と4,4−ジフェニルメタンジイソシアネートから得られるポリアミドイミド樹脂より強い機械的特性や硬さが求められており、従来のポリアミドイミド樹脂では耐摩耗性が満足しない不具合が発生している。
In addition, due to recent technological advances, strong wear resistance is required, and stronger mechanical properties and hardness are required than conventional polyamideimide resin obtained from trimellitic anhydride and 4,4-diphenylmethane diisocyanate. The conventional polyamide-imide resin has a problem that the wear resistance is not satisfied.
本発明は、ポリアミドイミド樹脂が有する耐熱性を保持し、汎用のポリアミドイミド樹脂より機械的特性に優れ、硬く、低温硬化が可能である芳香族系樹脂組成物、耐熱性塗料及び、摺動部コーティング塗料バインダーを提供するものである。 The present invention relates to an aromatic resin composition, a heat resistant paint, and a sliding part that retain the heat resistance of a polyamideimide resin, have superior mechanical properties than general-purpose polyamideimide resins, are hard, and can be cured at low temperatures. A coating paint binder is provided.
本発明は、(a)酸無水物基を有する3価のカルボン酸の誘導体、(b)一般式(I) The present invention relates to (a) a derivative of a trivalent carboxylic acid having an acid anhydride group, (b) a general formula (I)
で表されるジカルボン酸又はその水素化物であるジカルボン酸及び(c)一分子中に2個以上のアミノ基又はイソシアナト基を有し、一般式(II)で表される芳香族化合物及び一般式(III)で表される芳香族化合物を含有する芳香族化合物
And (c) an aromatic compound having two or more amino groups or isocyanato groups in one molecule, and represented by the general formula (II) and the general formula Aromatic compound containing aromatic compound represented by (III)
を反応させて得られアミド基数/イミド基数の比が51/49〜80/20の範囲にあるポリアミドイミド樹脂を含有する芳香族系樹脂組成物に関する。
なお、上記のポリアミドイミド樹脂、は一般式(IV−1)及び一般式(IV−2)で表される繰り返し単位を有する。
It is related with the aromatic resin composition containing the polyamidoimide resin which has the ratio of the number of amide groups / imide groups in the range of 51 / 49-80 / 20.
In addition, said polyamideimide resin has a repeating unit represented by general formula (IV-1) and general formula (IV-2).
また、本発明は、一般式(II)の式中R2がH又はメチル基であり、ポリアミドイミド樹脂が、R3がイソシアナト基であり、(a)、(b)及び(c)を、(a)と(b)の配合割合(a)/(b)が、当量比で0.99/0.01〜0.4/0.6であり、(a)と(b)のカルボキシル基及び酸無水物基の総数に対する(c)のアミノ基及びイソシアナト基の総数の比が0.6〜1.4である量で反応させて得られたものである上記の芳香族系樹脂組成物に関する。
また、本発明は、ポリアミドイミド樹脂が、数平均分子量8,000〜90,000のものである上記の芳香族系樹脂組成物に関する。
また、本発明は、ポリアミドイミド樹脂が樹脂末端をアルコール、オキシム又はフェノールでブロックしてなるものである上記の芳香族系樹脂組成物に関する。
Further, the present invention is wherein R 2 is H or a methyl group of the general formula (II), polyamide-imide resin, R 3 is an isocyanato group, a (a), (b) and (c), The mixing ratio (a) / (b) of (a) and (b) is 0.99 / 0.01 to 0.4 / 0.6 in terms of equivalent ratio, and the carboxyl groups of (a) and (b) And the aromatic resin composition obtained by reacting in such an amount that the ratio of the total number of amino groups and isocyanato groups in (c) to the total number of acid anhydride groups is 0.6 to 1.4. About.
The present invention also relates to the above aromatic resin composition, wherein the polyamideimide resin has a number average molecular weight of 8,000 to 90,000.
The present invention also relates to the above aromatic resin composition, wherein the polyamideimide resin is formed by blocking the resin terminal with alcohol, oxime or phenol.
また、本発明は、ポリアミドイミド樹脂100重量部に対して、さらに多官能エポキシ樹脂、ポリイソシアネート化合物及びメラミン化合物からなる群から選ばれる少なくとも1種を1〜40重量部含有してなる前記の芳香族系樹脂組成物に関する。
また、本発明は、前記の上記の芳香族系樹脂組成物を含有する塗料に関する。
さらに、本発明は、前記の上記の芳香族系樹脂組成物を含有する摺動部コーティング塗料バインダーに関する。
In addition, the present invention provides the fragrance further comprising 1 to 40 parts by weight of at least one selected from the group consisting of a polyfunctional epoxy resin, a polyisocyanate compound and a melamine compound with respect to 100 parts by weight of the polyamideimide resin. The present invention relates to a group resin composition.
Moreover, this invention relates to the coating material containing said aromatic resin composition.
Furthermore, this invention relates to the sliding part coating-coating binder containing said aromatic resin composition.
本発明になる芳香族系樹脂組成物は、機械的特性に優れ、硬く、低温での硬化が可能であり、種々の耐熱性塗料、摺動部コーティング塗料バインダー樹脂として応用することができる The aromatic resin composition according to the present invention has excellent mechanical properties, is hard and can be cured at low temperature, and can be applied as various heat resistant paints and sliding part coating paint binder resins.
本発明のポリアミドイミド樹脂の製造に用いられる(a)酸無水物基を有する3価のカルボン酸の誘導体としては、例えば一般式(V)及び(VI)で示す化合物を使用することができ、イソシアナト基又はアミノ基と反応する酸無水物基、又は酸無水物基及びカルボキシル基を有する3価のカルボン酸の誘導体であればよく、特に制限はない。耐熱性、コスト面等を考慮すれば、トリメリット酸無水物が特に好ましい。これらの酸無水物基を有する3価のカルボン酸の誘導体は、目的に応じて単独又は混合して用いられる。 As a derivative of a trivalent carboxylic acid having an acid anhydride group used in the production of the polyamideimide resin of the present invention, for example, compounds represented by the general formulas (V) and (VI) can be used, There is no particular limitation as long as it is an acid anhydride group that reacts with an isocyanato group or an amino group, or a derivative of a trivalent carboxylic acid having an acid anhydride group and a carboxyl group. In view of heat resistance, cost, etc., trimellitic anhydride is particularly preferable. These trivalent carboxylic acid derivatives having an acid anhydride group may be used alone or in combination depending on the purpose.
また、これらのほかに必要に応じて、テトラカルボン酸二無水物(ピロメリット酸二無水物、3,3′,4,4′−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、1,2,5,6−ナフタレンテトラカルボン酸二無水物、2,3,5,6−ピリジンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、3,4,9,10−ペリレンテトラカルボン酸二無水物、4,4′−スルホニルジフタル酸二無水物、m−ターフェニル−3,3′,4,4′−テトラカルボン酸二無水物、4,4′−オキシジフタル酸二無水物、1,1,1,3,3,3−ヘキサフルオロ−2,2−ビス(2,3−又は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−又は3,4−ジカルボキシフェニル)プロパン二無水物、2,2−ビス[4−(2,3−又は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、1,1,1,3,3,3−ヘキサフルオロ−2,2−ビス[4−(2,3−又は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、1,3−ビス(3,4−ジカルボキシフェニル)−1,1,3,3−テトラメチルジシロキサン二無水物、ブタ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等)などを使用することができる。 In addition to these, if necessary, tetracarboxylic dianhydride (pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4, 4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, m-terphenyl-3,3 ', 4 4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4 -Dicarboxyphenyl) propane dianhydride, 2,2 Bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1 , 1,1,3,3,3-hexafluoro-2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,3-bis (3 , 4-Dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, butanetetracarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene-2: 3: 5: 6-tetracarboxylic dianhydride etc.) etc. can be used.
本発明において、(b)成分のジカルボン酸を示す一般式(I)中、R1を示す芳香族基としては、フェニレン基、ナフチリレン基、ジフェニルメタンジイル基、ジフェニルエーテルジイル基等が挙げられ、脂肪族基としては、例えば炭素数1〜16の2価の飽和又は不飽和脂肪族基等が挙げられる。これらジカルボン酸の具体例としては、例えば、脂肪族ジカルボン酸(コハク酸、グルタル酸、アジピン酸、アゼライン酸、スベリン酸、セバシン酸、デカン二酸、ドデカン二酸、ダイマー酸等)、芳香族ジカルボン酸(イソフタル酸、テレフタル酸、フタル酸、ナフタレンジカルボン酸、オキシジ安息香酸等)などを使用することができる。また、これらの化合物の芳香環を水素化した化合物も用いることができる。 In the present invention, in the general formula (I) representing the dicarboxylic acid of component (b), examples of the aromatic group representing R 1 include a phenylene group, a naphthylylene group, a diphenylmethanediyl group, a diphenyletherdiyl group, and the like, and an aliphatic group. Examples of the group include a divalent saturated or unsaturated aliphatic group having 1 to 16 carbon atoms. Specific examples of these dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc.), aromatic dicarboxylic acids, and the like. Acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) can be used. Moreover, the compound which hydrogenated the aromatic ring of these compounds can also be used.
ジカルボン酸の使用により、アミド基数/イミド基数の比を、51/49〜80/20にすることができる。アミド基数/イミド基数の比は、好ましくは55/45〜78/22、最も好ましいのは65/35〜75/25である。これらの比が51/49未満であると、可とう性及び密着性が低下する傾向があり、80/20を超えると、耐熱性が低下する傾向がある。 By using dicarboxylic acid, the ratio of the number of amide groups / number of imide groups can be set to 51 / 49-80 / 20. The ratio of the number of amide groups / number of imide groups is preferably 55/45 to 78/22, and most preferably 65/35 to 75/25. If these ratios are less than 51/49, the flexibility and adhesion tend to decrease, and if it exceeds 80/20, the heat resistance tends to decrease.
本発明における(c)成分の芳香族化合物としては、例えば、芳香族ジアミン、4,4′−ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、4,4′−ジフェニルエーテルジイソシアネート、4,4′−[2,2−ビス(4−フェノキシフェニル)プロパン]ジイソシアネート、ビフェニル−4,4′−ジイソシアネート、ビフェニル−3,3′−ジイソシアネート、ビフェニル−3,4′−ジイソシアネート、3,3′−ジメチルビフェニル−4,4′−ジイソシアネート、2,2′−ジメチルビフェニル−4,4′−ジイソシアネート、3,3′−ジエチルビフェニル−4,4′−ジイソシアネート、2,2′−ジエチルビフェニル−4,4′−ジイソシアネート、3,3′−ジメトキシビフェニル−4,4′−ジイソシアネート、2,2′−ジメトキシビフェニル−4,4′−ジイソシアネート、ナフタレン−1,5−ジイソシアネート、ナフタレン−2,6−ジイソシアネート等の芳香族ジイソシアネートを使用することができる。 Examples of the aromatic compound of component (c) in the present invention include aromatic diamine, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 '-[ 2,2-bis (4-phenoxyphenyl) propane] diisocyanate, biphenyl-4,4'-diisocyanate, biphenyl-3,3'-diisocyanate, biphenyl-3,4'-diisocyanate, 3,3'-dimethylbiphenyl- 4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-diethylbiphenyl-4,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'- Diisocyanate, 3,3'-dimethoxy Aromatic diisocyanates such as phenyl-4,4'-diisocyanate, 2,2'-dimethoxybiphenyl-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate can be used. .
これらは、単独でもこれらを組み合わせて使用することもできる。必要に応じて、(c)成分の一部として、ヘキサメチレンジイソシアネート、2,2,4−トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4′−ジシクロヘキシルメタンジイソシアネート、トランスシクロヘキサン−1,4−ジイソシアネート、水添m−キシリレンジイソシアネート、リジンジイソシアネート等の脂肪族、脂環式ジイソシアネート及び3官能以上のポリイソシアネートを使用することもできる。 These can be used alone or in combination. If necessary, as part of component (c), hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, Aliphatic, alicyclic diisocyanates such as hydrogenated m-xylylene diisocyanate and lysine diisocyanate, and tri- or higher functional polyisocyanates can also be used.
本発明においては、機械的特性から、ビフェニル誘導体の構造を有する一般式(II)で表される芳香族化合物を(c)成分の必須成分として用いる。一般式(II)中、R2は各々独立にHであるか、又はアミノ基及びイソシアナト基のいずれでもない有機基を表すが、この有機基としては、例えば、炭素数1〜2のアルキル基等のアルキル基、炭素数1〜2のアルコキシ基等のアルコキシ基、水酸基等が挙げられる。なお、一般式(II)及び(III)中、R3はアミノ基又はイソシアナト基であるが、反応性の点から、イソシアナト基が好ましい。一般式(II)で表される芳香族ジイソシアネートとしては、例えば、3,3′−ジメチルビフェニル−4,4′−ジイソシアネート、2,2′−ジメチルビフェニル−4,4′−ジイソシアネート、3,3′−ジエチルビフェニル−4,4′−ジイソシアネート、2,2′−ジエチルビフェニル−4,4′−ジイソシアネート、3,3′−ジメトキシビフェニル−4,4′−ジイソシアネート、2,2′−ジメトキシビフェニル−4,4′−ジイソシアネート等が挙げられる。一般式(II)で表される芳香族ジイソシアネートの配合量は、(c)成分の芳香族化合物の総量中、55〜85モル%用いることが好ましく、最も好ましいのは70〜80モル%である。55モル%未満では、機械的特性が低下する傾向があり、85モル%を超えると、経日でワニス溶液が濁る傾向がある。 In the present invention, an aromatic compound represented by the general formula (II) having a structure of a biphenyl derivative is used as an essential component of the component (c) because of mechanical properties. In general formula (II), each R 2 is independently H, or represents an organic group that is neither an amino group nor an isocyanato group. Examples of the organic group include an alkyl group having 1 to 2 carbon atoms. An alkyl group such as an alkoxy group having 1 to 2 carbon atoms, a hydroxyl group, and the like. In general formulas (II) and (III), R 3 is an amino group or an isocyanato group, but isocyanato group is preferred from the viewpoint of reactivity. Examples of the aromatic diisocyanate represented by the general formula (II) include 3,3′-dimethylbiphenyl-4,4′-diisocyanate, 2,2′-dimethylbiphenyl-4,4′-diisocyanate, and 3,3. '-Diethylbiphenyl-4,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-dimethoxybiphenyl- 4,4'-diisocyanate and the like. The blending amount of the aromatic diisocyanate represented by the general formula (II) is preferably 55 to 85 mol%, and most preferably 70 to 80 mol% in the total amount of the aromatic compound as the component (c). . If it is less than 55 mol%, the mechanical properties tend to decrease, and if it exceeds 85 mol%, the varnish solution tends to become cloudy over time.
また、本発明においては、塗膜の硬さ向上のために、ナフタレン環を含む一般式(III)で表される芳香族化合物を(c)成分の必須成分として用いる。一般式(III)で表される芳香族化合物の具体例としては、例えば、ナフタレン−1,5−ジイソシアネート、ナフタレン−2,6−ジイソシアネート等の芳香族ジイソシアネートが挙げられる。一般式(III)で表される芳香族化合物の配合量は、(c)成分の芳香族化合物の総量中、5〜30モル%用いることが好ましく、最も好ましいのは10〜20モル%である。10モル%未満では、塗膜硬度が低下する傾向があり、30モル%を超えると、柔軟性及び密着性が低下する傾向がある。 Moreover, in this invention, the aromatic compound represented with general formula (III) containing a naphthalene ring is used as an essential component of (c) component for the hardness improvement of a coating film. Specific examples of the aromatic compound represented by the general formula (III) include aromatic diisocyanates such as naphthalene-1,5-diisocyanate and naphthalene-2,6-diisocyanate. The compounding amount of the aromatic compound represented by the general formula (III) is preferably 5 to 30 mol%, and most preferably 10 to 20 mol% in the total amount of the aromatic compound of component (c). . If it is less than 10 mol%, the coating film hardness tends to decrease, and if it exceeds 30 mol%, flexibility and adhesion tend to decrease.
一般式(II)及び(III)で表される芳香族化合物以外の(c)成分の芳香族化合物の配合量は、(c)成分の芳香族化合物の総量中、1〜40モル%とすることが好ましく、5〜40モル%とすることがより好ましく、10〜30モル%とすることが更に好ましい。このような残りの配合芳香族化合物は、コスト、機械的特性の伸び率の向上の点から4,4′−ジフェニルメタンジイソシアネートを配合することが好ましい。 The compounding amount of the aromatic compound of the component (c) other than the aromatic compound represented by the general formulas (II) and (III) is 1 to 40 mol% in the total amount of the aromatic compound of the component (c). It is preferably 5 to 40 mol%, more preferably 10 to 30 mol%. Such remaining blended aromatic compound is preferably blended with 4,4'-diphenylmethane diisocyanate from the viewpoint of cost and improvement in elongation of mechanical properties.
(c)芳香族化合物の配合割合は、(a)と(b)のカルボキシル基及び酸無水物基の総数に対する(c)のアミノ基及びイソシアネート基の総数の比が0.6〜1.4となるようにすることが好ましく、0.7〜1.3となるようにすることがより好ましく、0.8〜1.2となるようにすることが特に好ましい。0.6未満又は1.4を超えると、樹脂の分子量を高くすることが困難となる傾向がある。 (C) The mixing ratio of the aromatic compound is such that the ratio of the total number of amino groups and isocyanate groups in (c) to the total number of carboxyl groups and anhydride groups in (a) and (b) is 0.6 to 1.4. It is preferable to be set to 0.7, more preferably 0.7 to 1.3, and particularly preferably 0.8 to 1.2. If it is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the resin.
本発明に用いられるポリアミドイミド樹脂は例えば次の製造法で得ることができる。
(1)酸成分(a)及び(b)とアミン又はイソシアネート成分(c)とを一度に使用し、反応させてポリアミドイミド樹脂を得る方法。
(2)酸成分(b)とアミン又はイソシアネート成分(c)の過剰量とを反応させて末端にアミノ基又はイソシアナト基を有するアミドイミドオリゴマーを合成した後、酸成分(a)を追加し反応させてポリアミドイミド樹脂を得る方法。
(3)酸成分(a)の過剰量とアミン又はイソシアネート成分(c)を反応させて末端に酸又は酸無水物基を有するアミドイミドオリゴマーを合成した後、酸成分(b)とアミン又はイソシアネート成分(c)を追加し反応させてポリアミドイミド樹脂を得る方法。
The polyamideimide resin used in the present invention can be obtained, for example, by the following production method.
(1) A method in which an acid component (a) and (b) and an amine or isocyanate component (c) are used at a time and reacted to obtain a polyamideimide resin.
(2) After reacting an acid component (b) with an excess of amine or isocyanate component (c) to synthesize an amide-imide oligomer having an amino group or an isocyanate group at the end, the acid component (a) is added and reacted. To obtain a polyamide-imide resin.
(3) After reacting an excess amount of the acid component (a) with an amine or isocyanate component (c) to synthesize an amide-imide oligomer having an acid or acid anhydride group at the terminal, the acid component (b) and an amine or isocyanate A method of adding a component (c) and reacting to obtain a polyamideimide resin.
また、経日変化を避けるために、必要な場合、ブロック剤でポリマー末端のイソシアネート基を安定化したポリアミドイミド樹脂を使用してもよい。ブロック剤としてはアルコール、フェノール、オキシム等があるが、特に制限はない。 Moreover, in order to avoid a secular change, you may use the polyamide imide resin which stabilized the isocyanate group of the polymer terminal with the blocking agent as needed. The blocking agent includes alcohol, phenol, oxime, etc., but there is no particular limitation.
このようにして得られたポリアミドイミド樹脂の数平均分子量は8,000〜90,000のものであることが好ましい。数平均分子量が8,000未満であると、塗料としたときの成膜性が悪くなる傾向があり、90,000を超えると、塗料として適正な濃度で溶媒に溶解したときに粘度が高くなり、塗装時の作業性が劣る傾向にあり、又、塗料やワニスが吸湿白化しやすく作業性に劣る。このことから、ポリアミドイミド樹脂の数平均分子量は、9,000〜90,000にすることがより好ましい。
なお、ポリアミドイミド樹脂の数平均分子量は、樹脂合成時にサンプリングして、ゲルパーミエーションクロマトグラフ(GPC)により、標準ポリスチレンの検量線を用いて測定し、目的の数平均分子量になるまで合成を継続することにより上記範囲に管理される。
The polyamideimide resin thus obtained preferably has a number average molecular weight of 8,000 to 90,000. If the number average molecular weight is less than 8,000, the film formability when used as a paint tends to deteriorate, and if it exceeds 90,000, the viscosity increases when dissolved in a solvent at an appropriate concentration as a paint. The workability at the time of painting tends to be inferior, and the paint and varnish tend to be hygroscopically whitened and the workability is inferior. For this reason, the number average molecular weight of the polyamideimide resin is more preferably 9,000 to 90,000.
The number average molecular weight of the polyamideimide resin is sampled at the time of resin synthesis, measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve, and the synthesis is continued until the target number average molecular weight is reached. By doing so, it is managed within the above range.
本発明の芳香族系樹脂組成物は、上記ポリアミドイミド樹脂とともに、多官能エポキシ樹脂化合物、ポリイソシアネート化合物及びメラミン化合物からなる群より選ばれる少なくとも1種類を含有することが好ましい。これらの配合量は、ポリアミドイミド樹脂100重量部に対して、1〜40重量部とすることが好ましく、5〜30重量部とすることがより好ましい。この量が1重量部未満となると、密着性向上効果が小さくなり、40重量部を超えると、塗膜の耐熱性が著しく低下する傾向があり、さらに塗膜強度の低下を示す傾向がある。 The aromatic resin composition of the present invention preferably contains at least one selected from the group consisting of a polyfunctional epoxy resin compound, a polyisocyanate compound and a melamine compound together with the polyamideimide resin. These compounding amounts are preferably 1 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyamideimide resin. When this amount is less than 1 part by weight, the effect of improving the adhesion is reduced, and when it exceeds 40 parts by weight, the heat resistance of the coating film tends to be remarkably lowered, and further, the strength of the coating film tends to be lowered.
多官能エポキシ樹脂化合物としては、例えば、ビスフェノールA型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂等を用いることができる。 As the polyfunctional epoxy resin compound, for example, bisphenol A type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, and the like can be used.
ポリイソシアネート化合物としては、例えば、BL3475(商品名、住友バイエルウレタン(株)社製、β−ジケトンでブロックされたヘキサメチレンジイソシアネート化合物)、デスモジュールBL−1100(商品名、住友バイエルウレタン(株)製、ε−カプロラクタムでブロックされたトリレンジイソシアネート化合物)等を用いることができる。 Examples of the polyisocyanate compound include BL3475 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., hexamethylene diisocyanate compound blocked with β-diketone), Desmodur BL-1100 (trade name, Sumitomo Bayer Urethane Co., Ltd.) For example, a tolylene diisocyanate compound blocked with ε-caprolactam) can be used.
メラミン化合物としては、例えば、メチルエーテル化メラミン樹脂(三井サイテック(株)製商品名:サイメル300、サイメル303、サイメル325、サイメル327等、住友化学(株)製商品名:スミマールM−55、スミマールM−100、スミマールM−405等)、メチル化メラミン樹脂(三井サイテック(株)製商品名:サイメル232、サイメル266等)等を用いることができる。 Examples of the melamine compound include methyl etherified melamine resins (trade names: Mitmel Cytec Co., Ltd., trade name: Cymel 300, Cymel 303, Cymel 325, Cymel 327, etc., Sumitomo Chemical Co., Ltd. trade names: Sumimar M-55, Sumimar. M-100, Sumimar M-405, etc.), methylated melamine resin (trade name: Cymel 232, Cymel 266, etc. manufactured by Mitsui Cytec Co., Ltd.) and the like can be used.
本発明の芳香族系樹脂組成物は、N−メチル−2−ピロリドン、N,Nジメチルアセトアミド、N,N′−ジメチルホルムアミド及びγ―ブチロラクトン等の極性溶媒、キシレン、トルエン等の芳香族炭化水素溶媒、メチルエチルケトン、メチルイソブチルケトン等のケトン類などの溶媒に溶解され、適当な粘度に調整して塗料とすることができる。塗料とする場合、一般に固形分(芳香族系樹脂組成物の総量)は10〜50重量%とされる。 The aromatic resin composition of the present invention comprises N-methyl-2-pyrrolidone, N, N dimethylacetamide, N, N′-dimethylformamide, γ-butyrolactone and other aromatic solvents, xylene, toluene and other aromatic hydrocarbons. It can be dissolved in a solvent such as a solvent, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and adjusted to an appropriate viscosity to obtain a coating material. In the case of a paint, the solid content (total amount of the aromatic resin composition) is generally 10 to 50% by weight.
本発明の芳香族性樹脂組成物を用いて塗料とする場合、本発明の芳香族系樹脂組成物及び溶媒に加え、フッ素樹脂、グラファイトフレーク、ガラス化合物等を配合することができる。 In the case of using the aromatic resin composition of the present invention as a coating material, in addition to the aromatic resin composition and the solvent of the present invention, a fluororesin, graphite flakes, a glass compound and the like can be blended.
また、本発明の芳香族性樹脂組成物を用いて摺動部コーティング塗料バインダーとする場合、本発明の芳香族系樹脂組成物及び溶媒に加え、自動車工学シリーズ「自動車用ピストンリング」平成9年10月6日、(株)山海堂出版発行、第153−154頁に記載のMoS2等の固体潤滑剤等を配合することができる。 In addition, when using the aromatic resin composition of the present invention as a sliding part coating paint binder, in addition to the aromatic resin composition and solvent of the present invention, the automotive engineering series "Piston Ring for Automobile" 1997 On October 6, a solid lubricant such as MoS 2 described in Sankaidou Publishing Co., Ltd., pages 153 to 154 can be blended.
通常のポリアミドイミド樹脂組成物及び塗料は、基材に塗布した後、乾燥及び硬化のために熱処理され、少なくとも180℃以上で10分の加熱が必要である。これは、低温で硬化させると溶剤が残り、基材を保護する塗膜特性が劣る可能性がある。また、180℃未満の硬化では、塗膜の硬化が不十分で、極性溶媒に溶解又は膨じゅんする可能性がある。本発明の芳香族性樹脂組成物及び塗料は、通常、160〜380℃で10分〜60分の熱処理により、乾燥・硬化することができる。加熱時間は10分未満であると塗膜に残存溶媒がのこり、基材に塗布された塗膜の特性が劣ることがあり、60分を超えると、長期に熱を加えることにより、塗料として固体潤滑剤等を加えたときに副反応を起こすことがあり、塗膜の特性を劣化させることがある。 A normal polyamide-imide resin composition and a paint are heat-treated for drying and curing after being applied to a substrate, and need to be heated at least at 180 ° C. for 10 minutes. This may cause the solvent to remain when cured at a low temperature, resulting in poor coating properties that protect the substrate. Further, when the curing temperature is lower than 180 ° C., the coating film is not sufficiently cured and may be dissolved or swollen in a polar solvent. The aromatic resin composition and paint of the present invention can be dried and cured usually by heat treatment at 160 to 380 ° C. for 10 to 60 minutes. When the heating time is less than 10 minutes, the residual solvent remains on the coating film, and the characteristics of the coating film applied to the substrate may be inferior. When the heating time exceeds 60 minutes, it is solid as a paint by applying heat for a long time. When a lubricant or the like is added, a side reaction may occur and the properties of the coating film may be deteriorated.
以下、本発明を実施例により詳細に説明するが本発明はこれらに限定されるものではない。
実施例1
(1)撹拌機、冷却管、窒素導入管及び温度計を備えた2リットル四つ口フラスコにトリメリット酸無水物172.9g(0.9モル)、(b)成分としてのイソフタル酸16.6g(0.1モル)、(c)成分としての3,3′−ジメチルビフェニル−4,4′−ジイソシアネート185.0g(0.7モル)、ナフタレン−1,5−ジイソシアネート21.0g(0.1モル)、4,4′−ジフェニルメタンジイソシアネート50.1g(0.2モル)、N−メチル−2−ピロリドン1040gを仕込み、120℃まで昇温し、約6時間反応させる。数平均分子量が24,000となったらN−メチル−2−ピロリドン297gを仕込み、不揮発分25重量%のポリアミドイミド樹脂溶液を得た。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
Example 1
(1) 172.9 g (0.9 mol) of trimellitic anhydride in a 2 liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, and isophthalic acid as a component (b) 16. 6 g (0.1 mol), 3,3′-dimethylbiphenyl-4,4′-diisocyanate 185.0 g (0.7 mol) as component (c), 21.0 g of naphthalene-1,5-diisocyanate (0 .1 mol), 50.1 g (0.2 mol) of 4,4′-diphenylmethane diisocyanate and 1040 g of N-methyl-2-pyrrolidone, heated to 120 ° C., and reacted for about 6 hours. When the number average molecular weight reached 24,000, 297 g of N-methyl-2-pyrrolidone was charged to obtain a polyamideimide resin solution having a nonvolatile content of 25% by weight.
実施例2
(2)攪拌機、冷却管、窒素導入管及び温度計を備えた2リットル四つ口フラスコにトリメリット酸無水物153.7g(0.8モル)、(b)成分としてのイソフタル酸32.2g(0.2モル)、(c)成分としての3,3′−ジメチルビフェニル−4,4′−ジイソシアネート211.4g(0.8モル)、ナフタレン−1,5−ジイソシアネート21.0g(0.1モル)、4,4′−ジフェニルメタンジイソシアネート25.0g(0.1モル)、N−メチル−2−ピロリドン1037gを仕込み、120℃まで昇温し、約6時間反応させる。数平均分子量が29,000となったらN−メチル−2−ピロリドン296gを仕込み、不揮発分25重量%のポリアミドイミド樹脂溶液を得た。
Example 2
(2) Trimellitic anhydride 153.7 g (0.8 mol) in a 2 liter four-necked flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, and 32.2 g of isophthalic acid as component (b) (0.2 mol), 211.4 g (0.8 mol) of 3,3′-dimethylbiphenyl-4,4′-diisocyanate as component (c), 21.0 g of naphthalene-1,5-diisocyanate (0. 1 mol), 25.0 g (0.1 mol) of 4,4′-diphenylmethane diisocyanate, and 1037 g of N-methyl-2-pyrrolidone are heated to 120 ° C. and reacted for about 6 hours. When the number average molecular weight reached 29,000, 296 g of N-methyl-2-pyrrolidone was charged to obtain a polyamideimide resin solution having a nonvolatile content of 25% by weight.
実施例3
(3)攪拌機、冷却管、窒素導入管及び温度計を備えた2リットル四つ口フラスコにトリメリット酸無水物153.7g(0.8モル)、(b)成分としてのイソフタル酸32.2g(0.2モル)、(c)成分としての3,3′−ジメチルビフェニル−4,4′−ジイソシアネート158.6g(0.6モル)、ナフタレン−1,5−ジイソシアネート63.1g(0.3モル)、4,4′−ジフェニルメタンジイソシアネート25.0g(0.1モル)、N−メチル−2−ピロリドン1012gを仕込み、120℃まで昇温し、約6時間反応させる。数平均分子量が18,000となったらN−メチル−2−ピロリドン289gを仕込み、不揮発分25重量%のポリアミドイミド樹脂溶液を得た。
Example 3
(3) Trimellitic anhydride 153.7 g (0.8 mol) in a 2 liter four-necked flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, and 32.2 g of isophthalic acid as component (b) (0.2 mol), 158.6 g (0.6 mol) of 3,3′-dimethylbiphenyl-4,4′-diisocyanate as component (c), 63.1 g of naphthalene-1,5-diisocyanate (0. 3 mol), 45.0 ′ (0.1 mol) of 4,4′-diphenylmethane diisocyanate and 1012 g of N-methyl-2-pyrrolidone, heated to 120 ° C. and reacted for about 6 hours. When the number average molecular weight reached 18,000, 289 g of N-methyl-2-pyrrolidone was charged to obtain a polyamideimide resin solution having a nonvolatile content of 25% by weight.
比較例1
(1)攪拌機、冷却管、窒素導入管及び温度計を備えた2リットル四つ口フラスコに(a)成分としての無水トリメリット酸192.1g(1.00モル)、(c)成分としての4,4′−ジフェニルメタンジイソシアネート255.3g(1.02モル)及びN−メチル−2−ピロリドン1043.9gを仕込み、130℃まで昇温し、4時間反応させて、不揮発分30重量%のポリアミドイミド樹脂溶液(樹脂の数平均分子量:24,000)を得た。
Comparative Example 1
(1) In a 2 liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, 192.1 g (1.00 mol) of trimellitic anhydride as component (a), (c) as component Polyamide containing 255.3 g (1.02 mol) of 4,4′-diphenylmethane diisocyanate and 1043.9 g of N-methyl-2-pyrrolidone, heated to 130 ° C. and reacted for 4 hours to give a nonvolatile content of 30% by weight An imide resin solution (resin number average molecular weight: 24,000) was obtained.
比較例2
(2)攪拌機、冷却管、窒素導入管及び温度計を備えた2リットル四つ口フラスコに(a)成分としての無水トリメリット酸153.7g(0.80モル)、(b)成分としてイソフタル酸33.2g(0.2モル)(c)成分としての4,4′−ジフェニルメタンジイソシアネート100.1g(0.4モル)と3,3−ジメチル−4,4−ジイソシアネートビフェニル158.6g(0.6モル)及びN−メチル−2−ピロリドン1040gを仕込み、130℃まで昇温し、4時間反応させて、不揮発分30重量%のポリアミドイミド樹脂溶液を得た(樹脂の数平均分子量:28,000)。
Comparative Example 2
(2) 153.7 g (0.80 mol) of trimellitic anhydride as component (a) in a 2 liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, and isophthalic acid as component (b) 33.2 g (0.2 mol) of acid 100.1 g (0.4 mol) of 4,4'-diphenylmethane diisocyanate as component (c) and 158.6 g of 3,3-dimethyl-4,4-diisocyanate biphenyl (0) .6 mol) and 1040 g of N-methyl-2-pyrrolidone were heated to 130 ° C. and reacted for 4 hours to obtain a polyamideimide resin solution having a nonvolatile content of 30% by weight (number average molecular weight of the resin: 28 , 000).
比較例3
(3)攪拌機、冷却管、窒素導入管及び温度計を備えた2リットル四つ口フラスコに(a)成分としての無水トリメリット酸192.1g(1.0モル)、(c)成分としての4,4′−ジフェニルメタンジイソシアネート100.1g(0.4モル)とナフタレン−1,5−ジイソシアネート126.1g(0.6モル)、及びN−メチル−2−ピロリドン976gを仕込み、130℃まで昇温し、4時間反応させて、不揮発分30重量%のポリアミドイミド樹脂溶液を得た(樹脂の数平均分子量:22,000)。
Comparative Example 3
(3) 192.1 g (1.0 mol) of trimellitic anhydride as the component (a) and (c) as the component (c) in a 2 liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer Charge 100.1 g (0.4 mol) of 4,4′-diphenylmethane diisocyanate, 126.1 g (0.6 mol) of naphthalene-1,5-diisocyanate, and 976 g of N-methyl-2-pyrrolidone, and raise the temperature to 130 ° C. The mixture was heated and reacted for 4 hours to obtain a polyamideimide resin solution having a nonvolatile content of 30% by weight (the number average molecular weight of the resin: 22,000).
試験例
実施例1〜3及び比較例1〜3で得られたポリアミドイミド樹脂100重量部に対してビスフェノールA型エポキシ樹脂を15重量部加えて芳香族性樹脂組成物を調製し、アルミ板上に膜厚が30μmになるように塗布した後、180℃で30分加熱処理を行った。
評価は以下の方法で測定した。その測定した結果をまとめて表1に示す。
(1)外観:目視により、塗膜の濁り、表面の肌荒れを調べた。
(2)密着性(クロスカット試験):JIS D0202に準じて試験を行った。
(3)鉛筆硬度:JIS K5600に準じて試験を行なった。
(4)硬化性:それぞれの芳香族製樹脂組成物を20×50mmの鋼板上に膜厚が20μmになるように塗布した後、180℃で30分熱処理をした。これを、N−メチル−2−ピロリドン中に1時間浸漬した後に次記により抽出率を求めた。
Test Example An aromatic resin composition was prepared by adding 15 parts by weight of a bisphenol A type epoxy resin to 100 parts by weight of the polyamideimide resin obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and on an aluminum plate. After coating so that the film thickness was 30 μm, heat treatment was performed at 180 ° C. for 30 minutes.
Evaluation was measured by the following method. The measured results are summarized in Table 1.
(1) Appearance: The turbidity of the coating film and roughness of the surface were examined visually.
(2) Adhesiveness (cross cut test): A test was conducted in accordance with JIS D0202.
(3) Pencil hardness: The test was conducted according to JIS K5600.
(4) Curability: Each aromatic resin composition was coated on a 20 × 50 mm steel plate so as to have a film thickness of 20 μm, and then heat-treated at 180 ° C. for 30 minutes. This was immersed in N-methyl-2-pyrrolidone for 1 hour, and then the extraction rate was determined as follows.
(5)機械的特性:実施例及び比較例で得られた各々のポリアミドイミド樹脂溶液をガラス板に塗布し、180℃で30分間加熱して得られたフィルムを膜厚20μm、幅10mm、チャック間20mmに調整し、引張り速度5mm/minで引張り試験を行い、引張り強度、弾性率及び伸び率の測定を行った。
(6)安定性:ワニスの雰囲気温度25℃における経日粘度変化を次式により求めた。
(5) Mechanical properties: each polyamideimide resin solution obtained in Examples and Comparative Examples was applied to a glass plate and heated at 180 ° C. for 30 minutes to obtain a film having a thickness of 20 μm, a width of 10 mm, and a chuck The tension was adjusted to 20 mm, a tensile test was performed at a pulling speed of 5 mm / min, and the tensile strength, elastic modulus, and elongation were measured.
(6) Stability: The change in viscosity over time at an atmospheric temperature of 25 ° C. of the varnish was determined by the following formula.
表1に示した結果から、本発明の実施例で得られた芳香族性樹脂組成物は、低温で硬化した場合でも密着性及び抽出率が優れていることがわかる。塗膜の硬度及び弾性率は実施例1、2、3が比較例1、2より優れており、また、実施例1、2で得られたポリアミドイミド樹脂は比較例1、2、3で得られた芳香族性樹脂組成物より伸び率が優れることから、塗膜の硬さや柔軟性のバランスが優れていることがわかる。 From the results shown in Table 1, it can be seen that the aromatic resin compositions obtained in the examples of the present invention are excellent in adhesion and extraction rate even when cured at a low temperature. As for the hardness and elastic modulus of the coating film, Examples 1, 2, and 3 were superior to Comparative Examples 1 and 2, and the polyamideimide resins obtained in Examples 1 and 2 were obtained in Comparative Examples 1, 2, and 3. Since the elongation rate is superior to the obtained aromatic resin composition, it is understood that the balance of hardness and flexibility of the coating film is excellent.
Claims (7)
で表されるジカルボン酸又はその水素化物であるジカルボン酸及び(c)一分子中に2個以上のアミノ基又はイソシアナト基を有し、一般式(II)で表される芳香族化合物及び一般式(III)で表される芳香族化合物を含有する芳香族化合物
を反応させて得られアミド基数/イミド基数の比が51/49〜80/20の範囲にあるポリアミドイミド樹脂を含有する芳香族系樹脂組成物。 (A) a derivative of a trivalent carboxylic acid having an acid anhydride group, (b) a general formula (I)
And (c) an aromatic compound having two or more amino groups or isocyanato groups in one molecule, and represented by the general formula (II) and the general formula Aromatic compound containing aromatic compound represented by (III)
An aromatic resin composition containing a polyamide-imide resin obtained by reacting amide group and having a ratio of amide group number / imide group number in the range of 51/49 to 80/20.
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JP2011162733A (en) * | 2010-02-15 | 2011-08-25 | Hitachi Chem Co Ltd | Heat-resistant resin composition and coating using the same |
JP2012131856A (en) * | 2010-12-20 | 2012-07-12 | Dic Corp | Heat-resistant paint and article having coat formed by hardening heat-resistant paint |
JP2012224703A (en) * | 2011-04-18 | 2012-11-15 | Hitachi Chemical Co Ltd | Polyamide-imide resin, production method therefor, thermosetting resin composition, insulation coating material and electric insulated wire |
WO2017104461A1 (en) * | 2015-12-14 | 2017-06-22 | 日立化成株式会社 | Polyamide-imide resin and coating material |
WO2017204462A1 (en) * | 2016-05-24 | 2017-11-30 | 주식회사 엘지화학 | Polyamide-imide, method for preparing same, and polyamide-imide film using same |
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WO2017104461A1 (en) * | 2015-12-14 | 2017-06-22 | 日立化成株式会社 | Polyamide-imide resin and coating material |
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US11518852B2 (en) | 2017-03-01 | 2022-12-06 | Showa Denko Materials Co., Ltd. | Polyamideimide resin and use thereof |
CN113571704A (en) * | 2020-06-30 | 2021-10-29 | 深圳市研一新材料有限责任公司 | Polyamide-imide binder for lithium ion battery and electrode plate |
CN113571704B (en) * | 2020-06-30 | 2022-06-14 | 深圳市研一新材料有限责任公司 | Polyamide-imide binder for lithium ion battery and electrode plate |
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