JP2014031420A - Synthesizing method for polyamide-imide resin, polyamide-imide resin, and polyamide-imide resin composition - Google Patents
Synthesizing method for polyamide-imide resin, polyamide-imide resin, and polyamide-imide resin composition Download PDFInfo
- Publication number
- JP2014031420A JP2014031420A JP2012172122A JP2012172122A JP2014031420A JP 2014031420 A JP2014031420 A JP 2014031420A JP 2012172122 A JP2012172122 A JP 2012172122A JP 2012172122 A JP2012172122 A JP 2012172122A JP 2014031420 A JP2014031420 A JP 2014031420A
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- JP
- Japan
- Prior art keywords
- polyamideimide resin
- polyamide
- solvent
- synthesizing
- imide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 128
- 239000011347 resin Substances 0.000 title claims abstract description 128
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 121
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 22
- 239000011342 resin composition Substances 0.000 title claims description 10
- 239000002904 solvent Substances 0.000 claims abstract description 53
- -1 diisocyanate compound Chemical class 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 23
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000002966 varnish Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 230000001627 detrimental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 15
- 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 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- 150000001408 amides Chemical class 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 12
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920000515 polycarbonate Polymers 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000002253 acid Substances 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 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 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene 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
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 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
- 239000000049 pigment Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-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 compound 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
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
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- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-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
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明はポリアミドイミド樹脂の合成方法、および得られたポリアミドイミド樹脂、ならびにこのポリアミドイミド樹脂を用いたワニスとポリアミドイミド樹脂組成物とに関する。 The present invention relates to a method for synthesizing a polyamide-imide resin, the obtained polyamide-imide resin, and a varnish and a polyamide-imide resin composition using the polyamide-imide resin.
ポリアミドイミド樹脂は、高絶縁性、高耐熱性、高強度性、高耐摩耗性、高耐溶剤性等の優れた特性を多数有しているため、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、防錆塗料、基材保護膜等として使用されている。
ポリアミドイミド樹脂の一般的な製造法については公知（例えば、特許文献１参照）であり、従来のポリアミドイミド樹脂は、ジフェニルメタンジイソシアネートと無水トリメリット酸を材料に使用し、大量のポリアミドイミド樹脂を連続的かつ安価に製造できるという工業的に優れたイソシアネート法により製造されている。
このように、耐熱性、耐薬品性及び耐溶剤性に優れたポリアミドイミド樹脂の合成には、Ｎ−メチルピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド等のアミド系溶媒が用いられている。アミド系溶媒はポリアミドイミド樹脂を非常に良く溶解し、高沸点、低凝固点であることから非常に取り扱い易い溶媒である（例えば、特許文献２参照）。
しかし、上記アミド系溶媒は、ヨーロッパ圏において、生殖毒性があるとの報告があり、ヨーロッパを中心に塗布膜、構造物中の残存溶媒の取り扱いを含めアミド系溶媒の取り扱いに注意する必要がある（例えば、非特許文献１参照）。特に、ヨーロッパでは、アミド系溶媒を使用しない動きがある。
このようなアミド系溶媒に関する課題を解決するために、アミド系溶媒に代わる溶媒が種々検討されているが、耐熱性、耐薬品性及び耐溶剤性に優れた高分子量のポリアミドイミド樹脂を合成することができない状況である。
Polyamideimide resin has many excellent properties such as high insulation, high heat resistance, high strength, high wear resistance, and high solvent resistance, so it is widely used as a coating agent for various substrates. For example, it is used as a varnish for enameled wire, a heat resistant paint, a rust preventive paint, a substrate protective film and the like.
A general method for producing a polyamide-imide resin is known (see, for example, Patent Document 1). A conventional polyamide-imide resin uses diphenylmethane diisocyanate and trimellitic anhydride as materials, and a large amount of polyamide-imide resin is continuously used. It is manufactured by an industrially superior isocyanate method that can be manufactured inexpensively and inexpensively.
Thus, for the synthesis of a polyamideimide resin excellent in heat resistance, chemical resistance and solvent resistance, amides such as N-methylpyrrolidone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide, etc. A solvent is used. Amide solvents are very easy to handle because they dissolve polyamideimide resins very well and have high boiling points and low freezing points (see, for example, Patent Document 2).
However, it has been reported that the above amide solvents have reproductive toxicity in Europe, and it is necessary to pay attention to the handling of amide solvents including the handling of residual solvents in coating films and structures, mainly in Europe. (For example, refer nonpatent literature 1). Particularly in Europe, there is a movement not to use amide solvents.
In order to solve such problems related to amide solvents, various alternatives to amide solvents have been studied, and high molecular weight polyamideimide resins with excellent heat resistance, chemical resistance and solvent resistance are synthesized. It is a situation that cannot be done.
耐熱性、耐薬品性及び耐溶剤性に優れたポリアミドイミド樹脂の合成には、環境、人体への配慮からＮ−メチルピロリドン（ＮＭＰ）等アミド系溶媒を用いないことが求められている。
本発明は、上述した問題を解決するためになされたものであって、環境、人体へ悪影響を与え難い溶媒を用い、耐熱性、耐薬品性及び耐溶剤性に優れたポリアミドイミド樹脂を提供することを目的としている。
In order to synthesize a polyamide-imide resin excellent in heat resistance, chemical resistance and solvent resistance, it is required not to use an amide solvent such as N-methylpyrrolidone (NMP) in consideration of the environment and the human body.
The present invention has been made to solve the above-described problems, and provides a polyamide-imide resin excellent in heat resistance, chemical resistance and solvent resistance using a solvent that does not adversely affect the environment and the human body. The purpose is that.
本発明は、以下に関する。
１．尿素結合を有する溶媒中で、（１）ジイソシアネート化合物と、（２−ａ）酸無水物基を有する３価のカルボン酸誘導体とを重合させて得られるポリアミドイミド樹脂の合成方法。
２．前記（１）成分及び（２−ａ）成分に、さらに（２−ｂ）ジカルボン酸化合物又はジオール化合物の少なくとも１以上を重合成分として加える項１記載のポリアミドイミド樹脂の合成方法。
３．前記（１）成分及び（２−ａ）成分に、さらに（２−ｃ）酸無水物基を２個有する４価のカルボン酸誘導体を重合成分として加える項１又は２記載のポリアミドイミド樹脂の合成方法。
４．前記溶媒が、下記化学式（Ａ）で示す構造のものである項１乃至３の何れか一項記載のポリアミドイミド樹脂の合成方法。
５．前記化学式（Ａ）において、Ｒ1が炭素数１から３の飽和炭化水素基であり、ｎが２から５である項４記載のポリアミドイミド樹脂の合成方法。
６．前記（２−ａ）酸無水物基を有する３価のカルボン酸誘導体が、化学式（Ｂ）で示される化合物のうちの何れか１種以上である項１乃至５の何れか一項記載のポリアミドイミド樹脂の合成方法。
７．前記（１）成分が、化学式（Ｃ）で示される化合物のうちの何れか１種以上である項１乃至６の何れか一項記載のポリアミドイミド樹脂の合成方法。
８．項１乃至７の何れか一項記載のポリアミドイミド樹脂の合成方法によって得られるポリアミドイミド樹脂。
９．前記ポリアミドイミド樹脂の数平均分子量が１０，０００〜７５，０００である項８記載のポリアミドイミド樹脂。
１０．項１乃至７の何れか一項記載のポリアミドイミド樹脂の合成方法によって得られるポリアミドイミド樹脂を尿素結合を有する溶媒に溶解したワニス。
１１．前記溶媒が上記化学式（Ａ）で示す構造のものである項１０記載のワニス。
１２．前記化学式（Ａ）においてＲ1が炭素数１から３の飽和炭化水素基であり、ｎが２から５である項１１記載のワニス。
１３．項１乃至７の何れか一項記載のポリアミドイミド樹脂の合成方法によって得られるポリアミドイミド樹脂１００質量部に対して、１種類以上の硬化剤を１〜１００質量部含有するポリアミドイミド樹脂組成物。
１４．前記硬化剤が多官能型エポキシ化合物である項１３記載のポリアミドイミド樹脂組成物。
The present invention relates to the following.
1. A method for synthesizing a polyamideimide resin obtained by polymerizing (1) a diisocyanate compound and (2-a) a trivalent carboxylic acid derivative having an acid anhydride group in a solvent having a urea bond.
2. The method for synthesizing a polyamide-imide resin according to Item 1, wherein at least one of (2-b) dicarboxylic acid compound or diol compound is further added as a polymerization component to the component (1) and the component (2-a).
3. The synthesis | combination of the polyamidoimide resin of claim | item 1 or 2 which adds the tetravalent carboxylic acid derivative which has two (2-c) acid anhydride groups to the said (1) component and (2-a) component as a polymerization component further. Method.
4). Item 4. The method for synthesizing a polyamideimide resin according to any one of Items 1 to 3, wherein the solvent has a structure represented by the following chemical formula (A).
5. Item 5. The method for synthesizing a polyamideimide resin according to Item 4, wherein, in the chemical formula (A), R 1 is a saturated hydrocarbon group having 1 to 3 carbon atoms, and n is 2 to 5.
6). The polyamide according to any one of Items 1 to 5, wherein the (2-a) trivalent carboxylic acid derivative having an acid anhydride group is any one or more of the compounds represented by the chemical formula (B). Synthesis method of imide resin.
7). Item 7. The method for synthesizing a polyamideimide resin according to any one of Items 1 to 6, wherein the component (1) is any one or more of the compounds represented by the chemical formula (C).
8). Item 8. A polyamideimide resin obtained by the method for synthesizing a polyamideimide resin according to any one of Items 1 to 7.
9. Item 9. The polyamideimide resin according to item 8, wherein the polyamideimide resin has a number average molecular weight of 10,000 to 75,000.
10. Item 8. A varnish obtained by dissolving a polyamideimide resin obtained by the method for synthesizing a polyamideimide resin according to any one of items 1 to 7 in a solvent having a urea bond.
11. Item 11. The varnish according to Item 10, wherein the solvent has a structure represented by the chemical formula (A).
12 Item 12. The varnish according to Item 11, wherein in the chemical formula (A), R 1 is a saturated hydrocarbon group having 1 to 3 carbon atoms, and n is 2 to 5.
13. The polyamide-imide resin composition containing 1-100 mass parts of 1 or more types of hardening | curing agents with respect to 100 mass parts of polyamide-imide resins obtained by the synthesis method of the polyamide-imide resin as described in any one of claim | item 1 thru | or 7.
14 Item 14. The polyamideimide resin composition according to item 13, wherein the curing agent is a polyfunctional epoxy compound.
本発明によれば、環境、人体へ悪影響が少ない溶媒を使用し、耐熱性、耐薬品性及び耐溶剤性に優れたポリアミドイミド樹脂及びポリアミド樹脂組成物を提供することが可能となった。 ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the polyamideimide resin and the polyamide resin composition which were excellent in heat resistance, chemical resistance, and solvent resistance using the solvent with few bad influences on an environment and a human body.
本発明のポリアミドイミド樹脂の合成方法は、尿素結合を有する溶媒中で、ジイソシアネート化合物と酸無水物機を有する３価のカルボン酸誘導体などとを重合させるものである。
本発明で用いる尿素結合を有する溶媒としては、分子中に尿素結合を有するものであればよいが、これらのなかでも化学式（Ａ）で示されるものが好ましく、このようなものとしては、例えば、
As the solvent having a urea bond used in the present invention, any solvent having a urea bond in the molecule may be used, and among these, those represented by the chemical formula (A) are preferable.
本発明で用いる（２−ａ）酸無水物基を有する３価のカルボン酸誘導体としては、例えば一般式（Ｉ）及び（II）で示す化合物を使用することができ、イソシアネートまたはアミノ基と反応する酸無水物基を有する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 the trivalent carboxylic acid derivative having an (2-a) acid anhydride group used in the present invention, for example, compounds represented by the general formulas (I) and (II) can be used and reacted with an isocyanate or amino group. There is no particular limitation as long as it is a derivative of a trivalent carboxylic acid having an acid anhydride 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.
本発明で用いる（２−ｂ）成分のジカルボン酸としては、例えば、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、オキシジ安息香酸等の芳香族ジカルボン酸、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、シクロヘキサンジカルボン酸等の脂肪族ジカルボン酸を使用することができる。機械的特性のバランスの観点からアジピン酸が特に好ましい。これらのジカルボン酸は、目的に応じて単独又は混合して用いられる。 Examples of the dicarboxylic acid of component (2-b) used in the present invention include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and oxydibenzoic acid, succinic acid, glutaric acid, adipic acid, Aliphatic dicarboxylic acids such as azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, and cyclohexanedicarboxylic acid can be used. Adipic acid is particularly preferable from the viewpoint of balance of mechanical properties. These dicarboxylic acids are used alone or in combination depending on the purpose.
本発明で用いる（２−ｂ）成分のジオール化合物としては、例えば、レゾルシノール、ヒドロキノン、ビフェニルジオール、ビスフェノールＡ、ナフタレンジオール、芳香族ポリカーボネートジオール、芳香族ポリカーボネートジオール−クロロギ酸二エステル等の芳香族ポリカーボネートジオールの誘導体など芳香族ジオール化合物、エチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、脂肪族ポリカーボネートジオール、脂肪族ポリカーボネートジオール−クロロギ酸二エステル等の脂肪族ポリカーボネートジオールの誘導体など脂肪族ジオール化合物が挙げられる。これらのジオール化合物は、目的に応じて単独又は混合して用いられる。 Examples of the diol compound (2-b) used in the present invention include aromatic polycarbonates such as resorcinol, hydroquinone, biphenyl diol, bisphenol A, naphthalene diol, aromatic polycarbonate diol, and aromatic polycarbonate diol-chloroformate diester. Aromatic diol compounds such as diol derivatives, aliphatic glycol diol derivatives such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, aliphatic polycarbonate diol, aliphatic polycarbonate diol-chloroformate diester Group diol compounds. These diol compounds are used alone or in combination depending on the purpose.
脂肪族ポリカーボネートジオール又はそれらの誘導体よりなる群から選ばれた少なくとも１種類以上のモノマを共重合させることがより好ましい。 More preferably, at least one monomer selected from the group consisting of aliphatic polycarbonate diols or derivatives thereof is copolymerized.
脂肪族ポリカーボネートジオール又はその誘導体の量が脂肪族ポリカーボネートジオールを含まないポリアミドイミド樹脂に対して、脂肪族ポリカーボネートジオールが１モル％から５０モル％であると、従来のポリアミドイミド樹脂と比較して加工性及び密着性が向上するとともに、耐溶剤性にも優れるものが得られることから好ましいものとなる。
加工性及び密着性を向上させ、かつ耐溶剤性を保持するためには、脂肪族ポリカーボネートジオール又はその誘導体の量を５〜３０モル％とすることがより好ましい。
When the amount of the aliphatic polycarbonate diol or its derivative is 1 mol% to 50 mol% with respect to the polyamide imide resin containing no aliphatic polycarbonate diol, it is processed as compared with the conventional polyamide imide resin. In addition to improving the properties and adhesiveness, it is preferable because a solvent having excellent solvent resistance can be obtained.
In order to improve workability and adhesion and to maintain solvent resistance, the amount of aliphatic polycarbonate diol or a derivative thereof is more preferably 5 to 30 mol%.
本発明になるポリアミドイミド樹脂を重合するために使用しうる脂肪族ポリカーボネートジオール類としては、例えば、ダイセル化学（株）製、商品名ＰＬＡＣＣＥＬ ＣＤ−２０５、２０５ＰＬ、２０５ＨＬ、２１０、２１０ＰＬ、２１０ＨＬ、２２０、２２０ＰＬ、２２０ＨＬとして市販されているものが挙げられ、これらを単独又は２種類以上を組み合わせて使用することができる。 Examples of aliphatic polycarbonate diols that can be used for polymerizing the polyamideimide resin according to the present invention include, for example, trade names PLACEL CD-205, 205PL, 205HL, 210, 210PL, 210HL, and 220 manufactured by Daicel Chemical Industries, Ltd. , 220PL, and 220HL are listed, and these can be used alone or in combination of two or more.
本発明で用いる（２−ｃ）酸無水物基を２個有する４価のカルボン酸誘導体としては、例えば、ビフェニルテトラカルボン酸二無水物、無水ピロメリット酸、オキシジフタル酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ジフェニルスルホンテトラカルボン酸二無水物、（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物、ターフェニルテトラカルボン酸二無水物等が挙げられる。これらの化合物は、目的に応じて単独又は混合して用いられる。 Examples of the tetravalent carboxylic acid derivative having two (2-c) acid anhydride groups used in the present invention include biphenyltetracarboxylic dianhydride, pyromellitic anhydride, oxydiphthalic dianhydride, and benzophenonetetracarboxylic acid. Examples thereof include acid dianhydride, diphenylsulfone tetracarboxylic dianhydride, (hexafluoroisopropylidene) diphthalic dianhydride, terphenyl tetracarboxylic dianhydride and the like. These compounds are used alone or in combination depending on the purpose.
また、上記の化合物以外にも、必要に応じ、ヒドロキシナフトエ酸、オキシナフトエ酸、ヒドロキシビフェニルカルボン酸、１，２−アミノドデカン酸、トリメチロールエタン、トリメチロールプロパン、グルコン酸、乳酸、フマル酸、ＤＬ−リンゴ酸、キシリトール、Ｄ−ソルビトール、ＤＬ−アラニン等を用いてもよい。 In addition to the above compounds, hydroxynaphthoic acid, oxynaphthoic acid, hydroxybiphenylcarboxylic acid, 1,2-aminododecanoic acid, trimethylolethane, trimethylolpropane, gluconic acid, lactic acid, fumaric acid, DL-malic acid, xylitol, D-sorbitol, DL-alanine and the like may be used.
本発明で用いる（１）ジイソシアネート化合物としては、４，４′−ジフェニルメタ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、キシリレンジイソシアネート、３，３’−ジメチルビフェニル−４，４’−ジイソシアネート、３，３′−ジフェニルメタンジイソシアネート、３，３′−ジメトキシビフェニル−４，４′−ジイソシアネート、パラフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート、トリレンジイソシアレート等が挙げられる。機械的特性の引張り強度と弾性率の観点から芳香族系を使用することが好ましく、このようなものとしては、例えば前記化学式（Ｃ）で示した各化合物があげられ、これらのうちでもコストを考慮すると４，４′−ジフェニルメタンジイソシアネートとトリレンジイソシアネートが特に好ましい。これらのジイソシアネート化合物は、目的に応じて単独又は混合して用いられる。 (1) Diisocyanate compounds used in the present invention include 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3. Examples include '-diphenylmethane diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, paraphenylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and tolylene diisocyanate. From the viewpoint of tensile strength and elastic modulus of mechanical properties, it is preferable to use an aromatic system. Examples of such compounds include the compounds represented by the chemical formula (C). Considering 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate are particularly preferred. These diisocyanate compounds are used alone or in combination depending on the purpose.
前記（１）ジイソシアネート化合物からなる成分と、（２−ａ）酸無水物基を有する３価のカルボン酸誘導体と、必要により加える（２−ｂ）ジカルボン酸化合物又はジオール化合物、及び（２−ｃ）酸無水物基を２個有する４価のカルボン酸誘導体からなる群から選ばれる成分の合計との使用量は、生成されるポリアミドイミド樹脂の分子量、架橋度の観点から、（２）成分である（２−ａ）酸無水物基を有する３価のカルボン酸誘導体と、（２−ｂ）ジカルボン酸化合物又はジオール化合物、及び（２−ｃ）酸無水物基を２個有する４価のカルボン酸誘導体からなる群から選ばれ成分との総量１．０モルに対して（１）ジイソシアネート化合物からなる成分の量を０．８〜１．１モルとすることが好ましく、０．９５〜１．０８モルとすることがより好ましく、特に１．０〜１．０８モル使用されることが好ましい。 (1) a component comprising a diisocyanate compound, (2-a) a trivalent carboxylic acid derivative having an acid anhydride group, (2-b) a dicarboxylic acid compound or a diol compound added as necessary, and (2-c) ) The amount used with the sum of the components selected from the group consisting of tetravalent carboxylic acid derivatives having two acid anhydride groups is the component (2) from the viewpoint of the molecular weight of the polyamideimide resin produced and the degree of crosslinking. (2-a) a trivalent carboxylic acid derivative having an acid anhydride group, (2-b) a dicarboxylic acid compound or a diol compound, and (2-c) a tetravalent carboxylic acid having two acid anhydride groups The amount of the component consisting of (1) the diisocyanate compound is preferably 0.8 to 1.1 mol with respect to 1.0 mol in total with the component selected from the group consisting of the acid derivatives, and 0.95 to 1. 08 moles More preferably, it is preferred that in particular from 1.0 to 1.08 moles.
本発明において、（２−ａ）酸無水物基を有する３価のカルボン酸誘導体に加えて、（２−ｂ）ジカルボン酸化合物又はジオール化合物を用いる場合、両者の配合割合（２−ａ）／（２−ｂ）は、当量比で０．９５／０．０５〜０．５０／０．５０とすることが好ましく、０．８５／０．１５〜０．６０／０．４０とすることがより好ましく、０．７５／０．２５〜０．６５／０．３５とすることが特に好ましい。この範囲であると、塗膜の柔軟性と耐熱性とに優れたポリアミドイミド樹脂が得られるため好ましいものとなる。 In the present invention, when (2-b) a dicarboxylic acid compound or a diol compound is used in addition to the (2-a) trivalent carboxylic acid derivative having an acid anhydride group, the blending ratio of both (2-a) / (2-b) is preferably 0.95 / 0.05 to 0.50 / 0.50 in terms of equivalent ratio, and 0.85 / 0.15 to 0.60 / 0.40. More preferably, 0.75 / 0.25 to 0.65 / 0.35 is particularly preferable. Within this range, a polyamideimide resin excellent in flexibility and heat resistance of the coating film can be obtained, which is preferable.
また、（２−ａ）酸無水物基を有する３価のカルボン酸誘導体に加えて、（２−ｃ）酸無水物基を２個有する４価のカルボン酸誘導体を用いる場合、両者の配合割合（２−ａ）／（２−ｃ）は、当量比で０．９５／０．０５〜０．５０／０．５０とすることが好ましく、０．８５／０．１５〜０．６０／０．４０とすることがより好ましく、０．７５／０．２５〜０．６５／０．３５とすることが特に好ましい。この範囲であると、塗膜の強度が優れたポリアミドイミド樹脂が得られるため好ましいものとなる。 Moreover, in addition to the (2-a) trivalent carboxylic acid derivative having an acid anhydride group, when a tetravalent carboxylic acid derivative having two (2-c) acid anhydride groups is used, the blending ratio of the two (2-a) / (2-c) is preferably 0.95 / 0.05 to 0.50 / 0.50 in terms of equivalent ratio, and 0.85 / 0.15 to 0.60 / 0. .40 is more preferable, and 0.75 / 0.25 to 0.65 / 0.35 is particularly preferable. Within this range, a polyamideimide resin having excellent coating film strength can be obtained, which is preferable.
なお、（２−ｂ）ジカルボン酸化合物又はジオール化合物と（２−ｃ）酸無水物基を２個有する４価のカルボン酸誘導体とを両方用いる場合には、両者の配合割合（２−ｂ）／（２−ｃ）は、当量比で０．９５／０．０５〜０．５０／０．５０とすることが好ましく、０．８５／０．１５〜０．６０／０．４０であることがより好ましい。 In the case where both (2-b) dicarboxylic acid compound or diol compound and (2-c) tetravalent carboxylic acid derivative having two acid anhydride groups are used, the blending ratio of both (2-b) / (2-c) is preferably 0.95 / 0.05 to 0.50 / 0.50 in terms of equivalent ratio, and is 0.85 / 0.15 to 0.60 / 0.40. Is more preferable.
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．（２−ａ）成分及び必要に応じて（２−ｂ）成分や（２−ｃ）成分と、ジイソシアネート成分（１）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．（２−ｂ）成分と、ジイソシアネート成分（１）の過剰量とを反応させて末端にイソシアネート基を有するアミドオリゴマーを合成した後、酸成分（２−ａ）及び必要に応じて（２−ｃ）成分を追加反応しポリアミドイミド樹脂を得る方法。
３．（２−ａ）成分及び必要に応じて（２−ｃ）成分の過剰量と、ジイソシアネート成分（１）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、（２−ｂ）成分を追加し反応させてポリアミドイミド樹脂を得る方法。
なお、上記の反応において、反応温度としては、一般に、８０〜１８０℃程度の温度で行うことが好ましい。
The polyamideimide resin used in the present invention can be obtained, for example, by the following production method.
1. A method of obtaining a polyamide-imide resin by using the (2-a) component and, if necessary, the (2-b) component or the (2-c) component and the diisocyanate component (1) at a time.
2. After reacting the component (2-b) with an excess of the diisocyanate component (1) to synthesize an amide oligomer having an isocyanate group at the terminal, the acid component (2-a) and, if necessary, (2-c ) A method in which a component is additionally reacted to obtain a polyamideimide resin.
3. After reacting the (2-a) component and, if necessary, the excess amount of the (2-c) component with the diisocyanate component (1) to synthesize an amide-imide oligomer having an acid or acid anhydride group at the end, ( 2-b) A method in which a component is added and reacted to obtain a polyamideimide resin.
In addition, in said reaction, generally as reaction temperature, it is preferable to carry out at the temperature of about 80-180 degreeC.
このようにして得られたポリアミドイミド樹脂は、数平均分子量が１０，０００から７５，０００のものが好ましい。数平均分子量が１０，０００未満では塗膜の強度が低下する傾向があり、７５，０００を超えると、塗料として適切な濃度で溶媒に溶解した時に粘度が高くなり、塗装時の作業性が劣る傾向がある。これらの観点から、ポリアミドイミド樹脂の数平均分子量は１５，０００から５０，０００とすることが好ましく、２０，０００から３５，０００とすることがより好ましい。 The polyamideimide resin thus obtained preferably has a number average molecular weight of 10,000 to 75,000. When the number average molecular weight is less than 10,000, the strength of the coating film tends to decrease. Tend. From these viewpoints, the number average molecular weight of the polyamideimide resin is preferably 15,000 to 50,000, and more preferably 20,000 to 35,000.
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ル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 number average molecular weight of the polyamideimide resin is sampled during 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.
以上のようにして得られるポリアミドイミド樹脂は、反応終了後メタノールやアセトンなどの貧溶媒中に投入し、析出させて固形状の樹脂とすることもできるし、得られたポリアミドイミド樹脂を反応に用いた尿素結合を有する溶媒に溶解させた状態のワニスとすることもできる。なお、ここで溶解させる溶媒としては、ポリアミドイミド樹脂を溶解できるものであれば、いずれも用いることができるが、本発明の目的からいって、アミド系溶媒ではなく、上記の尿素結合を有する溶媒を用いることが好ましいものである。 The polyamideimide resin obtained as described above can be poured into a poor solvent such as methanol or acetone after the completion of the reaction and precipitated to form a solid resin, or the obtained polyamideimide resin can be reacted. It can also be set as the varnish of the state melt | dissolved in the solvent which has the used urea bond. Any solvent can be used as long as it can dissolve the polyamideimide resin, but for the purpose of the present invention, it is not an amide solvent but a solvent having the above urea bond. Is preferably used.
本発明で得られるポリアミドイミド樹脂は、通常、十分な耐溶剤性を得るために、加熱硬化時における樹脂同士の重合反応及び架橋反応を促進させる目的で、多官能型エポキシ化合物、イソシアネート化合物、アミン化合物、メラミン化合物、ポリエステル化合物等の硬化剤を配合し、ポリアミドイミド樹脂組成物として用いることが好ましい。 The polyamidoimide resin obtained in the present invention is usually a polyfunctional epoxy compound, an isocyanate compound, an amine for the purpose of accelerating the polymerization reaction and crosslinking reaction between the resins during heat curing in order to obtain sufficient solvent resistance. It is preferable that a curing agent such as a compound, a melamine compound, or a polyester compound is blended and used as a polyamideimide resin composition.
硬化剤としては、本発明で得られるポリアミドイミド樹脂との反応性及び得られる塗膜特性から、特に多官能型エポキシ化合物の併用が好ましい。
多官能型エポキシ化合物としては、ビスフェノールＡ型、ビスフェノールＦ型、ノボラック型、アミン型、アルコール型、ビフェニル型、エステル型等特に制限はなく、複数のものを同時に併用することができる。これらのうちでも、ビスフェノールＡ型、ビスフェノールＦ型、ビフェニル型を用いることが好ましい。
As the curing agent, combined use of a polyfunctional epoxy compound is particularly preferred in view of the reactivity with the polyamideimide resin obtained in the present invention and the obtained coating film properties.
The polyfunctional epoxy compound is not particularly limited, such as bisphenol A type, bisphenol F type, novolac type, amine type, alcohol type, biphenyl type, ester type, and a plurality of them can be used simultaneously. Among these, it is preferable to use bisphenol A type, bisphenol F type, and biphenyl type.
多官能型エポキシ化合物等の硬化剤の配合量は、ポリアミドイミド樹脂１００重量部に対して１〜１００重量部とすることが好ましい。
硬化剤の量をこの範囲とすることが、重合反応及び架橋反応の促進効果が十分に得られ、得られる塗膜の耐溶剤性に優れるものが得られる点で好ましく、１０〜６０重量部とすることがより好ましい。
The blending amount of the curing agent such as the polyfunctional epoxy compound is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyamideimide resin.
Setting the amount of the curing agent in this range is preferable in that the effect of promoting the polymerization reaction and the crosslinking reaction can be sufficiently obtained, and that the obtained coating film has excellent solvent resistance, and is preferably 10 to 60 parts by weight. More preferably.
以上のようにして得られる本発明のポリアミドイミド樹脂及びポリアミドイミド組成物は、尿素結合を有する溶媒等の極性溶媒、キシレン、トルエン等の芳香族炭化水素系溶媒、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化合物類、エタノール、２−プロパノール、エチレングリコール等のアルコール類、ジエチルエーテル、ジエチレングリコールジエチルエーテル等のエーテル化合物類などの溶媒に溶解され、適当な粘度に調整してワニスないしは塗料とすることができる。ワニスないし塗料とする場合、一般に固形分は１０〜５０重量％とされる。 Polyamideimide resin and polyamideimide composition of the present invention obtained as described above are polar solvents such as a solvent having a urea bond, aromatic hydrocarbon solvents such as xylene and toluene, ketones such as methyl ethyl ketone and methyl isobutyl ketone. It can be dissolved in a solvent such as a compound, an alcohol such as ethanol, 2-propanol, or ethylene glycol, or an ether compound such as diethyl ether or diethylene glycol diethyl ether, and adjusted to an appropriate viscosity to obtain a varnish or paint. When a varnish or paint is used, the solid content is generally 10 to 50% by weight.
本発明のポリアミドイミド樹脂又はポリアミドイミド樹脂組成物を塗膜成分として含有するワニスないし塗料には、通常、前記の溶媒に加え、必要に応じ、揺変性付与剤、顔料、充填材、硬化促進剤、重合禁止剤、等を配合することができる。
揺変性付与剤としては、例えば、微粒子シリカ、有機ベントナイト、有機高分子微粒子等が挙げられる。
顔料、充填材としては、例えば、酸化鉄、酸化チタン、酸化アルミニウム、硫酸バリウム、炭酸カルシウム、炭酸マグネシウム、タルク、クレーシリカ等が挙げられる。
The varnish or paint containing the polyamide-imide resin or the polyamide-imide resin composition of the present invention as a coating film component is usually added to the above-mentioned solvent, and if necessary, thixotropic agent, pigment, filler, curing accelerator. , Polymerization inhibitors and the like can be blended.
Examples of the thixotropic agent include fine particle silica, organic bentonite, and organic polymer fine particles.
Examples of the pigment and filler include iron oxide, titanium oxide, aluminum oxide, barium sulfate, calcium carbonate, magnesium carbonate, talc, and clay silica.
本発明で得られるポリアミドイミド樹脂やポリアミドイミド樹脂組成物を塗膜成分としてなるワニスないし塗料は、被塗物に塗布、硬化させて、被塗物表面に塗膜を形成することができる。 A varnish or a coating material comprising the polyamideimide resin or the polyamideimide resin composition obtained in the present invention as a coating film component can be applied to a coating material and cured to form a coating film on the surface of the coating material.
特に本発明のポリアミドイミド樹脂の合成方法は、従来のポリアミドイミド樹脂の合成方法と比較して、環境、人体への悪影響を与え難い尿素系溶媒を用いポリアミドイミド樹脂合成し、優れた加工性及び密着性を有する柔軟な塗膜を形成することができ、かつ耐溶剤性を保持することができることから、高加工性、高密着性及び高耐溶剤性の要求される多種多様な用途において多大な有益性を有している。 In particular, the method for synthesizing the polyamide-imide resin of the present invention synthesizes the polyamide-imide resin using a urea-based solvent that is unlikely to adversely affect the environment and the human body as compared with the conventional method for synthesizing the polyamide-imide resin, and has excellent processability and A flexible coating film having adhesion can be formed and solvent resistance can be maintained, so that it is very useful in a wide variety of applications requiring high workability, high adhesion and high solvent resistance. Has benefits.
次に本発明の実施例について説明するが、本発明はこれらの実施例に限定されるものではなく、発明の主旨に基づいたこれら以外の多くの実施態様を含むことは言うまでもない。 EXAMPLES Next, examples of the present invention will be described. However, the present invention is not limited to these examples, and it is needless to say that many other embodiments based on the gist of the invention are included.
実施例１
無水トリメリット酸２８８．２ｇ、４，４′−ジフェニルメタンジイソシアネート３７５．４ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア１２９０．９ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら１時間かけて徐々に昇温して１２０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら徐々に昇温して１４０℃まで上げ、加熱開始から６時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は３１．７重量％で、粘度（２５℃）は７．４Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は４８，０００であった。
Example 1
Nitrogen stream dried by placing 288.2 g of trimellitic anhydride, 375.4 g of 4,4'-diphenylmethane diisocyanate, and 1290.9 g of N, N'-dimethylethyleneurea in a flask equipped with a thermometer, stirrer, and condenser. The temperature was gradually raised to 120 ° C. over 1 hour with stirring. The temperature was gradually raised to 140 ° C. while paying attention to the sudden bubbling of carbon dioxide gas generated by the reaction, and after 6 hours of heating from the start of heating, the reaction was stopped to obtain a polyamideimide resin solution.
The nonvolatile content (200 ° C.-2 h) of this polyamideimide resin solution was 31.7% by weight, and the viscosity (25 ° C.) was 7.4 Pa · s. The number average molecular weight of the polyamideimide resin was 48,000.
なお、数平均分子量はＧＰＣを用い、次の条件にて測定し、標準ポリスチレンに換算した値として算出した。
機種：日立 Ｌ６０００
検出器：日立 Ｌ４０００型ＵＶ
波長：２７０ｎｍ
データ処理機：ＡＴＴ ８
カラム：Ｇｅｌｐａｃｋ ＧＬ−Ｓ３００ＭＤＴ−５×２
カラムサイズ：８ｍｍφ×３００ｍｍ
溶媒：ＤＭＦ／ＴＨＦ＝１／１（リットル）＋リン酸０．０６Ｍ＋臭化リチウム０．０６Ｍ
試料濃度：５ｍｇ／１ｍｌ
注入量：５μｌ
圧力：４９ｋｇｆ／ｃｍ2（４．８×１０6Ｐａ）
流量：１．０ｍｌ／ｍｉｎ
The number average molecular weight was measured under the following conditions using GPC and calculated as a value converted to standard polystyrene.
Model: Hitachi L6000
Detector: Hitachi L4000 type UV
Wavelength: 270nm
Data processor: ATT 8
Column: Gelpack GL-S300MDT-5 × 2
Column size: 8mmφ × 300mm
Solvent: DMF / THF = 1/1 (liter) + phosphoric acid 0.06M + lithium bromide 0.06M
Sample concentration: 5 mg / 1 ml
Injection volume: 5 μl
Pressure: 49 kgf / cm 2 (4.8 × 10 6 Pa)
Flow rate: 1.0 ml / min
実施例２
無水トリメリット酸２８８．２ｇ、４，４′−ジフェニルメタンジイソシアネート１８７．７ｇ、トリレンジイソシアネート１３０．６ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア１１８０．０ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら１時間かけて徐々に昇温して１２０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら徐々に昇温して１４０℃まで上げ、加熱開始から６時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は３１．５重量％で、粘度（２５℃）は３．６Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は３６，０００であった。
Example 2
Trimellitic anhydride 288.2g, 4,4'-diphenylmethane diisocyanate 187.7g, tolylene diisocyanate 130.6g, N, N'-dimethylethyleneurea 1180.0g was placed in a flask equipped with a thermometer, stirrer and condenser. The temperature was gradually raised to 120 ° C. over 1 hour with stirring in a nitrogen stream that had been put in and dried. The temperature was gradually raised to 140 ° C. while paying attention to the sudden bubbling of carbon dioxide gas generated by the reaction, and after 6 hours of heating from the start of heating, the reaction was stopped to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a nonvolatile content (200 ° C.-2 h) of 31.5% by weight and a viscosity (25 ° C.) of 3.6 Pa · s. The number average molecular weight of the polyamideimide resin was 36,000.
実施例３
無水トリメリット酸２８８．２ｇ、４，４′−ジフェニルメタンジイソシアネート１８７．７ｇ、４，４′−ジイソシアナト−３，３′−ジメチルビフェニル１９８．２ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア１３１０．９ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら１時間かけて徐々に昇温して１２０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら徐々に昇温して１４０℃まで上げ、加熱開始から６時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は３１．２重量％で、粘度（２５℃）は３．４Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は３３，０００であった。
Example 3
Temperature of 288.2 g of trimellitic anhydride, 187.7 g of 4,4′-diphenylmethane diisocyanate, 198.2 g of 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 1310.9 g of N, N′-dimethylethyleneurea The mixture was placed in a flask equipped with a meter, a stirrer, and a cooling tube, and gradually heated to 120 ° C. over 1 hour while stirring in a dried nitrogen stream. The temperature was gradually raised to 140 ° C. while paying attention to the sudden bubbling of carbon dioxide gas generated by the reaction, and after 6 hours of heating from the start of heating, the reaction was stopped to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a non-volatile content (200 ° C.-2 h) of 31.2 wt% and a viscosity (25 ° C.) of 3.4 Pa · s. The number average molecular weight of the polyamideimide resin was 33,000.
実施例４
無水トリメリット酸４３０．３ｇ、アジピン酸１４０．３ｇ、４，４′−ジフェニルメタンジイソシアネート８００．８ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア２８０９．９ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら２時間かけて徐々に昇温して１３０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら１３０℃を保持し、このまま７時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は３０．２重量％で、粘度（２５℃）は３．５Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は３５，０００であった。
Example 4
Put 430.3 g of trimellitic anhydride, 140.3 g of adipic acid, 800.8 g of 4,4'-diphenylmethane diisocyanate, and 2809.9 g of N, N'-dimethylethyleneurea in a flask equipped with a thermometer, stirrer and condenser. The temperature was gradually raised to 130 ° C. over 2 hours with stirring in a dried nitrogen stream. The temperature was kept at 130 ° C. while paying attention to the sudden foaming of carbon dioxide gas generated by the reaction, and the heating was continued for 7 hours, and the reaction was stopped to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a nonvolatile content (200 ° C.-2 h) of 30.2% by weight and a viscosity (25 ° C.) of 3.5 Pa · s. The number average molecular weight of the polyamideimide resin was 35,000.
実施例５
無水トリメリット酸３１２．８ｇ、アジピン酸９９．４ｇ、イソフタル酸２０．２ｇ、４，４′−ジフェニルメタンジイソシアネート５７７．７ｇ、トリレンジイソシアネート２７．５ｇをＮ，Ｎ’−ジメチルエチレンウレア２６６８．３ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら１時間かけて徐々に昇温して１１０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら１１０℃を保ち、加熱開始から８時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は２６．５重量％で、粘度（２５℃）は１．１Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は２０，０００であった。
Example 5
312.8 g of trimellitic anhydride, 99.4 g of adipic acid, 20.2 g of isophthalic acid, 577.7 g of 4,4'-diphenylmethane diisocyanate, 27.5 g of tolylene diisocyanate, 2668.3 g of N, N'-dimethylethyleneurea The flask was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and gradually heated to 110 ° C. over 1 hour with stirring in a dried nitrogen stream. The temperature was kept at 110 ° C. while paying attention to the sudden foaming of carbon dioxide gas generated by the reaction, and the reaction was stopped after continuing the heating for 8 hours from the start of heating to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a nonvolatile content (200 ° C.-2 h) of 26.5 wt% and a viscosity (25 ° C.) of 1.1 Pa · s. The number average molecular weight of the polyamideimide resin was 20,000.
実施例６
無水トリメリット酸２１６．１ｇ、セバシン酸７５．８ｇ、４，４′−ジフェニルメタンジイソシアネート３６７．９ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア１２８０．９ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら１時間かけて徐々に昇温して１２０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら徐々に昇温して１４０℃まで上げ、加熱開始から６時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は３１．８重量％で、粘度（２５℃）は７．６Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は５０，０００であった。
Example 6
Put 216.1 g of trimellitic anhydride, 75.8 g of sebacic acid, 367.9 g of 4,4'-diphenylmethane diisocyanate, 1280.9 g of N, N'-dimethylethyleneurea in a flask equipped with a thermometer, stirrer and condenser. The temperature was gradually raised to 120 ° C. over 1 hour with stirring in a dried nitrogen stream. The temperature was gradually raised to 140 ° C. while paying attention to the sudden bubbling of carbon dioxide gas generated by the reaction, and after 6 hours of heating from the start of heating, the reaction was stopped to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a nonvolatile content (200 ° C.-2 h) of 31.8% by weight and a viscosity (25 ° C.) of 7.6 Pa · s. The number average molecular weight of the polyamideimide resin was 50,000.
実施例７
無水トリメリット酸４３０．３ｇ、１，６−ヘキサンジオール１１３．４ｇ、４，４′−ジフェニルメタンジイソシアネート８００．８ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア２７５５．０ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら２時間かけて徐々に昇温して１３０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら１３０℃を保持し、このまま７時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は３０．３重量％で、粘度（２５℃）は３．３Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は３４，０００であった。
Example 7
Equipped with thermometer, stirrer, and condenser tube, 430.3 g trimellitic anhydride, 113.4 g 1,6-hexanediol, 800.8 g 4,4'-diphenylmethane diisocyanate, 2755.0 g N, N'-dimethylethyleneurea The mixture was gradually warmed up to 130 ° C. over 2 hours with stirring in a dry nitrogen stream. The temperature was kept at 130 ° C. while paying attention to the sudden foaming of carbon dioxide gas generated by the reaction, and the heating was continued for 7 hours, and the reaction was stopped to obtain a polyamideimide resin solution.
The nonvolatile content (200 ° C.-2 h) of this polyamideimide resin solution was 30.3% by weight, and the viscosity (25 ° C.) was 3.3 Pa · s. The number average molecular weight of the polyamideimide resin was 34,000.
実施例８
無水トリメリット酸４３４．９ｇ、ピロメリット酸無水物１０．１ｇ、４，４′−ジフェニルメタンジイソシアネート５７８．１ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア３８５０．０ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら２時間かけて徐々に昇温して１３０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら１３０℃を保持し、このまま７時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は１９．０重量％で、粘度（２５℃）は５．１Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は４１，０００であった。
Example 8
Trimellitic anhydride 434.9 g, pyromellitic anhydride 10.1 g, 4,4'-diphenylmethane diisocyanate 578.1 g, N, N'-dimethylethyleneurea 3850.0 g were equipped with a thermometer, stirrer and condenser. The mixture was gradually warmed up to 130 ° C. over 2 hours while stirring in a nitrogen stream that had been put into a flask and dried. The temperature was kept at 130 ° C. while paying attention to the sudden foaming of carbon dioxide gas generated by the reaction, and the heating was continued for 7 hours, and the reaction was stopped to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a non-volatile content (200 ° C.-2 h) of 19.0 wt% and a viscosity (25 ° C.) of 5.1 Pa · s. The number average molecular weight of the polyamideimide resin was 41,000.
実施例９
無水トリメリット酸３５２．８ｇ、イソフタル酸７６．８ｇ、ピロメリット酸無水物２．５ｇ、４，４′−ジフェニルメタンジイソシアネート５７８．１ｇアジピン酸１４０．３ｇ、４，４′−ジフェニルメタンジイソシアネート８００．８ｇ、Ｎ，Ｎ’−ジメチルエチレンウレア２７４９．９ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら２時間かけて徐々に昇温して１３０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら１３０℃を保持し、このまま７時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は２４．９重量％で、粘度（２５℃）は２．１Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は２５，０００であった。
Example 9
Trimellitic anhydride 352.8 g, isophthalic acid 76.8 g, pyromellitic anhydride 2.5 g, 4,4'-diphenylmethane diisocyanate 578.1 g adipic acid 140.3 g, 4,4'-diphenylmethane diisocyanate 800.8 g, 2749.9 g of N, N′-dimethylethyleneurea was put in a flask equipped with a thermometer, a stirrer, and a cooling tube, and gradually heated up to 130 ° C. over 2 hours while stirring in a dried nitrogen stream. It was. The temperature was kept at 130 ° C. while paying attention to the sudden foaming of carbon dioxide gas generated by the reaction, and the heating was continued for 7 hours, and the reaction was stopped to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a nonvolatile content (200 ° C.-2 h) of 24.9% by weight and a viscosity (25 ° C.) of 2.1 Pa · s. The number average molecular weight of the polyamideimide resin was 25,000.
比較例１
無水トリメリット酸１６７．１ｇ、４，４−ジフェニルメタンジイソシアネート２２２．１ｇ、Ｎ−メチル−２−ピロリドン８０８．４ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で攪拌しながら２時間かけて徐々に昇温して１３０℃まで上げた。反応により生ずる炭酸ガスの急激な発泡に注意しながら１３０℃を保持し、このまま６時間加熱を続けた後反応を停止させ、ポリアミドイミド樹脂溶液を得た。
このポリアミドイミド樹脂溶液の不揮発分（２００℃−２ｈ）は２９．３重量％で、粘度（２５℃）は４．０Ｐａ・ｓであった。また、ポリアミドイミド樹脂の数平均分子量は２５，０００であった。
Comparative Example 1
Trimellitic anhydride 167.1 g, 4,4-diphenylmethane diisocyanate 222.1 g, N-methyl-2-pyrrolidone 808.4 g were put in a flask equipped with a thermometer, a stirrer and a condenser tube, and dried in a nitrogen stream. The temperature was gradually raised to 130 ° C. over 2 hours with stirring. The temperature was kept at 130 ° C. while paying attention to the sudden foaming of carbon dioxide gas generated by the reaction, and the heating was continued for 6 hours, and the reaction was stopped to obtain a polyamideimide resin solution.
The polyamideimide resin solution had a nonvolatile content (200 ° C.-2 h) of 29.3% by weight and a viscosity (25 ° C.) of 4.0 Pa · s. The number average molecular weight of the polyamideimide resin was 25,000.
試験例１
実施例１から９、及び比較例１で得られたポリアミドイミド樹脂をガラス基板の上に塗布して機械的特性を、アルミニウム基板Ａ１０５０Ｐ（１．０×５０×１５０ｍｍ、（株）パルテック製）の上に塗布して鉛筆硬度と密着性をそれぞれ測定した。
Test example 1
The polyamideimide resin obtained in Examples 1 to 9 and Comparative Example 1 was coated on a glass substrate, and the mechanical properties of aluminum substrate A1050P (1.0 × 50 × 150 mm, manufactured by Partec Co., Ltd.) The pencil hardness and the adhesiveness were measured by coating on the top.
［機械的特性］
実施例１から９、及び比較例１で得られたポリアミドイミド樹脂を塗布した基板を８０℃で１０分間予備乾燥させた後、２５０℃で３０分間加熱硬化し、塗膜厚が５ヶ所の平均値が２０μｍ、幅１０ｍｍ、長さが６０ｍｍの塗膜を得た。得られた塗膜を、引張試験機（島津製作所製オートグラフＡＧＳ−５ｋＧ）を用いてチャック間長さ２０ｍｍ、引張速度５ｍｍ／分の条件で引張試験を行い、機械的特性（強度、弾性率および伸び率）を求めた。
[Mechanical properties]
Substrates coated with the polyamideimide resins obtained in Examples 1 to 9 and Comparative Example 1 were pre-dried at 80 ° C. for 10 minutes, and then heat-cured at 250 ° C. for 30 minutes. A coating film having a value of 20 μm, a width of 10 mm, and a length of 60 mm was obtained. The obtained coating film was subjected to a tensile test using a tensile tester (Autograph AGS-5kG manufactured by Shimadzu Corporation) under the conditions of a length between chucks of 20 mm and a tensile speed of 5 mm / min, and mechanical properties (strength, elastic modulus). And elongation).
［鉛筆硬度］
実施例１から９、及び比較例１で得られたポリアミドイミド樹脂を塗布した基板を８０℃で１０分間予備乾燥させた後、２５０℃で３０分間加熱硬化し、塗膜厚が５ヶ所の平均値が２０μｍの塗膜を得た。この塗膜を鉛筆で削り、傷発生時の鉛筆の硬さを記録した。
[Pencil hardness]
Substrates coated with the polyamideimide resins obtained in Examples 1 to 9 and Comparative Example 1 were pre-dried at 80 ° C. for 10 minutes, and then heat-cured at 250 ° C. for 30 minutes. A coating film having a value of 20 μm was obtained. The coating film was shaved with a pencil, and the hardness of the pencil at the time of scratching was recorded.
［密着性］
実施例１から９、及び比較例１で得られたポリアミドイミド樹脂を塗布した基板を８０℃で１０分間予備乾燥させた後、２５０℃で３０分間加熱硬化し、塗膜厚が５ヶ所の平均値が２０μｍの塗膜を得た。この塗膜を１ｍｍ四方のマスを１０×１０マス作製し、粘着テープ（ニチバン製）にて５回剥離を行い、残ったマス目の数を数えた。
[Adhesion]
Substrates coated with the polyamideimide resins obtained in Examples 1 to 9 and Comparative Example 1 were pre-dried at 80 ° C. for 10 minutes, and then heat-cured at 250 ° C. for 30 minutes. A coating film having a value of 20 μm was obtained. 10 × 10 squares of 1 mm square were produced from this coating film, peeled five times with an adhesive tape (manufactured by Nichiban), and the number of remaining squares was counted.
結果を表１に示す。
実施例１０
実施例１で得られたポリアミドイミド樹脂溶液３０ｇを２００ｍｌの三角フラスコに秤取り、Ｎ，Ｎ’−ジメチルエチレンウレア７０ｇで希釈し希釈溶液を準備した。次に、アセトン７５０ｇ及び精製水７５０ｇを２Ｌビーカーに入れた後、ビーカー内の溶液を攪拌機でよく混合する。溶液を攪拌機で攪拌しながら、準備した希釈溶液１００ｇを２Ｌビーカー内に徐々に滴下すると、溶液中に、樹脂が析出した。析出した樹脂をろ過により回収した後、回収した樹脂を７０℃の乾燥機中で９６時間乾燥して樹脂粉体を得た。
Example 10
30 g of the polyamideimide resin solution obtained in Example 1 was weighed into a 200 ml Erlenmeyer flask and diluted with 70 g of N, N′-dimethylethyleneurea to prepare a diluted solution. Next, after putting 750 g of acetone and 750 g of purified water in a 2 L beaker, the solution in the beaker is mixed well with a stirrer. While stirring the solution with a stirrer, 100 g of the prepared diluted solution was gradually dropped into a 2 L beaker, and a resin was precipitated in the solution. The precipitated resin was collected by filtration, and then the collected resin was dried in a dryer at 70 ° C. for 96 hours to obtain a resin powder.
樹脂粉体中に残存する、残存ＮＭＰ量はガスクロマトグラフィーを用い測定した。その結果を表２に示した。なお、ガスクロマトグラフィーの測定条件を以下に記載する。
機種：ＧＬサイエンス ＧＣ−４０００
Ｃａｒｒｉｅｒ ｇａｓ：ヘリウム ５．０ｍＬ／ｍｉｎ
検出器：ＦＩＤ
カラム：ＴＣ−ＷＡＸ ｐｏｌｙｅｔｈｙｌｅｎｅ Ｇｌｙｃｏｌ
カラムサイズ：０．５３ｍｍφ×３０ｍ
温度 ｉｎｊｅｃｔｉｏｎ：２５０℃
Ｄｅｔｅｃｔｏｒ ：２５０℃
Ｏｖｅｎ ：６０℃（５ｍｉｎ）→１５℃／ｍｉｎ→２２０℃
The amount of residual NMP remaining in the resin powder was measured using gas chromatography. The results are shown in Table 2. In addition, the measurement conditions of gas chromatography are described below.
Model: GL Science GC-4000
Carrier gas: Helium 5.0 mL / min
Detector: FID
Column: TC-WAX polyethylene Glycol
Column size: 0.53mmφ × 30m
Temperature injection: 250 ° C
Detector: 250 ° C
Oven: 60 ° C. (5 min) → 15 ° C./min→220° C.
比較例２
比較例１で得られたポリアミドイミド樹脂溶液３０ｇを２００ｍｌの三角フラスコに秤取り、Ｎ−メチル−２−ピロリドン７０ｇで希釈し希釈溶液を準備した。次に、アセトン７５０ｇ及び精製水７５０ｇを２Ｌビーカーに入れた後、ビーカー内の溶液を攪拌機でよく混合する。溶液を攪拌機で攪拌しながら、準備した希釈溶液１００ｇを２Ｌビーカー内に徐々に滴下すると、溶液中に、樹脂が析出した。析出した樹脂をろ過により回収した後、回収した樹脂を７０℃の乾燥機中で９６時間乾燥して樹脂粉体を得た。次いで、実施例１０と同様にして、樹脂粉体中に残存するＮＭＰ量を測定した。その結果を表２に示した。
Comparative Example 2
30 g of the polyamideimide resin solution obtained in Comparative Example 1 was weighed into a 200 ml Erlenmeyer flask and diluted with 70 g of N-methyl-2-pyrrolidone to prepare a diluted solution. Next, after putting 750 g of acetone and 750 g of purified water in a 2 L beaker, the solution in the beaker is mixed well with a stirrer. While stirring the solution with a stirrer, 100 g of the prepared diluted solution was gradually dropped into a 2 L beaker, and a resin was precipitated in the solution. The precipitated resin was collected by filtration, and then the collected resin was dried in a dryer at 70 ° C. for 96 hours to obtain a resin powder. Next, in the same manner as in Example 10, the amount of NMP remaining in the resin powder was measured. The results are shown in Table 2.
表１より実施例１から９で得られた、ポリアミドイミド樹脂から作製された塗膜は、比較例１で得られたポリアミドイミド樹脂から作製された塗膜と比較して、機械的特性の引張り強度、弾性率及び伸び率が同程度の値を示すことが分かった。また、樹脂粉体中に残存するＮＭＰ量は、実施例１０では、検出限界以下であったが、比較例２では１０００ｐｐｍと大きな値を示した。本発明はポリアミドイミド樹脂の合成にＮＭＰのようなアミド系溶媒以外の溶媒を用いポリアミドイミド樹脂を合成でき、塗膜の機械特性や鉛筆硬度、密着性などは従来の溶媒を用いた場合に比べて同等ないしは同等以上の性能を有するものであり、粉体中にＮＭＰ等のアミド溶媒を含まない合成方法が可能となることが分かる。 From Table 1, the coating film produced from the polyamideimide resin obtained in Examples 1 to 9 was more tensile than the coating film produced from the polyamideimide resin obtained in Comparative Example 1. It was found that the strength, elastic modulus, and elongation showed similar values. The amount of NMP remaining in the resin powder was below the detection limit in Example 10, but a large value of 1000 ppm was shown in Comparative Example 2. The present invention can synthesize a polyamide-imide resin by using a solvent other than an amide solvent such as NMP for the synthesis of the polyamide-imide resin, and the mechanical properties, pencil hardness, adhesion, etc. of the coating film are compared with those using a conventional solvent. Thus, it can be seen that a synthesis method in which the powder does not contain an amide solvent such as NMP is possible.
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| JP2017101197A (en) * | 2015-12-04 | 2017-06-08 | 日立化成株式会社 | Polyamide-imide resin composition and paint |
| JP2018120185A (en) * | 2017-01-27 | 2018-08-02 | 富士ゼロックス株式会社 | Transfer roller, image forming apparatus, transfer device, and transfer unit |
| JP2018136484A (en) * | 2017-02-23 | 2018-08-30 | 富士ゼロックス株式会社 | Cylindrical member for image forming apparatus, image forming apparatus, and cylindrical member unit |
| JPWO2018015998A1 (en) * | 2016-07-19 | 2019-05-09 | 日立化成株式会社 | Polyamideimide resin composition and paint |
| JPWO2018066395A1 (en) * | 2016-10-05 | 2019-07-25 | 東レ株式会社 | Resin composition, cured film, semiconductor device and method for manufacturing them |
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| JP2017101197A (en) * | 2015-12-04 | 2017-06-08 | 日立化成株式会社 | Polyamide-imide resin composition and paint |
| JPWO2018015998A1 (en) * | 2016-07-19 | 2019-05-09 | 日立化成株式会社 | Polyamideimide resin composition and paint |
| JP7107838B2 (en) | 2016-07-19 | 2022-07-27 | 昭和電工マテリアルズ株式会社 | Polyamideimide resin composition and paint |
| JPWO2018066395A1 (en) * | 2016-10-05 | 2019-07-25 | 東レ株式会社 | Resin composition, cured film, semiconductor device and method for manufacturing them |
| JP7013872B2 (en) | 2016-10-05 | 2022-02-15 | 東レ株式会社 | Resin compositions, cured films, semiconductor devices and methods for manufacturing them |
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