JP2003138134A - Heat-resistant resin composition, coating and aluminum substrate - Google Patents
Heat-resistant resin composition, coating and aluminum substrateInfo
- Publication number
- JP2003138134A JP2003138134A JP2001342077A JP2001342077A JP2003138134A JP 2003138134 A JP2003138134 A JP 2003138134A JP 2001342077 A JP2001342077 A JP 2001342077A JP 2001342077 A JP2001342077 A JP 2001342077A JP 2003138134 A JP2003138134 A JP 2003138134A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- heat
- resistant resin
- aluminum
- coating
- 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
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000758 substrate Substances 0.000 title claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 50
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 50
- -1 aluminum alkoxide Chemical class 0.000 claims abstract description 39
- 239000013522 chelant Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 18
- 125000004018 acid anhydride group Chemical group 0.000 claims description 14
- 239000004135 Bone phosphate Substances 0.000 claims description 13
- 150000007514 bases Chemical class 0.000 claims description 13
- 238000007142 ring opening reaction Methods 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 abstract description 10
- 230000006866 deterioration Effects 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 5
- 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 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 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 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 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
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-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
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- XNIOWJUQPMKCIJ-UHFFFAOYSA-N 2-(benzylamino)ethanol Chemical compound OCCNCC1=CC=CC=C1 XNIOWJUQPMKCIJ-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-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
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、アルミニウム基材
に優れた密着性を有する塗膜を形成する耐熱性樹脂組成
物及び塗料に関する。TECHNICAL FIELD The present invention relates to a heat-resistant resin composition and a coating material for forming a coating film having excellent adhesion on an aluminum substrate.
【0002】[0002]
【従来の技術】ポリアミドイミド樹脂が優れた耐熱性、
耐薬品性、機械的特性を有することは良く知られてお
り、耐熱電線用塗料、金属表面保護塗料等として広く実
用に供されている。ポリアミドイミド樹脂の一般的な製
造法についても公知(例えば特公昭44−19274号
公報)であるが、従来、この樹脂は一般の溶剤類には不
溶性のためN−メチル−2−ピロリドン、ジメチルアセ
トアミド、ジメチルホルムアミド、ジメチルスルホキシ
ド等の高価な極性型の有機溶剤類に溶解し、有機溶剤型
樹脂溶液として実用に供していた。2. Description of the Related Art Polyamide-imide resin has excellent heat resistance,
It is well known that it has chemical resistance and mechanical properties, and is widely put to practical use as a paint for heat-resistant wires, a metal surface protective paint, and the like. A general method for producing a polyamide-imide resin is also known (for example, Japanese Patent Publication No. 44-19274), but since this resin is insoluble in general solvents, N-methyl-2-pyrrolidone and dimethylacetamide have been conventionally used. , Dimethylformamide, dimethylsulfoxide, and the like, which have been dissolved in expensive polar type organic solvents, have been put to practical use as an organic solvent type resin solution.
【0003】しかし、これらの有機溶剤型樹脂溶液は加
熱及び乾燥工程において多量の溶剤を放出するため、大
気汚染や水質汚染等の環境汚染や、人体への有害性や作
業環境の悪化等の安全衛生面等で大きな問題となってい
る。However, since these organic solvent type resin solutions release a large amount of solvent in the heating and drying processes, environmental pollution such as air pollution and water pollution, and safety such as harmfulness to human body and deterioration of working environment, etc. It is a big problem in terms of hygiene.
【0004】また、これらの有機溶剤は高価であるた
め、有機溶剤の多量な使用により樹脂溶液が高価になる
という経済性の問題もある。さらに、これら極性溶媒は
親水性であるがゆえに、塗装作業中に吸湿して部分的に
樹脂が析出したり、場合によってはゲル化して、塗装作
業性に支障をきたすような問題もある。Further, since these organic solvents are expensive, there is a problem of economy in that the resin solution becomes expensive due to the large amount of the organic solvent used. Further, since these polar solvents are hydrophilic, there is a problem that they absorb moisture during the coating work and partially deposit the resin, or in some cases, they gel to impair the coating workability.
【0005】近年、環境保全に対する関心が高まり、有
機溶剤に代わり媒体に水を使用する水性樹脂溶液が注目
されている。媒体に無害で安価な水を使用することは、
環境汚染や安全衛生面だけでなく、経済性にも非常に有
効である。また、親水性溶媒の一部又は全部を水で置換
すれば、最初から組成物中に水分を含むわけであるか
ら、吸湿の問題を回避することができ、したがって吸湿
に起因する上述したような既存のポリアミドイミド組成
物の欠点をなくすことができる。In recent years, interest in environmental protection has increased, and an aqueous resin solution using water as a medium instead of an organic solvent has attracted attention. Using harmless and cheap water for the medium
It is very effective not only for environmental pollution and health and safety, but also for economic efficiency. Further, if a part or all of the hydrophilic solvent is replaced with water, the composition will contain water from the beginning, so that the problem of moisture absorption can be avoided, and therefore, as described above due to moisture absorption. The drawbacks of the existing polyamide-imide composition can be eliminated.
【0006】これらを受けて、水溶性ポリアミドイミド
樹脂の開発を検討し、安定的な製造方法を確立するに至
った(特願2001−138302)。In response to these, the development of a water-soluble polyamide-imide resin was examined and a stable manufacturing method was established (Japanese Patent Application No. 2001-138302).
【0007】現在、自動車部品、食品関係の器具などの
用途には軽量で放熱性に優れるアルミニウム基材が用い
られる例が増大している。しかし、ポリアミドイミド樹
脂系の耐熱塗料をアルミニウム基材に適用する場合、塗
膜とアルミニウム基材の密着性に難があり、一般に密着
性を向上させるためにアルミニウム基材を物理的(研磨
など)、化学的(酸、アルカリなどによるエッチング)
な方法により表面処理し、基材表面に凹凸を形成さえた
り、あるいはリン酸塩処理やクロメート処理などを施し
化成被膜を形成させ塗装している。このため、塗装工程
の複雑化、コストアップ、廃材の処理に関する公害対策
などの問題があり、アルミニウム基材の表面処理を省略
したいとのニーズが高まりつつある。At present, an example in which an aluminum base material which is lightweight and has excellent heat dissipation is used for applications such as automobile parts and food-related appliances is increasing. However, when a polyamide-imide resin heat-resistant paint is applied to an aluminum base material, the adhesion between the coating film and the aluminum base material is difficult, and the aluminum base material is generally physically (such as polished) to improve the adhesion. , Chemical (etching with acid, alkali, etc.)
The surface treatment is performed by various methods to form irregularities on the surface of the base material, or phosphate treatment or chromate treatment is applied to form a chemical conversion film for coating. For this reason, there are problems such as a complicated coating process, an increase in cost, and pollution control regarding the treatment of waste materials, and there is an increasing need to omit the surface treatment of the aluminum base material.
【0008】[0008]
【発明が解決しようとする課題】本発明の目的は、有機
溶剤含有量を低減させ、環境汚染や作業環境の悪化がな
く、安全衛生面に対して有利であり、かつ塗料及び塗膜
特性が良好であり、更に、アルミニウム基材に対して密
着性を向上させるための表面処理を行わずに優れた密着
性を有する塗膜を形成する耐熱性樹脂組成物、これを塗
膜成分としてなる塗料及びこの組成物を用いたアルミニ
ウム基材を提供することにある。The object of the present invention is to reduce the content of organic solvent, to prevent environmental pollution and deterioration of working environment, to be advantageous in terms of safety and hygiene, and to improve the characteristics of paint and coating film. A heat-resistant resin composition that is good and that forms a coating film having excellent adhesion without surface treatment for improving adhesion to an aluminum base material, and a coating composition using this as a coating film component And to provide an aluminum substrate using this composition.
【0009】[0009]
【課題を解決するための手段】本発明は、次のものに関
する。
(1)水溶性ポリアミドイミド樹脂及びアルミニウムキ
レート及び/またはアルミニウムアルコキシドを含有し
てなる耐熱性樹脂組成物。
(2) (A)塩基性極性溶媒中で、ジイソシアネート
化合物又はジアミン化合物と三塩基酸無水物又は三塩基
酸無水物クロライドとを反応させて得られるポリアミド
イミド樹脂と(B)塩基性化合物、(C)水及び(D)
アルミニウムキレート及び/またはアルミニウムアルコ
キシドとを配合してなる(1)記載の耐熱性樹脂組成
物。
(3) (B)成分の塩基性化合物が(A)成分のポリ
アミドイミド樹脂中に含まれるカルボキシル基及びポリ
アミドイミド樹脂中の酸無水物基を開環させたカルボキ
シル基を合わせた酸価に対して、1〜20当量配合され
ている(1)又は(2)記載の耐熱性樹脂組成物。
(4) (C)成分の水が(A)成分、(B)成分及び
(C)成分の合計量に対して、5〜99重量%配合され
ている(1)又は(2)記載の耐熱性樹脂組成物。
(5) ポリアミドイミド樹脂の数平均分子量が5,0
00〜50,000で、かつ、カルボキシル基及び酸無
水物基を開環させたカルボキシル基を合わせた酸価が1
0〜100である(1)〜(4)のいずれかに記載の耐
熱性樹脂組成物。
(6) (B)成分の塩基性化合物がアルキルアミン又
はアルカノールアミンである(1)〜(4)のいずれか
に記載の耐熱性樹脂組成物。
(7) ポリアミドイミド樹脂100重量%に対してア
ルミニウムキレート及び/またはアルミニウムアルコキ
シドを0.1〜10重量%を含有する(1)又は(2)
記載の耐熱性樹脂組成物。
(8) (1)〜(7)のいずれかに記載の耐熱性樹脂
組成物を塗膜成分としてなる塗料。
(9) (1)〜(8)のいずれかに記載の耐熱性樹脂
組成物を塗布、硬化させたアルミニウム基材。The present invention relates to the following. (1) A heat-resistant resin composition containing a water-soluble polyamideimide resin and an aluminum chelate and / or an aluminum alkoxide. (2) (A) a polyamideimide resin obtained by reacting a diisocyanate compound or a diamine compound with a tribasic acid anhydride or tribasic acid anhydride chloride in a basic polar solvent; and (B) a basic compound, ( C) Water and (D)
The heat-resistant resin composition according to (1), which comprises an aluminum chelate and / or an aluminum alkoxide. (3) The acid value of the basic compound of the component (B) combined with the carboxyl group contained in the polyamideimide resin of the component (A) and the carboxyl group obtained by ring-opening the acid anhydride group in the polyamideimide resin. The heat-resistant resin composition according to (1) or (2), which is blended in an amount of 1 to 20 equivalents. (4) The heat resistance according to (1) or (2), wherein the water of the component (C) is blended in an amount of 5 to 99% by weight based on the total amount of the components (A), (B) and (C). Resin composition. (5) The number average molecular weight of the polyamide-imide resin is 5,0.
An acid value of 0 to 50,000 and a combined carboxyl group and a carboxyl group obtained by ring-opening an acid anhydride group is 1
The heat resistant resin composition according to any one of (1) to (4), which is 0 to 100. (6) The heat resistant resin composition according to any one of (1) to (4), wherein the basic compound as the component (B) is an alkylamine or an alkanolamine. (7) An aluminum chelate and / or an aluminum alkoxide is contained in an amount of 0.1 to 10% by weight based on 100% by weight of a polyamide-imide resin (1) or (2).
The heat-resistant resin composition as described. (8) A paint comprising the heat resistant resin composition according to any one of (1) to (7) as a coating film component. (9) An aluminum substrate on which the heat resistant resin composition according to any one of (1) to (8) is applied and cured.
【0010】[0010]
【発明の実施の形態】本発明に用いられるポリアミドイ
ミド樹脂は、一般式(I)で示される繰り返し構造単位
を有するものが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The polyamide-imide resin used in the present invention preferably has a repeating structural unit represented by the general formula (I).
【0011】[0011]
【化1】
[式中、R1は3価の有機基を表し、 R2は2価の有
機基を表し、nは整数を表す。]
R1としては、芳香環を有する炭素数6〜20の3価の
有機基が好ましく、R 2としては、芳香環を有する炭素
数6〜20の2価の有機基が好ましい。nは繰り返し構
造単位(I)の数であり、R1及びR2の構造によって
異なるが、一般的に10〜200とするのが好ましい。
このようなポリアミドイミド樹脂は、塩基性極性溶媒中
でジイソシアネート化合物又はジアミン化合物と三塩基
酸無水物又は三塩基酸無水物クロライドとを反応させて
得ることができる。塩基性極性溶媒としては、N−メチ
ル−2−ピロリドン等の高沸点溶媒を用いるのが好まし
い。また、使用量に特に制限はないが、ジイソシアネー
ト化合物又はジアミン化合物と三塩基酸無水物の総量1
00重量%に対して100〜500重量%とするのが好
ましい。反応温度は、通常、80〜180℃である。[Chemical 1]
[In the formula, R1Represents a trivalent organic group, RTwoIs divalent
Represents a machine base, and n represents an integer. ]
R1Is a trivalent C6-C20 trivalent aromatic ring.
Organic groups are preferred, R TwoAs a carbon with an aromatic ring
A divalent organic group of the number 6 to 20 is preferable. n is a repeating structure
R is the number of building units (I)1And RTwoBy the structure of
Although different, it is generally preferred to be 10-200.
Such a polyamide-imide resin is used in a basic polar solvent.
With diisocyanate compound or diamine compound and tribasic
By reacting with acid anhydride or tribasic acid chloride
Obtainable. As the basic polar solvent, N-methyl ether is used.
It is preferable to use a high boiling point solvent such as ru-2-pyrrolidone
Yes. The amount of diisocyanate used is not particularly limited.
Total amount of tri- or diamine compound and tribasic acid anhydride 1
It is preferable to set 100 to 500% by weight with respect to 00% by weight.
Good The reaction temperature is usually 80 to 180 ° C.
【0012】ジイソシアネート化合物又はジアミン化合
物と三塩基酸無水物又は三塩基酸無水物クロライドは、
それぞれ芳香族化合物を使用することが好ましい。上記
製造法に用いられる代表的な化合物を次に列挙する。ま
ず、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、キシリレンジイソシア
ネート、3,3′−ジフェニルメタンジイソシアネー
ト、パラフェニレンジイソシアネート等が挙げられる。
また、ジアミンとしては、4,4′−ジアミノジフェニ
ルエーテル、4,4′−ジアミノジフェニルスルホン、
3,3′−ジアミノジフェニルスルホン、キシリレンジ
アミン、フェニレンジアミン等が挙げられる。The diisocyanate compound or diamine compound and the tribasic acid anhydride or tribasic acid anhydride chloride are
Preference is given to using aromatic compounds in each case. Representative compounds used in the above production method are listed below. First, examples of the diisocyanate compound include 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3′-diphenylmethane diisocyanate, and paraphenylene diisocyanate.
As the diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone,
3,3'-diaminodiphenyl sulfone, xylylenediamine, phenylenediamine and the like can be mentioned.
【0013】また、三塩基酸無水物としては、トリメリ
ット酸無水物等が挙げられ、三塩基酸無水物クロライド
としては、トリメリット酸無水物クロライド等が挙げら
れる。ポリアミドイミド樹脂を合成する際に、ジカルボ
ン酸、テトラカルボン酸二無水物等をポリアミドイミド
樹脂の特性を損なわない範囲で同時に反応させることが
できる。ジカルボン酸としては、テレフタル酸、イソフ
タル酸、アジピン酸等が挙げられ、テトラカルボン酸二
無水物としては、ピロメリット酸二無水物、ベンゾフェ
ノンテトラカルボン酸二無水物、ビフェニルテトラカル
ボン酸二無水物等が挙げられる。The tribasic acid anhydride includes trimellitic acid anhydride and the like, and the tribasic acid chloride includes trimellitic acid anhydride chloride and the like. When synthesizing the polyamide-imide resin, dicarboxylic acid, tetracarboxylic dianhydride and the like can be simultaneously reacted within a range that does not impair the characteristics of the polyamide-imide resin. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid and the like, and examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and the like. Is mentioned.
【0014】前記ジイソシアネート化合物又はジアミン
化合物と三塩基酸無水物又は三塩基酸無水物クロライド
と必要に応じて使用するジカルボン酸及びテトラカルボ
ン酸二無水物の使用量は、生成されるポリアミドイミド
樹脂の分子量、架橋度の観点から酸成分の総量1.0モ
ルに対してジイソシアネート化合物又はジアミン化合物
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。また、酸
成分中、ジカルボン酸及びテトラカルボン酸二無水物
は、これらの総量が0〜50モル%の範囲で使用される
のが好ましい。The amount of the diisocyanate compound or diamine compound, tribasic acid anhydride or tribasic acid anhydride chloride, and dicarboxylic acid and tetracarboxylic dianhydride, which are optionally used, depends on the polyamideimide resin to be produced. From the viewpoint of the molecular weight and the degree of cross-linking, the diisocyanate compound or the diamine compound is preferably 0.8 to 1.1 mol based on 1.0 mol of the total amount of the acid component, and 0.95.
To 1.08 mol is more preferable, and especially 1.
It is preferable to use 0 to 1.08 mol. Moreover, it is preferable that the total amount of the dicarboxylic acid and the tetracarboxylic dianhydride in the acid component is used in the range of 0 to 50 mol%.
【0015】なお、ポリアミドイミド樹脂の数平均分子
量は、樹脂合成時にサンプリングしてゲルパーミエーシ
ョンクロマトグラフ(GPC)により、標準ポリスチレ
ンの検量線を用いて測定し、目的の数平均分子量になる
まで合成を継続することにより上記範囲に管理される。The number average molecular weight of the polyamide-imide resin is sampled at the time of resin synthesis and measured by gel permeation chromatograph (GPC) using a calibration curve of standard polystyrene. It is controlled within the above range by continuing.
【0016】本発明に用いられるポリアミドイミド樹脂
は、数平均分子量が5,000〜50,000のものが
好ましい。数平均分子量が5,000未満では、塗膜と
したときの、塗膜の耐熱性や機械的特性等の諸特性が低
下する傾向があり、50,000を超えると、塗料とし
て適正な濃度で溶媒に溶解したときに粘度が高くなり、
塗装時の作業性に劣る傾向がある。このことから、数平
均分子量は10,000〜30,000とすることが好
ましく、15,000〜25,000とすることが特に
好ましい。The polyamide-imide resin used in the present invention preferably has a number average molecular weight of 5,000 to 50,000. When the number average molecular weight is less than 5,000, various properties such as heat resistance and mechanical properties of the coating film when formed into a coating film tend to be deteriorated. When dissolved in a solvent, the viscosity increases,
Workability during painting tends to be poor. From this, the number average molecular weight is preferably 10,000 to 30,000, and particularly preferably 15,000 to 25,000.
【0017】また、カルボキシル基及び酸無水物基を開
環させたカルボキシル基を合わせた酸価が10〜100
であることが好ましく、10未満であると塩基性化合物
と反応するカルボキシル基が不足するため、水溶化が困
難となり、100を超えると最終的に得られる耐熱性樹
脂組成物が経日にてゲル化しやすくなる。このことか
ら、カルボキシル基及び酸無水物基を開環させたカルボ
キシル基を合わせた酸価が20〜80とすることがより
好ましく、30〜60とすることが特に好ましい。The acid value of the combined carboxyl group obtained by ring-opening the carboxyl group and the acid anhydride group is 10 to 100.
Is preferable, and when it is less than 10, the carboxyl group that reacts with the basic compound is insufficient, so that it becomes difficult to solubilize water, and when it exceeds 100, the heat-resistant resin composition finally obtained is a gel over time. It is easy to convert. From this, it is more preferable that the acid value of the combined carboxyl group obtained by ring-opening the carboxyl group and the acid anhydride group is 20 to 80, particularly preferably 30 to 60.
【0018】なお、ポリアミドイミド樹脂のカルボキシ
ル基及び酸無水物基を開環させたカルボキシル基を合わ
せた酸価は、以下の方法で得ることができる。ます、ポ
リアミドイミド樹脂を約0.5gとり、これに1,4−
ジアザビシクロ[2,2,2]オクタンを約0.15g
加え、さらにN−メチル−2−ピロリドンを約60g及
びイオン交換水を約1ml加え、ポリアミドイミド樹脂
が完全に溶解するまで攪拌する。これを0.05モル/
lエタノール性水酸化カリウム溶液を使用して電位差滴
定装置で滴定し、ポリアミドイミド樹脂のカルボキシル
基及び酸無水物基を開環させたカルボキシル基を合わせ
た酸価を得る。The acid value obtained by combining the carboxyl group of the polyamideimide resin and the carboxyl group obtained by ring-opening the acid anhydride group can be obtained by the following method. First, take about 0.5g of polyamide-imide resin and add 1,4-
About 0.15 g of diazabicyclo [2,2,2] octane
In addition, about 60 g of N-methyl-2-pyrrolidone and about 1 ml of ion-exchanged water are added, and the mixture is stirred until the polyamideimide resin is completely dissolved. 0.05 mol /
Using an ethanolic potassium hydroxide solution, titration is carried out with a potentiometric titrator to obtain an acid value in which the carboxyl group of the polyamideimide resin and the carboxyl group obtained by ring-opening the acid anhydride group are combined.
【0019】本発明において、塩基性化合物としてはト
リエチルアミン、トリブチルアミン、トリエチレンジア
ミン、N−メチルモルフォリン等のアルキルアミン、メ
チルアニリン、ジメチルアニリン等のアルキルアニリ
ン、モノエタノールアミン、ジエタノールアミン、トリ
エタノールアミン、ジプロパノールアミン、トリプロパ
ノールアミン、N−エチルエタノールアミン、N,N−
ジメチルエタノールアミン、シクロヘキサノールアミ
ン、N−メチルシクロヘキサノールアミン、N−ベンジ
ルエタノールアミン等のアルカノールアミン類が適して
いるが、これら以外の塩基性化合物、例えば水酸化ナト
リウムや水酸化カリウム等の苛性アルカリ又はアンモニ
ア水等を使用してもよく特に制限はない。好ましくは、
トリエチルアミン、N−メチルモルフォリン、トリエチ
レンジアミン、N,N−ジメチルエタノールアミンが使
用される。In the present invention, examples of the basic compound include triethylamine, tributylamine, triethylenediamine, alkylamines such as N-methylmorpholine, alkylaniline such as methylaniline and dimethylaniline, monoethanolamine, diethanolamine, triethanolamine, Dipropanolamine, tripropanolamine, N-ethylethanolamine, N, N-
Alkanolamines such as dimethylethanolamine, cyclohexanolamine, N-methylcyclohexanolamine and N-benzylethanolamine are suitable, but other basic compounds such as caustic alkalis such as sodium hydroxide and potassium hydroxide. Alternatively, ammonia water or the like may be used without any particular limitation. Preferably,
Triethylamine, N-methylmorpholine, triethylenediamine, N, N-dimethylethanolamine are used.
【0020】塩基性化合物は、上記の有機溶媒中で反応
させて得られるポリアミドイミド樹脂中に含まれるカル
ボキシル基及び開環させた酸無水物基を合わせた酸価に
対して、1〜20当量用いられる。1当量未満では樹脂
の水溶化が困難となり、20当量を越えると樹脂の加水
分解が促進され、長期の保存により粘度又は特性低下を
きたすことがある。このことから、カルボキシル基及び
酸無水物基を開環させたカルボキシル基を合わせた酸価
に対して、2〜10当量とすることが好ましく、3〜8
当量とすることが特に好ましい。The basic compound is used in an amount of 1 to 20 equivalents based on the combined acid value of the carboxyl group and the ring-opened acid anhydride group contained in the polyamideimide resin obtained by the reaction in the above organic solvent. Used. If it is less than 1 equivalent, it becomes difficult to make the resin water-soluble, and if it exceeds 20 equivalents, hydrolysis of the resin is accelerated, and viscosity or characteristic deterioration may occur due to long-term storage. From this, it is preferable that the amount is 2 to 10 equivalents based on the combined acid value of the carboxyl group obtained by ring-opening the carboxyl group and the acid anhydride group, and 3 to 8 is preferable.
It is particularly preferable that the amount is equivalent.
【0021】塩基性化合物はポリアミドイミド樹脂の末
端にあるカルボキシル基と塩を形成して親水性基とな
る。塩形成に際しては水の共存下に行ってもよいし、塩
基性化合物を添加した後、水を加えてもよい。塩を形成
させる温度は0℃〜200℃、好ましくは40℃〜13
0℃の範囲で行われる。The basic compound forms a salt with the carboxyl group at the terminal of the polyamide-imide resin to become a hydrophilic group. The salt formation may be carried out in the presence of water, or the basic compound may be added and then water may be added. The temperature at which the salt is formed is 0 ° C to 200 ° C, preferably 40 ° C to 13 ° C.
It is carried out in the range of 0 ° C.
【0022】塩基性化合物の種類と量及び水の添加方法
によって、得られる水性樹脂組成物の形態はエマルジョ
ン状、半透明溶液、透明溶液等となるが、貯蔵安定性、
塗装作業性の点から、半透明あるいは透明溶液にするこ
とが好ましい。水としてはイオン交換水が好ましく用い
られ、(A)成分、(B)成分、(C)成分の合計量に
対して好ましくは5〜99重量%、より好ましくは20
〜60重量%配合される。この配合量が5重量%未満で
は含有する水が少ないことから一般に水溶性ポリマーと
して称されず、99重量%を超えると塗料として機能し
なくなる傾向がある。Depending on the type and amount of the basic compound and the method of adding water, the form of the obtained aqueous resin composition may be an emulsion, a translucent solution, a transparent solution, etc., but the storage stability,
From the viewpoint of coating workability, a semitransparent or transparent solution is preferable. Ion-exchanged water is preferably used as the water, and is preferably 5 to 99% by weight, more preferably 20% by weight based on the total amount of the components (A), (B) and (C).
-60 wt% is compounded. If the blending amount is less than 5% by weight, the amount of water contained is small, so that it is not generally called as a water-soluble polymer, and if it exceeds 99% by weight, it tends to fail as a coating material.
【0023】本発明に用いられるアルミニウムキレート
としてはアセチルアセトンを適用したアルミニウムアセ
チルアセトナート、アルミニウムアルコキシドとしては
アルミニウムエトキシド、アルミニウムイソプロポキシ
ド(いずれも和光純薬社製)などが挙げられる。アルミ
ニウムキレート及びアルミニウムアルコキシドは併用し
てもよい。Examples of the aluminum chelate used in the present invention include aluminum acetylacetonate to which acetylacetone is applied, and examples of the aluminum alkoxide include aluminum ethoxide and aluminum isopropoxide (all manufactured by Wako Pure Chemical Industries, Ltd.). The aluminum chelate and the aluminum alkoxide may be used in combination.
【0024】アルミニウムキレート及び/又はアルミニ
ウムアルコキシドの使用量は、ポリアミドイミド樹脂1
00重量%に対して0.1〜10重量%の範囲とされ、
好ましくは1〜5重量%とされる。アルミニウムキレー
ト及び/又はアルミニウムアルコキシドの使用量が0.
1重量%未満では、塗膜の密着性が低下し、10重量%
を越えると耐熱性が劣る。The amount of the aluminum chelate and / or the aluminum alkoxide used is the polyamide-imide resin 1
The range is 0.1 to 10% by weight with respect to 00% by weight,
It is preferably 1 to 5% by weight. The amount of aluminum chelate and / or aluminum alkoxide used is 0.
If it is less than 1% by weight, the adhesiveness of the coating film will decrease, and 10% by weight
If it exceeds, the heat resistance becomes poor.
【0025】アルミニウムキレート及び/又はアルミニ
ウムアルコキシドのポリアミドイミド樹脂への添加法に
ついて特に制限はないが、例えばアルミニウムキレート
及び/又はアルミニウムアルコキシド100重量%をジ
メチルホルムアミド、N−メチル−2−ピロリドンなど
の塩基性極性溶媒900〜4000重量%に溶解し、そ
の溶液をポリアミドイミド樹脂の溶液に添加する方法が
ある。There are no particular restrictions on the method of adding the aluminum chelate and / or aluminum alkoxide to the polyamideimide resin. For example, 100% by weight of the aluminum chelate and / or aluminum alkoxide may be added to a base such as dimethylformamide or N-methyl-2-pyrrolidone. There is a method in which the polar solvent is dissolved in 900 to 4000% by weight and the solution is added to the polyamideimide resin solution.
【0026】このようにして得られた耐熱性樹脂組成物
は使用する際に必要に応じて適当な濃度に希釈される。
希釈溶媒としては、水、ジメチルホルムアミド、ジメチ
ルアセトアミド、ジメチルスルフォキシド、N−メチル
−2−ピロリドン等の極性溶媒の他に、助溶媒として、
ポリオール類、これらの低級アルキルエーテル化物、ア
セチル化物等を用いてもよい。例えば、エチレングリコ
ール、ジエチレングリコール、トリエチレングリコー
ル、テトラエチレングリコール、グリセリン、トリメチ
ロールプロパン、イソプロピルアルコール、又はそれら
のモノメチルエーテル化物、モノエチルエーテル、モノ
イソプロピルエーテル化物、モノブチルエーテル化物、
ジメチルエーテル化物及びこれらのモノアセチル化物等
が使用される。The heat-resistant resin composition thus obtained is diluted to an appropriate concentration as needed when it is used.
As a diluting solvent, in addition to polar solvents such as water, dimethylformamide, dimethylacetamide, dimethylsulfoxide and N-methyl-2-pyrrolidone, as a cosolvent,
Polyols, their lower alkyl ether compounds, acetyl compounds, etc. may be used. For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, trimethylolpropane, isopropyl alcohol, or their monomethyl ether compound, monoethyl ether, monoisopropyl ether compound, monobutyl ether compound,
Dimethyl ether compounds and their monoacetyl compounds are used.
【0027】本発明の製造法によって得られる耐熱性樹
脂組成物は耐熱性、電気絶縁性、耐摩耗性及び耐薬品性
等の諸特性に優れ、コイル含浸ワニス、ワイヤエナメ
ル、ワニスクロス類等の電気絶縁用ワニスや、顔料又は
充填剤等と混合して耐熱性電気絶縁用塗料、又は表面仕
上げ剤等の用途に用いることができる。特に、塗料の塗
膜成分として好ましい。The heat-resistant resin composition obtained by the production method of the present invention is excellent in various properties such as heat resistance, electric insulation, abrasion resistance and chemical resistance, and can be used in coil impregnated varnish, wire enamel, varnish cloth and the like. It can be mixed with an electrical insulating varnish, a pigment, a filler or the like and used for a heat resistant electrical insulating coating material or a surface finish. Particularly, it is preferable as a coating film component of paint.
【0028】[0028]
【実施例】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, but it is needless to say that the present invention is not limited to these examples and includes many other embodiments based on the gist of the invention. .
【0029】実施例1
無水トリメリット酸1106.2g、4,4−ジフェニ
ルメタンジイソシアネート1455.8g、N−メチル
−2−ピロリドン2562.0g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
攪拌しながら約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、このまま約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。Example 1 1106.2 g of trimellitic anhydride, 1455.8 g of 4,4-diphenylmethane diisocyanate and 2562.0 g of N-methyl-2-pyrrolidone were placed in a flask equipped with a thermometer, a stirrer and a condenser, and dried. The temperature was gradually raised to 130 ° C. over about 2 hours while stirring in the nitrogen stream. The temperature was kept at 130 ° C while paying attention to the rapid foaming of carbon dioxide gas generated by the reaction, and the heating was continued for about 6 hours and then the reaction was stopped to obtain a polyamideimide resin solution.
【0030】このポリアミドイミド樹脂溶液の不揮発分
(200℃−2h)は約50重量%で、粘度(30℃)
は約85.0Pa・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約17,000で、カルボキシ
ル基及び酸無水物基を開環させたカルボキシル基を合わ
せた酸価は約40であった。なお、数平均分子量は次の
条件にて測定した。
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/minThe polyamide-imide resin solution has a nonvolatile content (200 ° C.-2 h) of about 50% by weight and a viscosity (30 ° C.).
Was about 85.0 Pa · s. The number average molecular weight of the polyamide-imide resin was about 17,000, and the acid value of the combined carboxyl group obtained by ring-opening the carboxyl group and the acid anhydride group was about 40. The number average molecular weight was measured under the following conditions. Model: Hitachi L6000 Detector: Hitachi L4000 type UV Wavelength: 270 nm Data processor: ATT 8 Column: Gelpack GL-S300MDT-5 × 2 Column size: 8 mmφ × 300 mm Solvent: DMF / THF = 1/1 (liter) + phosphorus 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
【0031】このポリアミドイミド樹脂溶液2,700
g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徐々に昇温して5
0℃まで上げた。50℃に達したところでトリエチルア
ミンを447.1g(4当量)添加し、50℃に保ちな
がら十分に攪拌した後、攪拌しながら徐々にイオン交換
水を加えた。最終的にイオン交換水が1348.8g
(30重量%)となるまで加えて、透明で均一な耐熱性
樹脂組成物を得た。上記方法で作製された耐熱性樹脂組
成物100重量%にアルミニウムイソプロポキシド溶液
(和光純薬社製、N−メチル−2−ピロリドン溶液、固
形分濃度10重量%)15重量%を配合し、耐熱性樹脂
組成物を得た。This polyamide-imide resin solution 2,700
g into a flask equipped with a thermometer, stirrer and condenser,
Gradually raise the temperature while stirring in a dry nitrogen stream 5
Raised to 0 ° C. When the temperature reached 50 ° C, 447.1 g (4 equivalents) of triethylamine was added, and after sufficiently stirring while maintaining the temperature at 50 ° C, ion-exchanged water was gradually added while stirring. Finally, deionized water is 1348.8g
(30% by weight), and a transparent and uniform heat resistant resin composition was obtained. 15% by weight of an aluminum isopropoxide solution (Wako Pure Chemical Industries, Ltd., N-methyl-2-pyrrolidone solution, solid content concentration 10% by weight) was added to 100% by weight of the heat-resistant resin composition produced by the above method, A heat resistant resin composition was obtained.
【0032】実施例2
無水トリメリット酸382.9g、4,4′−ジフェニ
ルメタンジイソシアネート503.9g、N−メチル−
2−ピロリドン886.8g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
しながら約1時間かけて徐々に昇温して80℃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80℃を保ち、加熱開始から約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)は約50重量%で、粘度(30℃)は約80.0
Pa・sであった。また、ポリアミドイミド樹脂の数平
均分子量は約15,000で、カルボキシル基及び酸無
水物基を開環させたカルボキシル基を合わせた酸価は約
50であった。このポリアミドイミド樹脂溶液200g
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徐々に昇温して90
℃まで上げた。90℃に達したところでN−メチルモル
ホリンを70.8g(8当量)添加し、90℃に保ちな
がら十分に攪拌した後、攪拌しながら徐々にイオン交換
水を加えた。最終的にイオン交換水が180.5g(4
0重量%)となるまで加えて、透明で均一な耐熱性樹脂
組成物を得た。上記方法で作製された耐熱性樹脂組成物
100重量%にアルミニウムアセチルアセトナート溶液
(和光純薬社製、ジメチルホルムアミド溶液、固形分濃
度5重量%)5重量%を配合し、耐熱性樹脂組成物を得
た。Example 2 382.9 g of trimellitic anhydride, 503.9 g of 4,4'-diphenylmethane diisocyanate, N-methyl-
886.8 g of 2-pyrrolidone was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was gradually raised to 80 ° C over about 1 hour while stirring in a dry nitrogen stream. The temperature was kept at 80 ° C. while paying attention to the rapid foaming of carbon dioxide gas generated by the reaction, the heating was continued for about 7 hours from the start of heating, and then the reaction was stopped to obtain a polyamideimide resin solution.
The nonvolatile content of this polyamide-imide resin solution (200 ° C-
2h) is about 50% by weight and the viscosity (30 ° C) is about 80.0
It was Pa · s. The number-average molecular weight of the polyamide-imide resin was about 15,000, and the combined acid value of the carboxyl groups obtained by ring-opening the carboxyl group and the acid anhydride group was about 50. 200g of this polyamide-imide resin solution
Was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was gradually raised to 90 while stirring in a dry nitrogen stream.
Raised to ℃. When the temperature reached 90 ° C, 70.8 g (8 equivalents) of N-methylmorpholine was added, and the mixture was sufficiently stirred while maintaining the temperature at 90 ° C, and then ion-exchanged water was gradually added while stirring. Finally, 180.5 g (4
0% by weight) to obtain a transparent and uniform heat resistant resin composition. A heat-resistant resin composition was prepared by adding 5% by weight of an aluminum acetylacetonate solution (manufactured by Wako Pure Chemical Industries, dimethylformamide solution, solid content concentration: 5% by weight) to 100% by weight of the heat-resistant resin composition produced by the above method. Got
【0033】実施例3
無水トリメリット酸233.8g、無水ベンゾフェノン
テトラカルボン酸98.0g、4,4′−ジフェニルメ
タンジイソシアネート384.6g、N−メチル−2−
ピロリドン1671.6g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
ながら約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150℃まで上げ、加熱開始から5
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)は約30重量%で、粘度(30
℃)は約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約23,000で、カルボキ
シル基及び酸無水物基を合わせた酸価は約30であっ
た。このポリアミドイミド樹脂溶液200g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徐々に昇温して110℃まで上
げた。110℃に達したところでN,N−ジメチルエタ
ノールアミンを17.6g(6当量)添加し、110℃
に保ちながら十分に攪拌した後、攪拌しながら徐々にイ
オン交換水を加えた。最終的にイオン交換水が217.
6g(50重量%)となるまで加えて、透明で均一な耐
熱性樹脂組成物を得た。上記方法で作製された耐熱性樹
脂組成物100重量%にアルミニウムアセチルアセトナ
ート溶液(和光純薬社製、ジメチルホルムアミド溶液、
固形分濃度10重量%)50重量%を配合し、耐熱性樹
脂組成物を得た。Example 3 233.8 g of trimellitic anhydride, 98.0 g of benzophenone tetracarboxylic acid anhydride, 384.6 g of 4,4'-diphenylmethane diisocyanate, N-methyl-2-
1671.6 g of pyrrolidone was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 120 ° C. over about 1 hour while stirring in a dry nitrogen stream. While paying attention to the rapid bubbling of carbon dioxide gas generated by the reaction, gradually raise the temperature to 150 ° C and start heating 5
After continuing heating for a period of time, the reaction was stopped and a polyamideimide resin solution was obtained. The nonvolatile content (200 ° C-2h) of this polyamide-imide resin solution is about 30% by weight, and the viscosity (30
C.) was about 2.1 Pa.s. Further, the number average molecular weight of the polyamide-imide resin was about 23,000, and the acid value of the combined carboxyl group and acid anhydride group was about 30. 200g of this polyamide-imide resin solution is thermometer,
The mixture was placed in a flask equipped with a stirrer and a condenser, and the temperature was gradually raised to 110 ° C while stirring in a dry nitrogen stream. When the temperature reached 110 ° C, 17.6 g (6 equivalents) of N, N-dimethylethanolamine was added, and the temperature was 110 ° C.
After sufficiently stirring the mixture while keeping it at 1, ion-exchanged water was gradually added while stirring. Finally, the ion-exchanged water was 217.
The amount was 6 g (50% by weight) to obtain a transparent and uniform heat-resistant resin composition. Aluminum acetylacetonate solution (manufactured by Wako Pure Chemical Industries, dimethylformamide solution, 100% by weight of the heat-resistant resin composition prepared by the above method)
A solid content concentration of 10% by weight) was mixed with 50% by weight to obtain a heat resistant resin composition.
【0034】比較例1
無水トリメリット酸876.9g、4,4′−ジフェニ
ルメタンジイソシアネート1153.8g、N−メチル
−2−ピロリドン4,738.3g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
で攪拌しながら約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
注意しながら徐々に昇温して120℃まで上げた。加熱
開始から約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)は約30重量%
で、粘度(30℃)は約1.8Pa・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約21,0
00で、カルボキシル基及び酸無水物基を開環させたカ
ルボキシル基を合わせた酸価は約35であった。このポ
リアミドイミド樹脂溶液2000g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
で攪拌しながら徐々に昇温して90℃まで上げた。90
℃に達したところでN−メチルモルホリンを365.7
g(7当量)添加し、90℃に保ちながら十分に攪拌し
た後、攪拌しながら徐々にイオン交換水を加えた。最終
的にイオン交換水が1577.1g(40重量%)とな
るまで加えて、透明で均一な耐熱性樹脂組成物を得た。Comparative Example 1 876.9 g of trimellitic anhydride, 1153.8 g of 4,4'-diphenylmethane diisocyanate and 4,738.3 g of N-methyl-2-pyrrolidone were used as a thermometer and a stirrer.
Put in a flask equipped with a cooling tube, gradually heat up for about 1 hour while stirring in a dry nitrogen stream, and raise the temperature to 110 ° C.
Raised. The temperature was gradually raised to 120 ° C while paying attention to the rapid foaming of carbon dioxide gas generated by the reaction. After continuing heating for about 8 hours from the start of heating, the reaction was stopped to obtain a polyamideimide resin solution. The nonvolatile content (200 ° C-2h) of this polyamide-imide resin solution is about 30% by weight.
The viscosity (30 ° C.) was about 1.8 Pa · s. The number average molecular weight of the polyamide-imide resin is about 21,0.
At 00, the acid value of the combined carboxyl group obtained by ring-opening the carboxyl group and the acid anhydride group was about 35. 2000 g of this polyamide-imide resin solution was mixed with a thermometer, a stirrer,
The flask was placed in a flask equipped with a cooling tube, and the temperature was gradually raised to 90 ° C. with stirring in a dry nitrogen stream. 90
When the temperature reached ℃, N-methylmorpholine was added to 365.7.
g (7 equivalents) was added, and the mixture was thoroughly stirred while maintaining the temperature at 90 ° C., and then ion-exchanged water was gradually added with stirring. Finally, ion-exchanged water was added to 1577.1 g (40% by weight) to obtain a transparent and uniform heat-resistant resin composition.
【0035】試験例
実施例1、2及び3、及び比較例1に記載の耐熱性樹脂
組成物を基材(アルミニウム板JIS H 4000、厚
み1mm、未研磨)に塗布した後250℃で30分間焼
付けて膜厚薬10μmの塗膜板を作製し、初期及びP.
C.T.劣化後の密着性を測定した。密着性はJIS K
5400に準じて測定し(%、クロスカット残率)、
P.C.T.は121℃、2.2気圧の条件で50及び10
0時間後に測定した。Test Example The heat-resistant resin composition described in Examples 1, 2 and 3 and Comparative Example 1 was applied to a substrate (aluminum plate JIS H 4000, thickness 1 mm, unpolished) and then at 250 ° C. for 30 minutes. After baking, a coated film plate with a film thickness of 10 μm was prepared, and the initial and P.
The adhesion after deterioration of CT was measured. Adhesion is JIS K
Measured according to 5400 (%, cross-cut residual rate),
PCT is 50 and 10 under the condition of 121 ° C and 2.2 atm.
The measurement was performed after 0 hours.
【0036】塗膜特性の耐熱性は、以下の方法で試験を
行った。実施例1、2及び3記載の耐熱性樹脂組成物及
び比較例1記載のポリアミドイミド樹脂溶液をガラス板
上に塗布し、100℃で10分間加熱し、さらに400
℃で15分間加熱して硬化させ、ガラス板から剥離させ
て塗膜を得た。この塗膜で熱重量分析(サンプル量10
mg、昇温速度10℃/分、窒素30ml/分)を行
い、それぞれの塗膜の耐熱性を比較した。試験の結果を
表1に示す。The heat resistance of the coating film characteristics was tested by the following method. The heat-resistant resin composition described in Examples 1, 2 and 3 and the polyamideimide resin solution described in Comparative Example 1 were applied on a glass plate and heated at 100 ° C. for 10 minutes, and further 400
The coating was obtained by heating at 15 ° C for 15 minutes to cure and peeling from the glass plate. Thermogravimetric analysis (sample amount 10
mg, temperature rising rate 10 ° C./min, nitrogen 30 ml / min), and the heat resistance of each coating film was compared. The test results are shown in Table 1.
【0037】[0037]
【表1】 [Table 1]
【0038】表1から、実施例1、2及び3で得られた
耐熱性樹脂組成物から得られる塗膜は比較例1の耐熱性
樹脂組成物から得られる塗膜と比較してP.C.T.劣化
後の密着性が優れていることが分かる。From Table 1, the coating films obtained from the heat-resistant resin compositions obtained in Examples 1, 2 and 3 were compared with the coating films obtained from the heat-resistant resin composition of Comparative Example 1 by P.C. .T. It can be seen that the adhesiveness after deterioration is excellent.
【0039】[0039]
【発明の効果】本発明の水溶性ポリアミドイミド樹脂系
耐熱性樹脂組成物は、イオン交換水含有により有機溶剤
量を低減させたため、環境汚染や作業環境の悪化等の安
全衛生面に対して有利であり、かつ、塗料及び塗膜特性
が良好であり、更に、アルミニウム基材に優れた密着性
を有することから、各種基材への絶縁皮膜をはじめ保護
コート等の各種耐熱塗料用途にも好適に利用することが
できる。EFFECTS OF THE INVENTION The water-soluble polyamideimide resin heat-resistant resin composition of the present invention reduces the amount of organic solvent by containing ion-exchanged water, which is advantageous for safety and hygiene aspects such as environmental pollution and deterioration of working environment. It is also suitable for various heat resistant paint applications such as insulating coatings on various base materials as well as protective coats because it has good paint and coating properties and has excellent adhesion to aluminum base materials. Can be used for.
フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C09D 179/08 C09D 179/08 B Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09D 179/08 C09D 179/08 B
Claims (8)
ネート化合物又はジアミン化合物と三塩基酸無水物又は
三塩基酸無水物クロライドとを反応させて得られるポリ
アミドイミド樹脂と(B)塩基性化合物、(C)水及び
(D)アルミニウムキレート及び/またはアルミニウム
アルコキシドを配合してなる耐熱性樹脂組成物。1. A polyamideimide resin obtained by reacting a diisocyanate compound or a diamine compound with a tribasic acid anhydride or a tribasic acid anhydride chloride in (A) a basic polar solvent, and (B) a basic compound. , (C) water and (D) aluminum chelate and / or aluminum alkoxide.
のポリアミドイミド樹脂中に含まれるカルボキシル基及
びポリアミドイミド樹脂中の酸無水物基を開環させたカ
ルボキシル基を合わせた酸価に対して、1〜20当量配
合されている請求項1記載の耐熱性樹脂組成物。2. An acid value in which the basic compound of the component (B) is a combination of the carboxyl group contained in the polyamideimide resin of the component (A) and the carboxyl group obtained by ring-opening the acid anhydride group in the polyamideimide resin. The heat resistant resin composition according to claim 1, which is blended in an amount of 1 to 20 equivalents.
分及び(C)成分の合計量に対して、5〜99重量%配
合されている請求項1記載の耐熱性樹脂組成物。3. The heat resistant resin according to claim 1, wherein the water as the component (C) is blended in an amount of 5 to 99% by weight based on the total amount of the components (A), (B) and (C). Composition.
5,000〜50,000で、かつ、カルボキシル基及
び酸無水物基を開環させたカルボキシル基を合わせた酸
価が10〜100である請求項1、2又は3記載の耐熱
性樹脂組成物。4. A polyamideimide resin having a number average molecular weight of 5,000 to 50,000 and an acid value of 10 to 100 inclusive of a carboxyl group and a carboxyl group obtained by ring-opening an acid anhydride group. Item 5. A heat resistant resin composition according to item 1 or 2.
ミン又はアルカノールアミンである請求項1、2又は3
記載の耐熱性樹脂組成物。5. The basic compound as the component (B) is an alkylamine or an alkanolamine.
The heat-resistant resin composition as described.
/またはアルミニウムアルコキシドが耐熱性樹脂組成物
100重量%に対して、0.1〜10重量%配合されて
いる請求項1記載の耐熱性樹脂組成物。6. The heat-resistant resin composition according to claim 1, wherein the component (D), an aluminum chelate and / or an aluminum alkoxide, is added in an amount of 0.1 to 10% by weight based on 100% by weight of the heat-resistant resin composition. object.
耐熱性樹脂組成物を塗膜成分としてなる塗料。7. A paint comprising the heat resistant resin composition according to claim 1, 2, 3, 4, 5 or 6 as a coating film component.
載の耐熱性樹脂組成物を塗布、硬化させたアルミニウム
基材。8. An aluminum substrate on which the heat resistant resin composition according to claim 1, 2, 3, 4, 5, 6 or 7 is applied and cured.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001342077A JP2003138134A (en) | 2001-11-07 | 2001-11-07 | Heat-resistant resin composition, coating and aluminum substrate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001342077A JP2003138134A (en) | 2001-11-07 | 2001-11-07 | Heat-resistant resin composition, coating and aluminum substrate |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2003138134A true JP2003138134A (en) | 2003-05-14 |
Family
ID=19155997
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2001342077A Pending JP2003138134A (en) | 2001-11-07 | 2001-11-07 | Heat-resistant resin composition, coating and aluminum substrate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2003138134A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007303670A (en) * | 2006-04-14 | 2007-11-22 | Hitachi Chem Co Ltd | Automobile sliding component and aerosol can each having coating formed of polyamideimide resin based heat resistant resin composition |
JP7021084B2 (en) | 2016-06-27 | 2022-02-16 | 昭和電工マテリアルズ株式会社 | Polyamide-imide resin compositions and paints |
-
2001
- 2001-11-07 JP JP2001342077A patent/JP2003138134A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007303670A (en) * | 2006-04-14 | 2007-11-22 | Hitachi Chem Co Ltd | Automobile sliding component and aerosol can each having coating formed of polyamideimide resin based heat resistant resin composition |
JP7021084B2 (en) | 2016-06-27 | 2022-02-16 | 昭和電工マテリアルズ株式会社 | Polyamide-imide resin compositions and paints |
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