JP2007217489A - Oh modified polybenzimidazole resin and method for preparation of the same - Google Patents
Oh modified polybenzimidazole resin and method for preparation of the same Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 151
- 229920005989 resin Polymers 0.000 title claims abstract description 151
- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 142
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 39
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 9
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 31
- 239000011342 resin composition Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000003607 modifier Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000005056 polyisocyanate Substances 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 150000003138 primary alcohols Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 17
- 238000012986 modification Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 4
- -1 polysiloxane structure Polymers 0.000 description 4
- 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 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- CDZXJJOGDCLNKX-UHFFFAOYSA-N 2,2,3,3-tetrafluorobutane-1,4-diol Chemical compound OCC(F)(F)C(F)(F)CO CDZXJJOGDCLNKX-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 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
- 230000001681 protective effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 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
- 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 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- GBXRUYNQDDTQQS-UHFFFAOYSA-N 1-O-dodecylglycerol Chemical compound CCCCCCCCCCCCOCC(O)CO GBXRUYNQDDTQQS-UHFFFAOYSA-N 0.000 description 1
- FQYIBTYPDCFSRE-UHFFFAOYSA-N 1-ethoxy-4-methylhexane-1,2-diol Chemical compound CC(CC)CC(C(O)OCC)O FQYIBTYPDCFSRE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AVSUMWIDHQEMPD-UHFFFAOYSA-N 2-(oxiran-2-yl)ethanol Chemical compound OCCC1CO1 AVSUMWIDHQEMPD-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- NULJIGCWBBPPOA-UHFFFAOYSA-N 3-(3,3-dimethoxybutoxy)propane-1,2-diol Chemical compound COC(CCOCC(CO)O)(C)OC NULJIGCWBBPPOA-UHFFFAOYSA-N 0.000 description 1
- SOGGLVJYVOCYTB-UHFFFAOYSA-N 3-(oxiran-2-yl)propan-1-ol Chemical compound OCCCC1CO1 SOGGLVJYVOCYTB-UHFFFAOYSA-N 0.000 description 1
- LOSWWGJGSSQDKH-UHFFFAOYSA-N 3-ethoxypropane-1,2-diol Chemical compound CCOCC(O)CO LOSWWGJGSSQDKH-UHFFFAOYSA-N 0.000 description 1
- GUPXYSSGJWIURR-UHFFFAOYSA-N 3-octoxypropane-1,2-diol Chemical compound CCCCCCCCOCC(O)CO GUPXYSSGJWIURR-UHFFFAOYSA-N 0.000 description 1
- ZTKZJXGLCCVMLJ-UHFFFAOYSA-N 3-propoxypropane-1,2-diol Chemical compound CCCOCC(O)CO ZTKZJXGLCCVMLJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-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
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- GCXZDAKFJKCPGK-UHFFFAOYSA-N heptane-1,2-diol Chemical compound CCCCCC(O)CO GCXZDAKFJKCPGK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 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
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LJZULWUXNKDPCG-UHFFFAOYSA-N nonane-1,2-diol Chemical compound CCCCCCCC(O)CO LJZULWUXNKDPCG-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、超耐熱性を有するポリベンゾイミダゾール樹脂を水酸基含有基で変性してなるＯＨ変性ポリベンゾイミダゾール樹脂及びその製造方法に関する。 The present invention relates to an OH-modified polybenzimidazole resin obtained by modifying a polybenzimidazole resin having super heat resistance with a hydroxyl group-containing group, and a method for producing the same.
近年に開発されたポリベンゾイミダゾール樹脂は、ポリイミド樹脂に比しても遥かに高い超耐熱性を有しており、各種基材の被覆用樹脂として使用されている（例えば特許文献１，２参照）。しかしながら、このようなポリベンゾイミダゾール樹脂は、超耐熱性を有していることに関連して、化学的に極めて安定であって反応性に乏しく、このため、各種基材に対する密着性が低いという欠点がある。従って、従来は、基材にシランカップリング剤を塗布することにより、その密着性の向上が図られていたが、このような手段では、密着性を十分に向上させることができず、さらなる密着性の向上が求められている。 Polybenzimidazole resins developed in recent years have much higher heat resistance than polyimide resins, and are used as coating resins for various substrates (see, for example, Patent Documents 1 and 2). ). However, such polybenzimidazole resin is chemically stable and poor in reactivity in connection with having super heat resistance, and therefore has low adhesion to various substrates. There are drawbacks. Therefore, conventionally, the adhesion has been improved by applying a silane coupling agent to the base material. However, with such means, the adhesion cannot be sufficiently improved, and further adhesion is achieved. There is a need for improvement in performance.
一方、ポリベンゾイミダゾール樹脂に離型性を付与するために、ポリシロキサン構造を有するマクロモノマーをグラフト重合させたり（特許文献３）、或いは導電性を付与するために、原料モノマーとしてイオン性官能基含有モノマーを使用し、主鎖中に官能基が導入されたポリベンゾイミダゾール樹脂が提案されている（特許文献４）。しかしながら、密着性を改善するために、ポリベンゾイミダゾール樹脂を変性することについての提案はなされていない。
従って、本発明の目的は、ポリベンゾイミダゾール樹脂に特有の超耐熱性が損なわれることなく、その密着性が向上した変性ポリベンゾイミダゾール樹脂及びその製造方法を提供することにある。
本発明の他の目的は、上記の変性ポリベンゾイミダゾール樹脂を含有する樹脂組成物を提供することにある。
Accordingly, an object of the present invention is to provide a modified polybenzimidazole resin having improved adhesion without impairing the super heat resistance characteristic of the polybenzimidazole resin and a method for producing the same.
Another object of the present invention is to provide a resin composition containing the modified polybenzimidazole resin.
本発明によれば、下記式（１）：
Ｂは、２価のアリール基である、
Ｒ１及びＲ２は、それぞれ水素原子である、
で表されるベンゾイミダゾール繰り返し単位の連鎖（但し、連鎖中、前記Ｒ１及びＲ２の一部はアルキル基で置換されていてもよい）からなるポリベンゾイミダゾール樹脂をＯＨ変性してなるＯＨ変性ポリベンゾイミダゾール樹脂であって、前記繰り返し単位におけるイミダゾール環中の窒素原子の少なくとも一部には、アミド結合を介して非ハロゲン系の水酸基含有変性基が結合しており、且つ１．０ｍｇＫＯＨ／ｇ以上の水酸基価を有していることを特徴とするＯＨ変性ポリベンゾイミダゾール樹脂が提供される。
According to the present invention, the following formula (1):
B is a divalent aryl group.
R 1 and R 2 are each a hydrogen atom,
An OH-modified product obtained by OH-modifying a polybenzimidazole resin comprising a chain of benzimidazole repeating units represented by the formula (wherein, part of R 1 and R 2 may be substituted with an alkyl group). A polybenzimidazole resin, wherein a non-halogen-based hydroxyl group-containing modifying group is bonded to at least a part of nitrogen atoms in the imidazole ring in the repeating unit via an amide bond, and 1.0 mgKOH / g An OH-modified polybenzimidazole resin having the above hydroxyl value is provided.
本発明のＯＨ変性ポリベンゾイミダゾール樹脂においては、
（１）前記水酸基含有変性基は、前記窒素原子にアミド結合を介して導入されたカルボキシル基含有基のカルボキシル基にエステル結合を介して水酸基含有基が結合したものであること、
が好ましい。
In the OH-modified polybenzimidazole resin of the present invention,
(1) The hydroxyl group-containing modifying group is a group in which a hydroxyl group-containing group is bonded via an ester bond to a carboxyl group of a carboxyl group-containing group introduced into the nitrogen atom via an amide bond,
Is preferred.
本発明によれば、また、前記式（１）で表されるベンゾイミダゾール繰り返し単位からなる未変性ポリベンゾイミダゾール樹脂を、多価カルボン酸と反応させることにより、前記繰り返し単位におけるイミダゾール環中の窒素原子の少なくとも一部に、アミド結合を介して多価カルボン酸由来の変性基を導入してＣＯＯＨ変性ポリベンゾイミダゾール樹脂を調製し、
次いで、１級アルコール由来のＯＨ基を少なくとも２個有する非ハロゲン系多価アルコール化合物または１級アルコール由来のＯＨ基と末端エポキシ基とを有する非ハロゲン系アルコール性エポキシ化合物を変性剤として使用し、該変性剤を前記ポリベンゾイミダゾール樹脂と混合して加熱することにより、該変性剤を前記ＣＯＯＨ変性ポリベンゾイミダゾールに導入されている変性基中のカルボキシル基と反応させて、前記多価アルコール化合物またはアルコール性エポキシ化合物に由来するＯＨ含有基を前記変性基に導入することを特徴とするＯＨ変性ポリベンゾイミダゾール樹脂の製造方法が提供される。
According to the present invention, the nitrogen in the imidazole ring in the repeating unit can be obtained by reacting an unmodified polybenzimidazole resin composed of the benzimidazole repeating unit represented by the formula (1) with a polyvalent carboxylic acid. A COOH-modified polybenzimidazole resin is prepared by introducing a modifying group derived from a polyvalent carboxylic acid via an amide bond into at least a part of the atoms,
Next, a non-halogen polyhydric alcohol compound having at least two OH groups derived from a primary alcohol or a non-halogen alcohol-based epoxy compound having an OH group and a terminal epoxy group derived from a primary alcohol is used as a modifier. By mixing and heating the modifier with the polybenzimidazole resin, the modifier is reacted with a carboxyl group in the modifier group introduced into the COOH-modified polybenzimidazole, and the polyhydric alcohol compound or Provided is a method for producing an OH-modified polybenzimidazole resin, wherein an OH-containing group derived from an alcoholic epoxy compound is introduced into the modified group.
本発明において、前記ＣＯＯＨ変性ポリベンゾイミダゾール樹脂は、１．０ｍｇＫＯＨ／ｇ以上、特に１０〜１５０ｍｇＫＯＨ／ｇの酸価を有していることが好ましい。 In the present invention, the COOH-modified polybenzimidazole resin preferably has an acid value of 1.0 mgKOH / g or more, particularly 10 to 150 mgKOH / g.
本発明によれば、さらに、前記ＯＨ変性ポリベンゾイミダゾール樹脂と、前記ＣＯＯＨ変性ポリベンゾイミダゾール樹脂と、ポリイソシアネート化合物とからなる樹脂組成物が提供される。
かかる樹脂組成物においては、前記ＯＨ変性ポリベンゾイミダゾール樹脂１００重量部当り、ＣＯＯＨ変性ポリベンゾイミダゾール樹脂を１０乃至１０００重量部、特に３０乃至３００重量部の量で含有していることが好ましい。
According to the present invention, there is further provided a resin composition comprising the OH-modified polybenzimidazole resin, the COOH-modified polybenzimidazole resin, and a polyisocyanate compound.
In such a resin composition, the COOH-modified polybenzimidazole resin is preferably contained in an amount of 10 to 1000 parts by weight, particularly 30 to 300 parts by weight, per 100 parts by weight of the OH-modified polybenzimidazole resin.
本発明のＯＨ変性ポリベンゾイミダゾール樹脂は、ポリベンゾイミダゾール樹脂の繰り返し単位中のイミダゾール環の窒素原子の少なくとも一部に、アミド結合を介して非ハロゲン系の水酸基含有変性基が導入されていることが顕著な特徴である。即ち、このような水酸基含有変性基が導入されているため、超耐熱性を損なうことなく、各種樹脂や金属に対する密着性が顕著に向上するのである。 In the OH-modified polybenzimidazole resin of the present invention, a non-halogen-based hydroxyl group-containing modifying group is introduced into at least a part of the nitrogen atom of the imidazole ring in the repeating unit of the polybenzimidazole resin through an amide bond. Is a prominent feature. That is, since such a hydroxyl group-containing modifying group is introduced, adhesion to various resins and metals is remarkably improved without impairing super heat resistance.
＜ＯＨ変性ポリベンゾイミダゾール樹脂の製造＞
本発明のＯＨ変性ポリベンゾイミダゾール樹脂は、未変性のポリベンゾイミダゾール樹脂（以下、ＰＢＩ樹脂と呼ぶ）を、ＣＯＯＨ変性及びＯＨ変性の２段で変性することにより得られる。
<Production of OH-modified polybenzimidazole resin>
The OH-modified polybenzimidazole resin of the present invention can be obtained by modifying an unmodified polybenzimidazole resin (hereinafter referred to as PBI resin) in two stages of COOH modification and OH modification.
出発原料として使用される未変性のＰＢＩ樹脂は、それ自体公知であり、式（１）：
Ｂは、２価のアリール基である、
Ｒ１及びＲ２は、それぞれ水素原子である、
で表されるベンゾイミダゾール繰り返し単位の連鎖からなるものであり、本発明においては、数平均分子量が１０００〜１，０００，０００、特に１０，０００〜５００，０００、特に好ましくは５０，０００〜１５０，０００程度の範囲のポリベンゾイミダゾール樹脂を使用することが好ましい。また、式（１）中のＲ１及びＲ２は、水素原子であるが、連鎖中、これらの水素原子の一部は、アルキル基、例えばメチル基、エチル基、プロピル基等の低級アルキル基で置換されていてもよい。但し、後述するＣＯＯＨ変性は、ＮＨ基との反応により行われるため、アルキル基による置換量は、ＣＯＯＨ変性を阻害せず、所望の変性が行われる程度の量に止めておく必要がある。
Unmodified PBI resins used as starting materials are known per se and have the formula (1):
B is a divalent aryl group.
R 1 and R 2 are each a hydrogen atom,
In the present invention, the number average molecular weight is 1000 to 1,000,000, particularly 10,000 to 500,000, particularly preferably 50,000 to 150. It is preferable to use a polybenzimidazole resin in the range of about 1,000. In addition, R 1 and R 2 in the formula (1) are hydrogen atoms, and in the chain, some of these hydrogen atoms are alkyl groups such as lower alkyl groups such as methyl, ethyl, and propyl groups. May be substituted. However, since COOH modification, which will be described later, is performed by a reaction with an NH group, the substitution amount with an alkyl group must be kept at an amount that does not inhibit COOH modification and allows desired modification.
上記式（１）中の４価のアリール基Ａとしては、例えば下記式：
また、上記式（１）中の２価のアリール基Ｂとしては、上記の４価のアリール基に対応する２価の基、例えば下記式：
上記構造を有するＰＢＩ樹脂は、非常に剛直性が高く、耐熱性や強度に優れている。このようなＰＢＩ樹脂を原料として用いることにより、特に耐熱性や強度に優れ、さらに密着性の優れた樹脂を得ることができる。このような式（１）で表されるベンゾイミダゾール繰り返し単位からなるＰＢＩ樹脂は、それ自体公知の方法で製造される。 The PBI resin having the above structure is very rigid and excellent in heat resistance and strength. By using such a PBI resin as a raw material, a resin having particularly excellent heat resistance and strength and excellent adhesion can be obtained. Such a PBI resin comprising a benzimidazole repeating unit represented by the formula (1) is produced by a method known per se.
本発明においては、先ず、上記の未変性ＰＢＩ樹脂を、ＣＯＯＨ変性剤を用いてＣＯＯＨ変性する。 In the present invention, first, the unmodified PBI resin is COOH-modified using a COOH modifier.
このＣＯＯＨ変性は、未変性ＰＢＩ樹脂を溶媒に溶解させ、ＰＢＩ樹脂溶液を調製し、これにＣＯＯＨ変性剤を混合して反応させることにより行われる。この際の溶媒としては、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドンなどが使用できるが、特にＮ，Ｎ−ジメチルアセトアミドが好適である。また、ＰＢＩ樹脂溶液の濃度は、通常、５乃至１５重量％程度であり、一般に、５乃至１５ｋｇｆ／ｃｍ２程度の加圧下で２００乃至３００℃程度でＰＢＩ樹脂と溶媒とを加熱混合することによりＰＢＩ溶液を調製することができる。
尚、ＰＢＩ樹脂は、上記のような溶媒に溶解させた溶液状の形態で市販されている。
This COOH modification is performed by dissolving an unmodified PBI resin in a solvent to prepare a PBI resin solution, and mixing and reacting with a COOH modifier. As the solvent in this case, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be used, and N, N-dimethylacetamide is particularly preferable. The concentration of the PBI resin solution is usually about 5 to 15% by weight. Generally, the PBI resin and the solvent are heated and mixed at about 200 to 300 ° C. under a pressure of about 5 to 15 kgf / cm 2. A PBI solution can be prepared.
The PBI resin is commercially available in the form of a solution dissolved in the above solvent.
またＣＯＯＨ変性剤としては、マレイン酸、フマル酸、コハク酸、アジピン酸、フタル酸、イソフタル酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、ダイマー酸、セバチン酸、アゼライン酸、５−Ｎａスルホイソフタル酸、イタコン酸、シトラコン酸、ノルボルネンジカルボン酸、ビシクロ［２，２，１］ヘプト−２−エン−５，６−ジカルボン酸、及びこれらの酸無水物などの多価カルボン酸化合物を例示することができ、特にマレイン酸或いは無水マレイン酸が、反応性等の点で特に好適である。このようなＣＯＯＨ変性剤は、通常、原料ＰＢＩ樹脂のアミノ基に対して０．０１〜１０当量、特に０．０５〜０．５当量となるように、例えば原料ＰＢＩ樹脂１００重量部当り０．５重量部以上、特に３乃至１５重量部の量で使用し、得られるＣＯＯＨ変性ＰＢＩ樹脂の酸価が１．０ｍｇＫＯＨ／ｇ以上、特に１０乃至１００ｍｇＫＯＨ／ｇとなるようにするのがよい。即ち、ＣＯＯＨ変性剤の使用量が少ないと、得られるＣＯＯＨ変性ＰＢＩ樹脂の酸価が小さくなり、このため、所定量のＯＨ基を導入することが困難となってしまう。また、必要以上に多量のＣＯＯＨ変性剤を使用し、得られるＣＯＯＨ変性ＰＢＩ樹脂の酸価を必要以上に大きくすると、後述するＯＨ変性工程で未反応物などの生成量が多くなり、密着性の低下やＰＢＩ樹脂が本来有している超耐熱性が低下するおそれがある。 Examples of the COOH modifier include maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-Na sulfoisophthalic acid, Examples thereof include polycarboxylic acid compounds such as itaconic acid, citraconic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid, and acid anhydrides thereof. In particular, maleic acid or maleic anhydride is particularly preferred in terms of reactivity. Such a COOH modifier is usually 0.01 to 10 equivalents, particularly 0.05 to 0.5 equivalents relative to the amino group of the raw material PBI resin, for example, 0.000 per 100 parts by weight of the raw material PBI resin. It is preferable that the acid value of the obtained COOH-modified PBI resin is 1.0 mgKOH / g or more, particularly 10 to 100 mgKOH / g. That is, if the amount of COOH modifier used is small, the acid value of the resulting COOH-modified PBI resin will be small, and it will be difficult to introduce a predetermined amount of OH groups. In addition, if an unnecessarily large amount of COOH modifier is used and the acid value of the resulting COOH-modified PBI resin is increased more than necessary, the amount of unreacted products generated in the OH modification step described later increases, and adhesion is improved. There exists a possibility that the superheat resistance which PBI resin originally has and a fall may fall.
また、ＣＯＯＨ変性剤による反応は、通常、副反応等を抑制するため、窒素雰囲気等の不活性ガス雰囲気中で行うことが好ましく、また５０乃至１５０℃程度の温度で、加熱還流下で行うことが好適である。 In addition, the reaction with the COOH modifier is usually preferably performed in an inert gas atmosphere such as a nitrogen atmosphere in order to suppress side reactions and the like, and is performed at a temperature of about 50 to 150 ° C. under heating and reflux. Is preferred.
上記のようにして適度な酸価を有するＣＯＯＨ変性ＰＢＩ樹脂が得られる。かかるＣＯＯＨ変性ＰＢＩ樹脂においては、ベンゾイミダゾール環中の窒素原子（特にＮＨ基）にＣＯＯＨ変性剤の一方のカルボキシル基がアミド結合し、下記式（２）：
＞ＮＣＯ−Ｘ−ＣＯＯＨ …（２）
式中、Ｘは、ＣＯＯＨ変性剤に由来する２価の基である、
で表されるようにしてＣＯＯＨ変性基が導入されている。
As described above, a COOH-modified PBI resin having an appropriate acid value can be obtained. In such a COOH-modified PBI resin, one carboxyl group of the COOH modifier is amide-bonded to a nitrogen atom (particularly an NH group) in the benzimidazole ring, and the following formula (2):
> NCO-X-COOH (2)
In the formula, X is a divalent group derived from a COOH modifier.
A COOH-modified group is introduced as represented by:
本発明において、上記のようにしてＣＯＯＨ変性を行った後は、ＯＨ変性剤を用いて引き続きＯＨ変性を行うことにより、ＣＯＯＨ変性基にＯＨ含有基を導入する。 In the present invention, after COOH modification is performed as described above, an OH-containing group is introduced into the COOH-modified group by subsequent OH modification using an OH modifier.
このようなＯＨ変性に用いる変性剤としては、非ハロゲン系の化合物が使用される。非ハロゲン系の化合物を使用するのは、ハロゲン含有の化合物を用いて変性を行うと、ハロゲンの導入により、密着性が損なわれてしまうからである。このような非ハロゲン系の化合物としては、１級アルコール由来のＯＨ基を少なくとも２個有する非ハロゲン系多価アルコール化合物または１級アルコール由来のＯＨ基と末端エポキシ基とを有する非ハロゲン系アルコール性エポキシ化合物が使用される。中でも、−ＣＯＯＨとの反応性が高く、ゲル化を起こし難い点で、非ハロゲン系のアルコール性エポキシ化合物が好適である。 As the modifier used for such OH modification, a non-halogen compound is used. The reason for using a non-halogen compound is that if modification is performed using a halogen-containing compound, the adhesion is impaired by the introduction of halogen. Such non-halogen compounds include non-halogen polyhydric alcohol compounds having at least two primary alcohol-derived OH groups or non-halogen alcohols having primary alcohol-derived OH groups and terminal epoxy groups. Epoxy compounds are used. Among these, non-halogen alcoholic epoxy compounds are preferable because they are highly reactive with —COOH and hardly cause gelation.
尚、上記の非ハロゲン系アルコール性エポキシ化合物において、１級アルコール由来のＯＨ基と末端エポキシ基とでは、エポキシ基の方がＣＯＯＨ基との反応性が高い。このため、非ハロゲン系アルコール性エポキシ化合物を用いた場合にも、ＰＢＩには、フリーのＯＨ基が導入されることとなる。また、このようなエポキシ基は、末端にのみ存在していることが好ましい。 In the above non-halogen alcoholic epoxy compound, the OH group derived from the primary alcohol and the terminal epoxy group are more reactive with the COOH group. For this reason, even when a non-halogen alcoholic epoxy compound is used, a free OH group is introduced into PBI. Moreover, it is preferable that such an epoxy group exists only at the terminal.
上記の非ハロゲン系多価アルコール化合物の例としては、これに限定されるものではないが、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、３−エトキシ−１，２−ジヒドロキシプロパン、３−ｎ−オクトキシ−１，２−ジヒドロキシプロパン、３−ラウロキシ−１，２−ジヒドロキシプロパン、３−プロポキシ−１，２−ジヒドロキシプロパン、３−（２−ｎ−ブチル）エトキシ−１，２−ジヒドロキシプロパン、３−（３，３−ジメトキシブチル）オキシ−１，２−ジヒドロキシプロパン、３−（ｎ−ブチル）−１，２−ジヒドロキシプロパン、３−（ｎ−ヘキシル）−１，２−ジヒドロキシプロパン、１，４−ビス（１，２−ジヒドロキシプロピル）−ｎ−ブタンなどを例示することができる。また、上記の非ハロゲン系アルコール性エポキシ化合物としては、２，３−エポキシ−１−プロパノール、３，４−エポキシ−１−ブタノール、４，５−エポキシ−１−ペンタノール、５，６−エポキシ−１−ヘキサノールなどを例示することができる。 Examples of the non-halogen polyhydric alcohol compound include, but are not limited to, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. 1,8-octanediol, 3-ethoxy-1,2-dihydroxypropane, 3-n-octoxy-1,2-dihydroxypropane, 3-lauroxy-1,2-dihydroxypropane, 3-propoxy-1,2 -Dihydroxypropane, 3- (2-n-butyl) ethoxy-1,2-dihydroxypropane, 3- (3,3-dimethoxybutyl) oxy-1,2-dihydroxypropane, 3- (n-butyl) -1 , 2-dihydroxypropane, 3- (n-hexyl) -1,2-dihydroxypropane, 1,4-bis (1, - and the like can be exemplified dihydroxypropyl)-n-butane. Examples of the non-halogen alcoholic epoxy compound include 2,3-epoxy-1-propanol, 3,4-epoxy-1-butanol, 4,5-epoxy-1-pentanol, and 5,6-epoxy. Examples thereof include -1-hexanol.
上記のようなＯＨ変性剤は、ＣＯＯＨ基に対して０．１〜１０当量、特に０．５〜５当量の量で使用するのがよく、例えば原料ＰＢＩ樹脂１００重量部当り１．０重量部以上、特に３乃至１５重量部の量で使用することが好ましい。かかるＯＨ変性剤を用いての反応は、前述したＣＯＯＨ変性と同様、不活性雰囲気中、５０乃至１５０℃の温度で加熱還流下に行うことが好ましい。 The OH modifier as described above is preferably used in an amount of 0.1 to 10 equivalents, particularly 0.5 to 5 equivalents, based on COOH groups, for example, 1.0 part by weight per 100 parts by weight of the raw material PBI resin. As described above, it is particularly preferable to use in an amount of 3 to 15 parts by weight. The reaction using such an OH modifier is preferably performed under heating and refluxing at a temperature of 50 to 150 ° C. in an inert atmosphere as in the case of the COOH modification described above.
上記のような反応により、前述したＣＯＯＨ変性基中のカルボキシル基に１級アルコール由来のＯＨ基或いはエポキシ基が反応してエステル結合を形成し、下記式（３）：
＞ＮＣＯ−Ｘ−ＣＯＯ−Ｙ−ＯＨ …（３）
式中、Ｘは、ＣＯＯＨ変性剤に由来する２価の基であり、
Ｙは、ＯＨ変性剤に由来する２価の基である、
で表されるようにして、所定量の水酸基が導入され、目的とするＯＨ変性ＰＢＩ樹脂が得られる。
By the reaction as described above, the OH group or epoxy group derived from the primary alcohol reacts with the carboxyl group in the COOH-modified group described above to form an ester bond, and the following formula (3):
> NCO-X-COO-Y-OH (3)
In the formula, X is a divalent group derived from a COOH modifier,
Y is a divalent group derived from an OH modifier.
As shown, a predetermined amount of hydroxyl group is introduced to obtain the target OH-modified PBI resin.
＜ＯＨ変性ＰＢＩ樹脂＞
このようにして水酸基が導入されたＯＨ変性ＰＢＩ樹脂は、水酸基価が１．０ｍｇＫＯＨ／ｇ以上、好ましくは１０乃至１００ｍｇＫＯＨ／ｇ、さらに好ましくは２０〜９０ｍｇＫＯＨ／ｇの範囲にあり、このような量で水酸基が導入されることにより、ＰＢＩ樹脂の超耐熱性を損なうことなく、金属や各種樹脂に対する高い密着性を確保することができる。即ち、水酸基価が上記範囲よりも少ないと、密着性が損なわれ、また、水酸基価が上記範囲を超えて過度に高いと、ＯＨ変性の際にゲル化を伴うため、安定的に製造することが困難となり、塗膜形成時の作業性も悪くなる。
<OH-modified PBI resin>
The hydroxyl group-introduced OH-modified PBI resin has a hydroxyl value of 1.0 mgKOH / g or more, preferably 10 to 100 mgKOH / g, more preferably 20 to 90 mgKOH / g. By introducing a hydroxyl group, it is possible to ensure high adhesion to metals and various resins without impairing the super heat resistance of the PBI resin. That is, if the hydroxyl value is less than the above range, the adhesion is impaired, and if the hydroxyl value is excessively high beyond the above range, gelation occurs during OH modification, so that it can be stably produced. Becomes difficult, and workability at the time of forming the coating film also deteriorates.
上述した本発明のＯＨ変性ＰＢＩ樹脂は、溶液状態で得られるため、通常、そのままの形態で使用され、例えば金属や各種樹脂からなる成形品の表面にコーティングし、加熱乾燥して硬化皮膜を形成することにより、超耐熱性保護皮膜として、例えば電線被覆など、各種の用途に適用される。 Since the above-described OH-modified PBI resin of the present invention can be obtained in a solution state, it is usually used as it is. For example, it is coated on the surface of a molded product made of metal or various resins, and dried by heating to form a cured film. By doing so, the super heat resistant protective film is applied to various uses such as a wire coating.
＜樹脂組成物＞
また、本発明のＯＨ変性ＰＢＩ樹脂は、ＣＯＯＨ変性ＰＢＩ樹脂及びポリイソシアネート化合物と混合した樹脂組成物として、保護皮膜の形成等の用途に供することもできる。即ち、このＯＨ変性ＰＢＩ樹脂は、ＣＯＯＨ変性ＰＢＩ樹脂と相溶性が高く、ＣＯＯＨ変性ＰＢＩ樹脂との併用により、ＣＯＯＨ変性ＰＢＩのＣＯＯＨ基とＯＨ変性ＰＢＩのＯＨ基とが塗膜形成中に反応して硬化するため、３次元的な架橋構造が導入され、機械的強度が向上する。またＯＨ変性ＰＢＩ樹脂のＯＨ基とポリイソシアネート化合物とがウレタン結合し、ＰＢＩ樹脂中にウレタン結合による架橋構造を形成することができ、緻密で高硬度の皮膜（即ち、部分ウレタン化硬化樹脂）を形成することができるからである。
<Resin composition>
The OH-modified PBI resin of the present invention can also be used for applications such as the formation of a protective film as a resin composition mixed with a COOH-modified PBI resin and a polyisocyanate compound. That is, the OH-modified PBI resin is highly compatible with the COOH-modified PBI resin, and when used in combination with the COOH-modified PBI resin, the COOH group of the COOH-modified PBI reacts with the OH group of the OH-modified PBI during the coating film formation. Therefore, a three-dimensional cross-linked structure is introduced and the mechanical strength is improved. In addition, the OH group of the OH-modified PBI resin and the polyisocyanate compound are urethane-bonded to form a crosslinked structure due to the urethane bond in the PBI resin, thereby forming a dense and high-hardness film (that is, partially urethane-cured cured resin). It is because it can form.
かかる樹脂組成物において、用いるＣＯＯＨ変性ＰＢＩ樹脂としては、前述した範囲の酸価を有するものが、ＯＨ変性ＰＢＩ樹脂との相溶性の観点から特に好適であり、通常、ＯＨ変性ＰＢＩ樹脂１００重量部当り、１０乃至１０００重量部、特に３０乃至３００重量部の量で使用するのがよい。即ち、必要以上に多量のＣＯＯＨ変性ＰＢＩ樹脂を用いると、ＯＨ変性ＰＢＩ樹脂による密着性が損なわれるおそれがあり、またＣＯＯＨ変性ＰＢＩ樹脂の使用量があまり少ないと、架橋構造の形成による強度の向上等のメリットが希薄なものとなるからである。 In such a resin composition, as the COOH-modified PBI resin to be used, those having an acid value in the above-mentioned range are particularly suitable from the viewpoint of compatibility with the OH-modified PBI resin, and usually 100 parts by weight of the OH-modified PBI resin. It may be used in an amount of 10 to 1000 parts by weight, especially 30 to 300 parts by weight. That is, if a larger amount of COOH-modified PBI resin is used than necessary, the adhesion by the OH-modified PBI resin may be impaired, and if the amount of COOH-modified PBI resin used is too small, the strength is improved by forming a crosslinked structure. This is because the merits such as are sparse.
また、ポリイソシアネート化合物としては、これに限定されるものではないが、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’−ジフェニルメタンジイソシアネート、１，５−ナフタレンジイソシアネート、３，３’−ジメチル−４，４’−ジフェニルメタンジイソシアネート等の芳香族系ジイソシアネートや、１，６−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、１，３−ビス（イソシアネートメチル）シクロヘキサン、トリメチルヘキサメチレンジイソシアネート等の脂肪族系ジイソシアネートを例示することができる。特にＯＨ変性ＰＢＩ樹脂との相溶性や耐熱性の観点からは、芳香族系ジイソシアネートが好適である。 Moreover, as a polyisocyanate compound, although not limited to this, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4, Aromatic diisocyanates such as 4′-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, trimethylhexamethylene diisocyanate, etc. Aliphatic diisocyanates can be exemplified. In particular, aromatic diisocyanates are preferable from the viewpoint of compatibility with OH-modified PBI resins and heat resistance.
このようなポリイソシアネート化合物は、通常、ＯＨ変性ＰＢＩ樹脂１００重量部当り、０．１乃至２０重量部、特に１乃至１０重量部の量で使用するのがよい。即ち、必要以上に多量のイソシアネート架橋剤を用いても技術的メリットはなく、むしろ経済的に不利となり、またあまり少量の場合には、ウレタン架橋による硬化が不十分で、塗膜性能の向上があまり見込めないおそれがある。 Such a polyisocyanate compound is usually used in an amount of 0.1 to 20 parts by weight, particularly 1 to 10 parts by weight, per 100 parts by weight of the OH-modified PBI resin. That is, there is no technical advantage even if an excessive amount of isocyanate cross-linking agent is used, rather it is economically disadvantageous, and when it is too small, curing by urethane cross-linking is insufficient and the coating film performance is improved. There is a possibility that it cannot be expected.
上記のＣＯＯＨ変性ＰＢＩ樹脂及びイソシアネート架橋剤をＯＨ変性ＰＢＩ樹脂と混合するには、前述したＰＢＩ樹脂用の溶媒を用いて行うのがよい。また、かかる樹脂組成物には、ＯＨ変性ＰＢＩ樹脂の特性を損なわない範囲の量で、それ自体公知の各種添加剤、例えば染料、顔料等の着色剤、帯電防止剤、充填材、可塑剤、分散剤などを適宜配合することが可能である。 In order to mix the COOH-modified PBI resin and the isocyanate cross-linking agent with the OH-modified PBI resin, the above-described solvent for the PBI resin is preferably used. In addition, the resin composition includes various additives known per se, for example, colorants such as dyes and pigments, antistatic agents, fillers, plasticizers, in amounts that do not impair the properties of the OH-modified PBI resin. A dispersant or the like can be appropriately blended.
以下の実施例及び比較例において用いた原料ＰＢＩ樹脂、ＯＨ変性剤の種類、及び試料の評価は、以下の通りである。 The raw material PBI resin, the kind of OH modifier, and the evaluation of the sample used in the following examples and comparative examples are as follows.
原料ＰＢＩ樹脂（未変性ＰＢＩ樹脂）：
下記式：
Following formula:
ＯＨ変性剤：
（ａ）１，４−ブタンジオール
（ｂ）エチレングリコール
（ｃ）２，３−エポキシ−１−プロパノール
（ｄ）２，２，３，３−テトラフルオロ−１，４−ブタンジオール
OH modifier:
(A) 1,4-butanediol (b) ethylene glycol (c) 2,3-epoxy-1-propanol (d) 2,2,3,3-tetrafluoro-1,4-butanediol
密着性：
碁盤目試験法（JIS K 5400）により評価した。
即ち、アルミニウム板上に、乾燥後の塗膜の厚さが１０μｍとなるように試料を塗布し、１５０℃×１分の乾燥を行った後、２５０℃×１時間熱処理を行って塗膜を形成した。塗膜に幅１ｍｍの傷を碁盤目状（１００マス）に作り、次いで、この塗膜にセロハンテープを貼着し、密着させたのち、セロハンテープを剥がし、剥がれなかった碁盤目の個数により、次の基準で密着性を評価した。
◎：１００／１００
○：９０〜９９／１００
△：８０〜８９／１００
×：０〜７９／１００
Adhesion:
It was evaluated by a cross cut test method (JIS K 5400).
That is, a sample was applied on an aluminum plate so that the thickness of the coating film after drying was 10 μm, dried at 150 ° C. for 1 minute, and then heat treated at 250 ° C. for 1 hour to form the coating film. Formed. Make a scratch with a width of 1 mm on the coating film in a grid pattern (100 squares), and then paste the cellophane tape on this coating film and make it adhere, then peel off the cellophane tape, depending on the number of grids that did not peel off, Adhesion was evaluated according to the following criteria.
A: 100/100
○: 90 to 99/100
Δ: 80-89 / 100
X: 0 to 79/100
耐熱性：
アルミニウム板上に、乾燥後の塗膜の厚さが１０μｍになるように試料を塗布し、１５０℃×１分の乾燥を行った後、２５０℃×１時間熱処理を行って塗膜を形成した。形成した塗膜を５００℃で１時間加熱し、加熱前後の塗膜の重量変化により、耐熱性を評価した。評価基準は次の通りである。
○：重量変化１０％以内
×：重量変化が１０％より大
Heat-resistant:
A sample was applied on an aluminum plate so that the thickness of the dried coating film was 10 μm, dried at 150 ° C. for 1 minute, and then heat treated at 250 ° C. for 1 hour to form a coating film. . The formed coating film was heated at 500 ° C. for 1 hour, and the heat resistance was evaluated by the weight change of the coating film before and after heating. The evaluation criteria are as follows.
○: Change in weight within 10% ×: Change in weight greater than 10%
ＣＯＯＨ変性ＰＢＩ樹脂の製造例１：
攪拌装置、窒素ガス導入管、温度計及び還流冷却管を備えたフラスコに、
前記ＰＢＩ樹脂溶液；１０００重量部（ＰＢＩ樹脂：１００重量部）
無水マレイン酸（ＣＯＯＨ変性剤）；５重量部
を仕込み、フラスコ内に窒素ガスを導入しながら３０分攪拌して窒素置換を行った。その後、フラスコの内容物を９５℃まで昇温し、そのまま９５℃に維持しながら３時間反応させた。反応後、室温まで冷却し、ＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）の溶液を得た。
得られたＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）は、数平均分子量が８万（ＰＢＩ繰り返し単位数ｎ＝２６０）で、酸価が２７ｍｇＫＯＨ／ｇであった。
Production Example 1 of COOH-modified PBI resin 1:
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser,
1000 parts by weight of the PBI resin solution (PBI resin: 100 parts by weight)
Maleic anhydride (COOH modifier); 5 parts by weight were charged, and nitrogen substitution was performed by stirring for 30 minutes while introducing nitrogen gas into the flask. Thereafter, the contents of the flask were heated to 95 ° C. and reacted for 3 hours while maintaining the temperature at 95 ° C. as it was. After the reaction, it was cooled to room temperature to obtain a solution of COOH-modified PBI resin (E).
The obtained COOH-modified PBI resin (E) had a number average molecular weight of 80,000 (PBI repeating unit number n = 260) and an acid value of 27 mgKOH / g.
ＣＯＯＨ変性ＰＢＩ樹脂の製造例２：
無水マレイン酸の量を０．１重量部に変えた以外は製造例１と全く同様にしてＣＯＯＨ変性ＰＢＩ樹脂（Ｈ）の溶液を得た。
得られたＣＯＯＨ変性ＰＢＩ樹脂（Ｈ）は、数平均分子量が８万（ＰＢＩ繰り返し単位数ｎ＝２６０）で、酸価が０．５ｍｇＫＯＨ／ｇであった。
Production Example 2 of COOH-modified PBI resin:
A COOH-modified PBI resin (H) solution was obtained in exactly the same manner as in Production Example 1, except that the amount of maleic anhydride was changed to 0.1 parts by weight.
The obtained COOH-modified PBI resin (H) had a number average molecular weight of 80,000 (number of PBI repeating units n = 260) and an acid value of 0.5 mgKOH / g.
（実施例１）
上記の製造例１で得られたＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）が入れられたフラスコに、
ＯＨ変性剤（ａ）［１，４−ブタンジオール］ ５重量部
を入れ、フラスコ内の窒素ガスを導入しながら３０分攪拌して窒素置換を行った。
次いで、フラスコ内の内容物を９５℃まで昇温し、そのまま９５℃に維持しながら３時間反応させた。反応後、室温まで冷却し、ＯＨ変性ＰＢＩ樹脂（Ｅ１）の溶液を得た。
得られたＯＨ変性樹脂の水酸基価は２９ｍｇＫＯＨ／ｇであった。
また、このＯＨ変性樹脂（Ｅ１）の溶液を用いて、前述した方法にしたがって密着性及び耐熱性の評価を行い、その結果を表１に示した。
Example 1
In a flask containing the COOH-modified PBI resin (E) obtained in Production Example 1 above,
5 parts by weight of OH modifier (a) [1,4-butanediol] was added, and nitrogen substitution was performed by stirring for 30 minutes while introducing nitrogen gas in the flask.
Next, the contents in the flask were heated to 95 ° C. and reacted for 3 hours while maintaining the temperature at 95 ° C. as it was. After the reaction, it was cooled to room temperature to obtain a solution of OH-modified PBI resin (E1).
The hydroxyl value of the obtained OH-modified resin was 29 mgKOH / g.
Further, using this OH-modified resin (E1) solution, the adhesion and heat resistance were evaluated according to the methods described above, and the results are shown in Table 1.
（実施例２）
ＯＨ変性剤（ａ）の代わりにＯＨ変性剤（ｂ）［エチレングリコール］を用いた以外は、実施例１と全く同様にしてＯＨ変性ＰＢＩ樹脂（Ｅ２）の溶液を得た。
得られたＯＨ変性樹脂（Ｅ２）について、実施例１と同様にして水酸基価、密着性及び耐熱性を測定し、その結果を表１に示した。
(Example 2)
A solution of OH-modified PBI resin (E2) was obtained in the same manner as in Example 1 except that OH-modified agent (b) [ethylene glycol] was used instead of OH-modified agent (a).
For the obtained OH-modified resin (E2), the hydroxyl value, adhesion and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.
（実施例３）
ＯＨ変性剤（ａ）の代わりにＯＨ変性剤（ｃ）［２，３−エポキシ−１−プロパノール］を用いた以外は、実施例１と全く同様にしてＯＨ変性ＰＢＩ樹脂（Ｅ３）の溶液を得た。
得られたＯＨ変性樹脂（Ｅ３）について、実施例１と同様にして水酸基価、密着性及び耐熱性を測定し、その結果を表１に示した。
(Example 3)
A solution of OH-modified PBI resin (E3) was prepared in exactly the same manner as in Example 1 except that OH-modified agent (c) [2,3-epoxy-1-propanol] was used instead of OH-modified agent (a). Obtained.
For the obtained OH-modified resin (E3), the hydroxyl value, adhesion, and heat resistance were measured in the same manner as in Example 1, and the results are shown in Table 1.
（比較例１）
ＯＨ変性剤（ａ）の使用量を０．１重量部に代えた以外は実施例１と全く同様にしてＯＨ変性ＰＢＩ樹脂（Ｈ１）の溶液を得た。
得られたＯＨ変性樹脂（Ｈ１）について、実施例１と同様にして水酸基価、密着性及び耐熱性を測定し、その結果を表１に示した。
(Comparative Example 1)
A solution of OH-modified PBI resin (H1) was obtained in exactly the same manner as in Example 1 except that the amount of OH-modifying agent (a) used was changed to 0.1 parts by weight.
The obtained OH-modified resin (H1) was measured for hydroxyl value, adhesion and heat resistance in the same manner as in Example 1, and the results are shown in Table 1.
（比較例２）
ＯＨ変性剤（ｃ）の使用量を０．１重量部に変更した以外は実施例１と全く同様にしてＯＨ変性ＰＢＩ樹脂（Ｈ２）の溶液を得た。
得られたＯＨ変性樹脂（Ｈ２）について、実施例１と同様にして水酸基価、密着性及び耐熱性を測定し、その結果を表１に示した。
(Comparative Example 2)
A solution of OH-modified PBI resin (H2) was obtained in exactly the same manner as in Example 1 except that the amount of OH-modifying agent (c) used was changed to 0.1 parts by weight.
The obtained OH-modified resin (H2) was measured for hydroxyl value, adhesion and heat resistance in the same manner as in Example 1, and the results are shown in Table 1.
（比較例３）
製造例１で得られたＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）の代わりに製造例２で得られたＣＯＯＨ変性ＰＢＩ樹脂（Ｈ）を用いた以外は、実施例１と全く同様にしてＯＨ変性ＰＢＩ樹脂（Ｈ３）の溶液を得た。
得られたＯＨ変性樹脂（Ｈ３）について、実施例１と同様にして水酸基価、密着性及び耐熱性を測定し、その結果を表１に示した。
(Comparative Example 3)
The OH-modified PBI resin (H) was obtained in the same manner as in Example 1 except that the COOH-modified PBI resin (H) obtained in Production Example 2 was used instead of the COOH-modified PBI resin (E) obtained in Production Example 1. A solution of H3) was obtained.
The obtained OH-modified resin (H3) was measured for hydroxyl value, adhesion and heat resistance in the same manner as in Example 1, and the results are shown in Table 1.
（比較例４）
製造例１で得られたＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）の代わりに製造例２で得られたＣＯＯＨ変性ＰＢＩ樹脂（Ｈ）を用いた以外は、実施例３と全く同様にしてＯＨ変性ＰＢＩ樹脂（Ｈ４）の溶液を得た。
得られたＯＨ変性樹脂（Ｈ４）について、実施例１と同様にして水酸基価、密着性及び耐熱性を測定し、その結果を表１に示した。
(Comparative Example 4)
An OH-modified PBI resin (in the same manner as in Example 3 except that the COOH-modified PBI resin (H) obtained in Production Example 2 was used instead of the COOH-modified PBI resin (E) obtained in Production Example 1. A solution of H4) was obtained.
The obtained OH-modified resin (H4) was measured for hydroxyl value, adhesion and heat resistance in the same manner as in Example 1, and the results are shown in Table 1.
（比較例５）
ＯＨ変性剤（ａ）の代わりにＯＨ変性剤（ｄ）［２，２，３，３−テトラフルオロ−１，４−ブタンジオール］を用いた以外は、実施例１と全く同様にしてＯＨ変性ＰＢＩ樹脂（Ｈ５）の溶液を得た。
得られたＯＨ変性樹脂（Ｈ５）について、実施例１と同様にして水酸基価、密着性及び耐熱性を測定し、その結果を表１に示した。
(Comparative Example 5)
OH modification was carried out in the same manner as in Example 1 except that OH modification agent (d) [2,2,3,3-tetrafluoro-1,4-butanediol] was used instead of OH modification agent (a). A solution of PBI resin (H5) was obtained.
The obtained OH-modified resin (H5) was measured for hydroxyl value, adhesion and heat resistance in the same manner as in Example 1, and the results are shown in Table 1.
（比較例６）
原料として用いた未変性のＰＢＩ樹脂の溶液を用いて、実施例１とまったく同様に密着性及び耐熱性を評価し、その結果を表１に示した。
(Comparative Example 6)
Using the unmodified PBI resin solution used as a raw material, adhesion and heat resistance were evaluated in exactly the same manner as in Example 1, and the results are shown in Table 1.
（応用例１）
実施例１で得られたＯＨ変性ＰＢＩ樹脂（Ｅ１）の溶液に、ＯＨ変性ＰＢＩ樹脂１００重量部当り、５重量部の量でポリイソシアネート化合物（トリレンジイソシアネート）を混合して樹脂組成物を調製した。この樹脂組成物について、実施例１と同様に密着性及び耐熱性を評価し、その結果を表２に示した。
(Application 1)
A resin composition was prepared by mixing a polyisocyanate compound (tolylene diisocyanate) in an amount of 5 parts by weight per 100 parts by weight of the OH-modified PBI resin (E1) obtained in Example 1. did. About this resin composition, adhesiveness and heat resistance were evaluated similarly to Example 1, and the result was shown in Table 2.
（応用例２）
実施例３で得られたＯＨ変性ＰＢＩ樹脂（Ｅ３）の溶液を用いた以外は、応用例１と全く同様にして樹脂組成物を調製し、その評価を行った。結果を表２に示す。
(Application example 2)
A resin composition was prepared and evaluated in exactly the same manner as in Application Example 1 except that the OH-modified PBI resin (E3) solution obtained in Example 3 was used. The results are shown in Table 2.
（応用例３）
実施例１で得られたＯＨ変性ＰＢＩ樹脂（Ｅ１）の溶液に、ＯＨ変性ＰＢＩ樹脂１００重量部当り、１００重量部の量で、製造例１で調製されたＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）を混合して樹脂組成物を調製した。この樹脂組成物について、応用例１と同様に密着性及び耐熱性を評価し、その結果を表２に示した。
(Application 3)
The COOH-modified PBI resin (E) prepared in Production Example 1 was mixed with the solution of the OH-modified PBI resin (E1) obtained in Example 1 in an amount of 100 parts by weight per 100 parts by weight of the OH-modified PBI resin. Thus, a resin composition was prepared. The resin composition was evaluated for adhesion and heat resistance in the same manner as in Application Example 1, and the results are shown in Table 2.
（応用例４）
実施例３で得られたＯＨ変性ＰＢＩ樹脂（Ｅ３）の溶液を用いた以外は、応用例３と全く同様にして樹脂組成物を調製し、その評価を行った。結果を表２に示す。
(Application 4)
A resin composition was prepared and evaluated in exactly the same manner as in Application Example 3 except that the solution of OH-modified PBI resin (E3) obtained in Example 3 was used. The results are shown in Table 2.
（応用例５）
応用例３で調製された樹脂組成物に、さらに、ＯＨ変性ＰＢＩ樹脂（Ｅ１）１００重量部当り、５重量部の量でポリイソシアネート化合物（トリレンジイソシアネート）を混合して樹脂組成物を調製した。この樹脂組成物について密着性及び耐熱性を評価し、その結果を表２に示した。
(Application example 5)
A resin composition was prepared by further mixing a polyisocyanate compound (tolylene diisocyanate) in an amount of 5 parts by weight per 100 parts by weight of the OH-modified PBI resin (E1) with the resin composition prepared in Application Example 3. . The resin composition was evaluated for adhesion and heat resistance, and the results are shown in Table 2.
（応用例６）
応用例４で調製された樹脂組成物に、さらに、ＯＨ変性ＰＢＩ樹脂（Ｅ３）１００重量部当り、５重量部の量でポリイソシアネート化合物（トリレンジイソシアネート）を混合して樹脂組成物を調製した。この樹脂組成物について密着性及び耐熱性を評価し、その結果を表２に示した。
(Application example 6)
The resin composition prepared in Application Example 4 was further mixed with a polyisocyanate compound (tolylene diisocyanate) in an amount of 5 parts by weight per 100 parts by weight of the OH-modified PBI resin (E3) to prepare a resin composition. . The resin composition was evaluated for adhesion and heat resistance, and the results are shown in Table 2.
（応用例７）
比較例１で調整されたＯＨ変性ＰＢＩ樹脂（Ｈ１）の溶液を用いた以外は、応用例１と全く同様にして樹脂組成物を調製し、密着性及び耐熱性の評価を行った。その結果を表２に示す。
(Application example 7)
A resin composition was prepared in exactly the same manner as in Application Example 1 except that the OH-modified PBI resin (H1) solution prepared in Comparative Example 1 was used, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.
（応用例８）
比較例１で調整されたＯＨ変性ＰＢＩ樹脂（Ｈ１）の溶液を用いた以外は、応用例３と全く同様にして樹脂組成物を調製し、密着性及び耐熱性の評価を行った。その結果を表２に示す。
(Application 8)
A resin composition was prepared in exactly the same manner as in Application Example 3 except that the solution of OH-modified PBI resin (H1) prepared in Comparative Example 1 was used, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.
（応用例９）
比較例１で調整されたＯＨ変性ＰＢＩ樹脂（Ｈ１）の溶液を用いた以外は、応用例５と全く同様にして樹脂組成物を調製し、密着性及び耐熱性の評価を行った。その結果を表２に示す。
(Application example 9)
A resin composition was prepared in exactly the same manner as in Application Example 5 except that the OH-modified PBI resin (H1) solution prepared in Comparative Example 1 was used, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.
（応用例１０）
ＯＨ変性ＰＢＩ樹脂を全く使用せず、製造例１で調製されたＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）の溶液と、該ＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）１００重量部当り５重量部のポリイソシアネート化合物（トリレンジイソシアネート）を混合して樹脂組成物を調製した。この樹脂組成物について密着性及び耐熱性を評価し、その結果を表２に示した。
(Application example 10)
Without using any OH-modified PBI resin, a solution of the COOH-modified PBI resin (E) prepared in Production Example 1 and 5 parts by weight of a polyisocyanate compound (tolylene diene) per 100 parts by weight of the COOH-modified PBI resin (E). Isocyanate) was mixed to prepare a resin composition. The resin composition was evaluated for adhesion and heat resistance, and the results are shown in Table 2.
（応用例１１）
ＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）の量を２５００重量部とした以外は、応用例３と全く同様にして樹脂組成物を調製し、密着性及び耐熱性を評価した。その結果を表２に示す。
(Application Example 11)
A resin composition was prepared in exactly the same manner as in Application Example 3 except that the amount of the COOH-modified PBI resin (E) was 2500 parts by weight, and the adhesion and heat resistance were evaluated. The results are shown in Table 2.
（応用例１２）
ＣＯＯＨ変性ＰＢＩ樹脂（Ｅ）の量を５０００重量部とした以外は、応用例３と全く同様にして樹脂組成物を調製し、密着性及び耐熱性を評価した。その結果を表２に示す。
(Application 12)
A resin composition was prepared in the same manner as in Application Example 3 except that the amount of the COOH-modified PBI resin (E) was 5000 parts by weight, and adhesion and heat resistance were evaluated. The results are shown in Table 2.
Claims (7)
Ｂは、２価のアリール基であり、
Ｒ１及びＲ２は、それぞれ水素原子である、
で表されるベンゾイミダゾール繰り返し単位の連鎖（但し、連鎖中、前記Ｒ１及びＲ２の一部はアルキル基で置換されていてもよい）からなるポリベンゾイミダゾール樹脂をＯＨ変性してなるＯＨ変性ポリベンゾイミダゾール樹脂であって、前記繰り返し単位におけるイミダゾール環中の窒素原子の少なくとも一部には、アミド結合を介して非ハロゲン系の水酸基含有変性基が結合しており、且つ１．０ｍｇＫＯＨ／ｇ以上の水酸基価を有していることを特徴とするＯＨ変性ポリベンゾイミダゾール樹脂。 Following formula (1):
B is a divalent aryl group,
R 1 and R 2 are each a hydrogen atom,
An OH-modified product obtained by OH-modifying a polybenzimidazole resin comprising a chain of benzimidazole repeating units represented by the formula (wherein, part of R 1 and R 2 may be substituted with an alkyl group). A polybenzimidazole resin, wherein a non-halogen-based hydroxyl group-containing modifying group is bonded to at least a part of nitrogen atoms in the imidazole ring in the repeating unit via an amide bond, and 1.0 mgKOH / g An OH-modified polybenzimidazole resin having the above hydroxyl value.
Ｂは、２価のアリール基である、
Ｒ１及びＲ２は、それぞれ水素原子である、
で表されるベンゾイミダゾール繰り返し単位の連鎖（但し、連鎖中、前記Ｒ１及びＲ２の一部はアルキル基で置換されていてもよい）からなる未変性ポリベンゾイミダゾール樹脂を、多価カルボン酸と反応させることにより、前記繰り返し単位におけるイミダゾール環中の窒素原子の少なくとも一部に、アミド結合を介して多価カルボン酸由来の変性基を導入してＣＯＯＨ変性ポリベンゾイミダゾール樹脂を調製し、
次いで、１級アルコール由来のＯＨ基を少なくとも２個有する非ハロゲン系多価アルコール化合物または１級アルコール由来のＯＨ基と末端エポキシ基とを有する非ハロゲン系アルコール性エポキシ化合物を変性剤として使用し、該変性剤を前記ポリベンゾイミダゾール樹脂と混合して加熱することにより、該変性剤を前記ＣＯＯＨ変性ポリベンゾイミダゾールに導入されている変性基中のカルボキシル基と反応させて、前記多価アルコール化合物またはアルコール性エポキシ化合物に由来するＯＨ含有基を前記変性基に導入することを特徴とするＯＨ変性ポリベンゾイミダゾール樹脂の製造方法。 Following formula (1):
B is a divalent aryl group.
R 1 and R 2 are each a hydrogen atom,
An unmodified polybenzimidazole resin comprising a chain of benzimidazole repeating units represented by the formula (wherein, part of R 1 and R 2 may be substituted with an alkyl group). And a COOH-modified polybenzimidazole resin is prepared by introducing a modifying group derived from a polyvalent carboxylic acid via an amide bond into at least a part of the nitrogen atom in the imidazole ring in the repeating unit.
Next, a non-halogen polyhydric alcohol compound having at least two OH groups derived from a primary alcohol or a non-halogen alcohol-based epoxy compound having an OH group and a terminal epoxy group derived from a primary alcohol is used as a modifier. By mixing and heating the modifier with the polybenzimidazole resin, the modifier is reacted with a carboxyl group in the modifier group introduced into the COOH-modified polybenzimidazole, and the polyhydric alcohol compound or A method for producing an OH-modified polybenzimidazole resin, wherein an OH-containing group derived from an alcoholic epoxy compound is introduced into the modifying group.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100983761B1 (en) | 2008-05-23 | 2010-09-24 | 엘에스전선 주식회사 | Highly heat-resistant electrical wire |
| CN102910840A (en) * | 2012-10-31 | 2013-02-06 | 东华大学 | High-temperature resistant benzimidazole optical fiber coating and preparation method of coating |
| CN117106405A (en) * | 2023-08-07 | 2023-11-24 | 广东多柏斯化工新材料有限公司 | High Tg value and light-resistant aqueous polyurethane adhesive and preparation method and application thereof |
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| JPH08253732A (en) * | 1994-12-22 | 1996-10-01 | Hoechst Japan Ltd | Polymer-coated metal part and its production |
| JP2007522615A (en) * | 2004-02-04 | 2007-08-09 | ザトーリウス アクチエン ゲゼルシャフト | Membrane for a fuel cell, method for producing the membrane, and production of a fuel cell using this type of membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03134048A (en) * | 1989-10-12 | 1991-06-07 | Hoechst Ag | Alloy with one glass transition temperatuer |
| JPH08253732A (en) * | 1994-12-22 | 1996-10-01 | Hoechst Japan Ltd | Polymer-coated metal part and its production |
| JP2007522615A (en) * | 2004-02-04 | 2007-08-09 | ザトーリウス アクチエン ゲゼルシャフト | Membrane for a fuel cell, method for producing the membrane, and production of a fuel cell using this type of membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100983761B1 (en) | 2008-05-23 | 2010-09-24 | 엘에스전선 주식회사 | Highly heat-resistant electrical wire |
| CN102910840A (en) * | 2012-10-31 | 2013-02-06 | 东华大学 | High-temperature resistant benzimidazole optical fiber coating and preparation method of coating |
| CN102910840B (en) * | 2012-10-31 | 2015-01-07 | 东华大学 | High-temperature resistant benzimidazole optical fiber coating and preparation method of coating |
| CN117106405A (en) * | 2023-08-07 | 2023-11-24 | 广东多柏斯化工新材料有限公司 | High Tg value and light-resistant aqueous polyurethane adhesive and preparation method and application thereof |
| CN117106405B (en) * | 2023-08-07 | 2024-03-19 | 广东多柏斯化工新材料有限公司 | High Tg value and light-resistant aqueous polyurethane adhesive and preparation method and application thereof |
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