JP3559328B2 - Polyester resin composition for paint and coated steel sheet using the same - Google Patents
Polyester resin composition for paint and coated steel sheet using the same Download PDFInfo
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- JP3559328B2 JP3559328B2 JP32492294A JP32492294A JP3559328B2 JP 3559328 B2 JP3559328 B2 JP 3559328B2 JP 32492294 A JP32492294 A JP 32492294A JP 32492294 A JP32492294 A JP 32492294A JP 3559328 B2 JP3559328 B2 JP 3559328B2
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- Prior art keywords
- polyester resin
- steel sheet
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- resin composition
- acid
- Prior art date
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- 229920001225 polyester resin Polymers 0.000 title claims description 31
- 239000004645 polyester resin Substances 0.000 title claims description 31
- 239000000203 mixture Substances 0.000 title claims description 15
- 229910000831 Steel Inorganic materials 0.000 title claims description 14
- 239000010959 steel Substances 0.000 title claims description 14
- 239000003973 paint Substances 0.000 title description 8
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 21
- 229920003180 amino resin Polymers 0.000 claims description 15
- 150000002009 diols Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000000539 dimer Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- -1 isocyanate compound Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は硬度、加工性、及び耐汚染性に優れ、かつ特に耐候性に優れた塗膜が得られる塗料用ポリエステル樹脂組成物及びそれを用いた塗装鋼板に関するものである。
【０００２】
【従来の技術】
近年、冷蔵庫、電子レンジ等の家電製品の用途を中心として、あらかじめ鋼板に塗装を施した後、加工、成形を行うプレコート鋼板の用途が拡大している。プレコート鋼板に用いられる塗料は、光沢、密着性、耐候性等の特性の他に加工性と硬度という相反する特性が要求される。従来、このような相反する特性を解決するために、共重合ポリエステル樹脂とアミノ樹脂またはイソシアネート化合物とを組み合わせた樹脂組成物が多く用いられており、ある程度硬度と加工性のバランスは改善され実用化されている例もある。しかしながら従来のポリエステル樹脂組成物では、硬度、加工性、耐汚染性といった性能は満足してもエアーコンディショナー等の屋外で使用されるものの用途に要求される耐候性を同時に満足させることは困難であった。また耐候性が満足できるような樹脂組成物であれば、その他の諸性能のバランスが取れにくくなるという問題が生じた。
【０００３】
【発明が解決しようとする課題】
このような状況に鑑み、本発明の課題は、硬度、加工性及び耐汚染性に優れ、かつ特に耐候性に優れた塗膜が得られる塗料用ポリエステル樹脂及びそれを用いた塗装鋼板を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題を達成すべく鋭意検討を重ねた結果、特定の成分組成よりなるポリエステル樹脂にアミノ樹脂を特定量配合してなる樹脂組成物は上述の課題を解決するものであることを見いだし、本発明を完成するに至った。
【０００５】
すなわち、本発明の要旨は、第１に、酸成分の少なくとも８０モル％が芳香族ジカルボン酸であり、かつジオール成分のうち０．１〜１０モル％が下記式（１）で示される水添型ダイマージオールであり、数平均分子量が１０，０００〜２５，０００で、ガラス転移温度が１０〜５０℃であるポリエステル樹脂９０〜６０重量部に対して、アミノ樹脂を１０〜４０重量部で配合してなる塗料用ポリエステル樹脂組成物である。
【０００６】
【化２】
また、第２に、この塗料用ポリエステル樹脂組成物を鋼板上に焼付け塗装してなる塗装鋼板である。
【０００８】
以下本発明を詳細に説明する。
本発明において、ポリエステル樹脂における芳香族ジカルボン酸としては、テレフタル酸、イソフタル酸、無水フタル酸、ナフタレンジカルボン酸等が挙げられるが、十分な塗膜強度、塗膜硬度を得るためにテレフタル酸又はイソフタル酸を用いることが好ましい。これらの芳香族ジカルボン酸の含有量は、硬度、耐候性、耐汚染性の面から酸成分の少なくとも８０モル％は必要である。
【０００９】
芳香族ジカルボン酸と併用しうる他の酸成分としてはアジピン酸、セバシン酸、コハク酸、アゼライン酸、１、４−シクロヘキサンジカルボン酸等の脂肪族カルボン酸があげられるが、これらのカルボン酸の含量は全酸成分中の２０モル％未満とする必要がある。この量が２０モル％以上であると硬度の低下は言うまでもないが、耐候性、耐汚染性の低下が著しい。
【００１０】
また、ポリエステル樹脂のジオール成分の０．１〜１０モル％、好ましくは３〜６モル％を式（１）で示される水添型ダイマージオールを用いる。水添型ダイマージオールの量が０．１モル％未満であると鮮映性に優れた塗膜が得られるものの、加工性ばかりでなく目的とする耐候性の性能が不十分である。またこの量が１０モル％を超えると目的とする耐候性は満足するものの、鮮映性の低下及び硬度の低下が著しく塗膜性能のバランスが大きく崩れる。
【００１１】
また本発明で併用しうるその他のジオール成分としては各種公知のものが使用でき、具体的にはエチレングリコール、ネオペンチルグリコール、プロピレングリコール、１、３−ブタンジオール、１、４−ブタンジオール、１、５−ペンタンジオール、１、６−ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、１、４−シクロヘキサンジメタノール等が挙げられる。
また３価以上のポリオールを使用することも任意であるが、ポリオール成分中５モル％以下とするのが好ましい。５モル％を超えて使用すると加工性が低下する傾向にある。３価以上のポリオールとしてはトリメチロールプロパン、トリメチロールエタン、グリセリン、ペンタエリスリトール等が挙げられる。
【００１２】
本発明におけるポリエステル樹脂は以上述べた酸成分及びジオール成分を満足するものであるばかりでなく、数平均分子量が１０，０００〜２５，０００で、かつガラス転移温度が１０〜５０℃という特性を満足するものである必要がある。数平均分子量が１０，０００未満であると塗膜は脆弱となり加工性が低下し、２５，０００を超えると耐汚染性及び耐候性が低下する。またガラス転移温度が１０℃未満であると加工性を除くその他の物性が共に低下し、５０℃を超えると加工性が不十分となる。
【００１３】
本発明におけるポリエステル樹脂は、公知の重合法すなわちエステル交換または直接エステル化とそれに続く溶融重縮合反応にて製造可能であり、その際使用される触媒も同様である。
【００１４】
また、上記ポリエステル樹脂に対して、アミノ樹脂を配合する。アミノ樹脂は硬化剤として作用する。アミノ樹脂としては、例えばメラミン、尿素、ベンゾグアナミン等のアミン成分とホルムアルデヒドとの縮合物、及び該縮合物をメタノール、エタノール、ブタノール等の低級アルコールでエーテル化して得られるエーテル化物が挙げられ、末端がメチル基でエーテル化されたメラミン樹脂が最も好適に用いられる。この樹脂は、性能のバランスを取るのに好適である。自己縮合反応が極めて少なくかつ、架橋密度の高い塗膜が得られる。この樹脂の末端のエーテル化度としてはｎ＝３〜６が好ましい。
【００１５】
本発明において、ポリエステル樹脂とアミノ樹脂の配合比は固形分重量比で９０／１０〜６０／４０、好ましくは８０／２０〜７０／３０である。ポリエステルの割合が９０重量％を超えると目的とする耐候性が不足して好ましくない。また６０重量％未満であると加工性が劣り、性能のバランスがとれなくなる。
さらに、本発明の塗料用ポリエステル樹脂組成物には任意の硬化触媒を添加することができる。硬化触媒としてはｐ−トルエンスルホン酸、ドデシルベンゼンスルホン酸が挙げられ、使用量としては前記アミノ樹脂に対して１〜５重量％が適当である。
さらに、本発明の組成物には目的、用途に応じて顔料、分散剤、酸化防止剤、レベリング剤、紫外線吸収剤等の添加剤を使用することができる。
【００１６】
上記のポリエステル樹脂、アミノ樹脂及びその他の添加物を溶媒に加えて、塗料とする。溶剤としては、ポリエステル樹脂及びアミノ樹脂を希釈可能な溶剤であればなんら制限なく使用可能である。例えば、トルエン、キシレン、ソルベッソ１００、ソルベッソ１５０等の芳香族系炭化水素、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族系炭化水素、他に酢酸エチル、酢酸ブチル、メチルセロソルブ、ブチルセロソルブ、メチルエチルケトン、シクロヘキサノン、ブタノール、オクタノール等の溶剤がその溶解性、蒸発速度によって任意に選択されうる。
【００１７】
溶媒として、一般的には高沸点溶剤を２〜３種類以上混合して使用することが望ましく、特にワキ、ピンホール等の塗膜欠陥を生じないような溶剤としては、芳香族系炭化水素あるいは脂肪族系炭化水素を７０〜３０重量部、エステル類、ケトン類等の極性溶媒を３０〜７０重量部の割合で混合し使用することが望ましい。
【００１８】
塗装方法は、カーテンフロー塗装、ロール塗装、スプレー塗装、静電スプレー塗装方法を用い、冷延鋼板、亜鉛メッキ鋼板、、ステンレス鋼板等への焼付け塗装が可能であり、通常焼付け後の乾燥膜厚が１０〜３０μｍになるよう塗装する。
塗装後の塗膜の焼付け条件としては、塗料が硬化する温度及び焼付け時間は適宜選択できるが、本発明のねらいであるプレコートメタル分野においては通常１５０〜２５０℃で３０〜１２０秒間、特に１８０〜２３０℃で５０〜９０秒間が望ましい。
このようにして焼付け塗装された塗装鋼板はそれだけでも目的とする諸性能を有しているが、特に耐蝕性を要求される用途に対してはプライマーをあらかじめ３〜１０μｍ焼付けておくことが好ましい。
【００１９】
【実施例】
以下、本発明を実施例にて具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、各例中、部は表記しない限りすべて重量基準である。また、各試験方法については次に示す。
【００２０】
（ａ）光沢
６０℃反射光沢保持率を測定した。
【００２１】
（ｂ）鉛筆硬度
塗装鋼板の塗面を、ＪＩＳ Ｋ−５４００に準じて鉛筆引っかき試験を行い、キズがつかない硬度を測定した。
【００２２】
（ｃ）加工性
５℃の環境下、塗面を外側にして試験板を１８０°折り曲げて、折り曲げ部分にワレが発生しなくなるＴ数を表示した。Ｔ数とは、折り曲げ部分の内側に何もはさまずに、１８０°折り曲げを行った場合を０Ｔ、試験板と同じ厚さの板を１枚はさんで折り曲げた場合１Ｔ、２枚の場合２Ｔとした。
【００２３】
（ｄ）耐候性
サンシャインウェザーメータを用いて１０００時間照射後の光沢（６０°鏡面反射率）を初期の光沢に対する１００分率で示した。
【００２４】
（ｅ）耐汚染性
マジックインキ（赤）で塗面に線を引き、室温で２４時間放置後、エタノールを含浸したガーゼで拭き取った時の汚れの程度を５段階に分けて判定した。
５：マジックインキの痕が全く残らない
４：マジックインキの痕がわずかに残る
３：マジックインキの痕がかなり残る
２：マジックインキの痕が濃く残る
１：マジックインキが拭き取れない
【００２５】
（１）製造例１
温度計、窒素導入管、真空装置及び攪はん装置をつけたフラスコにテレフタル酸８３．０部、イソフタル酸６６．４部、セバシン酸２０．２部、エチレングリコール７４．７部、ネオペンチルグリコール８７．６部、前記式の水添型ダイマージオール１５．１部及び反応触媒として酢酸亜鉛０．４部を仕込み、１７０℃から２２０℃まで４時間かけて徐々に昇温させエステル交換反応を行った。次に６０分かけて５ｍｍＨｇまで減圧し、さらに１〜３ｍｍＨｇの減圧下２３０℃〜２５０℃で２時間重縮合反応を行った。これにより数平均分子量１５、０００、ガラス転移温度（Ｔｇ）４０℃である飽和ポリエステル樹脂（Ａ）が得られた。
【００２６】
（２）製造例２〜４
製造例１に準じて、表１に示した成分組成及び数平均分子量、ガラス転移温度を有する飽和ポリエステル樹脂Ｂ、Ｃ、Ｄ、Ｅを製造した。なお、表１中の酸成分及びジオール成分の単位は各成分におけるモル％である。
【００２７】
（３）比較製造例１〜４
製造例１に準じて、表１に示した組成及び数平均分子量、ガラス転移温度を有する飽和ポリエステル樹脂Ｅ、Ｆ、Ｇ、Ｈを製造した。比較製造例１〜３は本発明においてポリエステル樹脂のモノマーとして不可欠な水添型ダイマージオールが含まれていない場合であり、比較製造例４は水添型ダイマージオールの含量が好ましい適量を越えている場合である。
【００２８】
【表１】
実施例１〜４及び比較例１〜４
得られた共重合ポリエステルＡ〜Ｈを各々シクロヘキサノン／ソルベッソ１５０混合溶液（重量比５０／５０）に溶解し、不揮発分３０％に調製した。上記ポリエステル樹脂溶液１０７部、酸化チタン（商標名：タイペークＣＲ−５０、石原産業製）３８部、ヘキサメトキシメチロールメラミン（商標名：サイメル３０３、不揮発分９８％、住友化学工業製）８部、レベリング剤（商標名：ミキレベリング、共栄社油脂化学工業製）２部、硬化触媒（商標名：キャタリスト４０４０）０．２部、シクロヘキサノン／ソルベッソ１５０（１：１）混合溶液３０部をペイントシェーカーを使用して１時間分散混練して塗料〔ポリエステル樹脂：アミノ樹脂＝８：２（固形分重量）〕を製造した。得られた塗料を厚さ０．７ｍｍのリン酸亜鉛処理軟鋼板（商標名：ボンデ鋼板、日本テストパネル社製）上に乾燥膜厚１５〜２０ミクロンとなるように塗装し、軟鋼板の最終到達温度が２２０℃になるように６０秒間熱風乾燥機で焼付けを行った。得られた塗膜の特性を、前記の試験方法により試験した。評価結果を表２に示す。
【００３０】
比較例５
ポリエステル樹脂とアミノ樹脂の配合割合を１：１（ポリエステル樹脂２０部、アミノ樹脂２０部）とする他は実施例１と同様にして塗料を作製し、焼付け塗装した。得られた塗膜の特性を表２に示す。
【００３１】
比較例６
アミノ樹脂を用いない（ポリエステル樹脂４０部）とする他は実施例１と同様にして塗料を作製し、焼付け塗装した。得られた塗膜の特性を表２に示す。
【００３２】
【表２】
【発明の効果】
本発明の塗料用ポリエステル樹脂組成物を用いると、硬度、加工性及び耐汚染性に優れ、従来のポリエステル樹脂の欠点でもあった耐候性に特に優れた塗膜が得られ、この塗膜が鋼板上に形成された塗装鋼板はこれらの特性に優れたものである。[0001]
[Industrial applications]
TECHNICAL FIELD The present invention relates to a polyester resin composition for paint which is excellent in hardness, workability, and stain resistance, and in particular, can provide a coating film having excellent weather resistance, and a coated steel sheet using the same.
[0002]
[Prior art]
2. Description of the Related Art In recent years, the use of precoated steel sheets, in which steel sheets are painted in advance, then processed and formed, has been expanding, mainly for use in home electric appliances such as refrigerators and microwave ovens. The paint used for the precoated steel sheet is required to have not only properties such as gloss, adhesion, and weather resistance, but also conflicting properties such as workability and hardness. Conventionally, in order to solve such contradictory properties, a resin composition combining a copolyester resin and an amino resin or an isocyanate compound has been often used. There are also examples. However, conventional polyester resin compositions can be used outdoors, such as air conditioners, but cannot satisfy the weather resistance required for the application at the same time, even though the properties such as hardness, workability, and stain resistance are satisfied. Was. In addition, if the resin composition has satisfactory weather resistance, a problem arises in that it is difficult to balance other properties.
[0003]
[Problems to be solved by the invention]
In view of such a situation, an object of the present invention is to provide a polyester resin for paint capable of obtaining a coating film having excellent hardness, workability and stain resistance, and particularly having excellent weather resistance, and a coated steel sheet using the same. It is in.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, a resin composition obtained by mixing a specific amount of an amino resin with a polyester resin having a specific component composition solves the above-described problems. This led to the completion of the present invention.
[0005]
That is, the gist of the present invention is that, first, at least 80 mol% of the acid component is an aromatic dicarboxylic acid, and 0.1 to 10 mol% of the diol component is hydrogenated represented by the following formula (1). An amino resin is blended in an amount of 10 to 40 parts by weight with respect to 90 to 60 parts by weight of a polyester resin having a number average molecular weight of 10,000 to 25,000 and a glass transition temperature of 10 to 50 ° C. And a polyester resin composition for coatings.
[0006]
Embedded image
Secondly, there is provided a coated steel sheet obtained by baking the polyester resin composition for coating onto a steel sheet.
[0008]
Hereinafter, the present invention will be described in detail.
In the present invention, examples of the aromatic dicarboxylic acid in the polyester resin include terephthalic acid, isophthalic acid, phthalic anhydride, and naphthalenedicarboxylic acid. Preferably, an acid is used. The content of these aromatic dicarboxylic acids is required to be at least 80 mol% of the acid component in view of hardness, weather resistance and stain resistance.
[0009]
Other acid components that can be used in combination with the aromatic dicarboxylic acid include aliphatic carboxylic acids such as adipic acid, sebacic acid, succinic acid, azelaic acid, and 1,4-cyclohexanedicarboxylic acid, and the content of these carboxylic acids. Should be less than 20 mol% of the total acid component. When the amount is 20 mol% or more, the hardness is obviously reduced, but the weather resistance and stain resistance are significantly reduced.
[0010]
Also, 0.1 to 10 mol%, preferably 3 to 6 mol% of the diol component of the polyester resin is a hydrogenated dimer diol represented by the formula (1). When the amount of the hydrogenated dimer diol is less than 0.1 mol%, a coating film having excellent clarity can be obtained, but not only the workability but also the intended weather resistance performance is insufficient. If this amount exceeds 10 mol%, the desired weather resistance is satisfied, but the sharpness and hardness are significantly reduced, and the balance of the coating film performance is greatly lost.
[0011]
Various other known diol components that can be used in the present invention can be used. Specifically, ethylene glycol, neopentyl glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, , 5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol and the like.
It is also optional to use a polyol having a valency of 3 or more, but it is preferably 5 mol% or less in the polyol component. If it is used in an amount exceeding 5 mol%, the processability tends to decrease. Examples of the trivalent or higher polyol include trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol.
[0012]
The polyester resin in the present invention not only satisfies the above-mentioned acid component and diol component, but also has a number average molecular weight of 10,000 to 25,000 and a glass transition temperature of 10 to 50 ° C. Need to be When the number average molecular weight is less than 10,000, the coating film becomes brittle and the workability decreases, and when it exceeds 25,000, the stain resistance and weather resistance decrease. When the glass transition temperature is less than 10 ° C., all the other physical properties except the workability are reduced, and when it exceeds 50 ° C., the workability becomes insufficient.
[0013]
The polyester resin in the present invention can be produced by a known polymerization method, that is, transesterification or direct esterification followed by a melt polycondensation reaction, and the catalyst used in this case is also the same.
[0014]
An amino resin is blended with the polyester resin. The amino resin acts as a curing agent. Examples of the amino resin include melamine, urea, a condensate of an amine component such as benzoguanamine and formaldehyde, and an etherified product obtained by etherifying the condensate with a lower alcohol such as methanol, ethanol and butanol. Melamine resins etherified with methyl groups are most preferably used. This resin is suitable for balancing performance. A coating film having a very low self-condensation reaction and a high crosslinking density can be obtained. The degree of etherification at the terminal of the resin is preferably n = 3 to 6.
[0015]
In the present invention, the compounding ratio of the polyester resin and the amino resin is 90/10 to 60/40, preferably 80/20 to 70/30 in terms of solid content weight ratio. If the proportion of the polyester exceeds 90% by weight, the intended weather resistance is insufficient, which is not preferable. On the other hand, if it is less than 60% by weight, workability is inferior and performance cannot be balanced.
Further, an optional curing catalyst can be added to the polyester resin composition for coating of the present invention. Examples of the curing catalyst include p-toluenesulfonic acid and dodecylbenzenesulfonic acid. An appropriate amount is 1 to 5% by weight based on the amino resin.
Furthermore, additives such as a pigment, a dispersant, an antioxidant, a leveling agent, and an ultraviolet absorber can be used in the composition of the present invention depending on the purpose and application.
[0016]
The above polyester resin, amino resin and other additives are added to a solvent to form a paint. As the solvent, any solvent can be used as long as it can dilute the polyester resin and the amino resin. For example, aromatic hydrocarbons such as toluene, xylene, Solvesso 100 and Solvesso 150, aliphatic hydrocarbons such as hexane, heptane, octane, decane, and others, ethyl acetate, butyl acetate, methyl cellosolve, butyl cellosolve, methyl ethyl ketone, and cyclohexanone , Butanol, octanol and the like can be arbitrarily selected depending on their solubility and evaporation rate.
[0017]
As the solvent, it is generally desirable to use a mixture of two or more kinds of high-boiling solvents. Particularly, as a solvent which does not cause coating defects such as armpits and pinholes, aromatic hydrocarbons or It is desirable to use 70 to 30 parts by weight of an aliphatic hydrocarbon and 30 to 70 parts by weight of a polar solvent such as an ester or a ketone.
[0018]
The coating method is curtain flow coating, roll coating, spray coating, electrostatic spray coating, and can be baked on cold rolled steel sheet, galvanized steel sheet, stainless steel sheet, etc., and usually dry film thickness after baking Is applied so as to be 10 to 30 μm.
As the baking conditions of the coated film after the coating, the temperature at which the coating is cured and the baking time can be appropriately selected. Desirably at 230 ° C. for 50 to 90 seconds.
Although the coated steel sheet thus baked has the desired various properties by itself, it is preferable to bake the primer in advance by 3 to 10 μm in particular for applications requiring corrosion resistance.
[0019]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In each example, all parts are by weight unless otherwise indicated. Each test method is described below.
[0020]
(A) Gloss The reflection gloss retention at 60 ° C. was measured.
[0021]
(B) Pencil hardness A pencil scratch test was performed on the painted surface of the coated steel sheet according to JIS K-5400, and the hardness at which no scratches were formed was measured.
[0022]
(C) Workability In an environment of 5 ° C., the test plate was bent 180 ° with the coated surface facing outward, and the T number at which no cracks occurred in the bent portion was indicated. The T number is 0T when 180 ° bending is performed without putting anything inside the bent portion, 1T when two plates of the same thickness as the test plate are bent and 1T and two sheets 2T.
[0023]
(D) Weather resistance The gloss (60 ° specular reflectance) after irradiation for 1000 hours using a sunshine weather meter was expressed as a percentage of the initial gloss.
[0024]
(E) Stain resistance A line was drawn on the coated surface with the magic ink (red), left for 24 hours at room temperature, and the degree of stain when wiped with gauze impregnated with ethanol was determined in five stages.
5: No trace of magic ink remains 4: Slight trace of magic ink 3: Severe trace of magic ink 2: Slight trace of magic ink remains 1: Magic ink cannot be wiped off
(1) Production Example 1
83.0 parts of terephthalic acid, 66.4 parts of isophthalic acid, 20.2 parts of sebacic acid, 74.7 parts of ethylene glycol, 74.7 parts of neopentyl glycol in a flask equipped with a thermometer, a nitrogen inlet tube, a vacuum device and a stirring device. 87.6 parts, 15.1 parts of the hydrogenated dimer diol of the above formula and 0.4 parts of zinc acetate as a reaction catalyst were charged, and the temperature was gradually raised from 170 ° C. to 220 ° C. over 4 hours to carry out a transesterification reaction. Was. Next, the pressure was reduced to 5 mmHg over 60 minutes, and the polycondensation reaction was further performed at 230 ° C to 250 ° C for 2 hours under a reduced pressure of 1 to 3 mmHg. As a result, a saturated polyester resin (A) having a number average molecular weight of 15,000 and a glass transition temperature (Tg) of 40 ° C. was obtained.
[0026]
(2) Production Examples 2 to 4
According to Production Example 1, saturated polyester resins B, C, D, and E having the component compositions, number average molecular weights, and glass transition temperatures shown in Table 1 were produced. In addition, the unit of the acid component and the diol component in Table 1 is mol% in each component.
[0027]
(3) Comparative Production Examples 1-4
According to Production Example 1, saturated polyester resins E, F, G, and H having the composition, number average molecular weight, and glass transition temperature shown in Table 1 were produced. Comparative Production Examples 1 to 3 are cases in which the hydrogenated dimer diol which is indispensable as a monomer of the polyester resin in the present invention is not included, and Comparative Production Example 4 has a hydrogenated dimer diol content exceeding a preferable suitable amount. Is the case.
[0028]
[Table 1]
Examples 1-4 and Comparative Examples 1-4
The obtained copolymerized polyesters A to H were each dissolved in a mixed solution of cyclohexanone / solvesso 150 (weight ratio: 50/50) to prepare a nonvolatile content of 30%. 107 parts of the above polyester resin solution, 38 parts of titanium oxide (trade name: Taipaque CR-50, manufactured by Ishihara Sangyo), 8 parts of hexamethoxymethylol melamine (trade name: Cymel 303, 98% non-volatile content, manufactured by Sumitomo Chemical), leveling 2 parts of an agent (trade name: Miki Leveling, manufactured by Kyoeisha Yushi Kagaku Kogyo), 0.2 parts of curing catalyst (trade name: Catalyst 4040), 30 parts of a mixed solution of cyclohexanone / solvesso 150 (1: 1) using a paint shaker Then, the mixture was dispersed and kneaded for 1 hour to prepare a coating material [polyester resin: amino resin = 8: 2 (weight of solid content)]. The obtained paint is applied on a 0.7 mm-thick zinc phosphate-treated mild steel sheet (trade name: Bonde steel sheet, manufactured by Nippon Test Panel Co.) so as to have a dry film thickness of 15 to 20 μm. Baking was performed with a hot air drier for 60 seconds so that the ultimate temperature was 220 ° C. The properties of the obtained coating film were tested by the test method described above. Table 2 shows the evaluation results.
[0030]
Comparative Example 5
A coating material was prepared and baked in the same manner as in Example 1 except that the mixing ratio of the polyester resin and the amino resin was 1: 1 (20 parts of the polyester resin and 20 parts of the amino resin). Table 2 shows the properties of the obtained coating film.
[0031]
Comparative Example 6
A paint was prepared and baked in the same manner as in Example 1 except that the amino resin was not used (polyester resin 40 parts). Table 2 shows the properties of the obtained coating film.
[0032]
[Table 2]
【The invention's effect】
By using the polyester resin composition for coating of the present invention, a coating film excellent in hardness, workability and stain resistance, particularly excellent in weather resistance, which was also a disadvantage of the conventional polyester resin, is obtained. The coated steel sheet formed above has excellent properties.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32492294A JP3559328B2 (en) | 1994-12-27 | 1994-12-27 | Polyester resin composition for paint and coated steel sheet using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32492294A JP3559328B2 (en) | 1994-12-27 | 1994-12-27 | Polyester resin composition for paint and coated steel sheet using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08176419A JPH08176419A (en) | 1996-07-09 |
| JP3559328B2 true JP3559328B2 (en) | 2004-09-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32492294A Expired - Fee Related JP3559328B2 (en) | 1994-12-27 | 1994-12-27 | Polyester resin composition for paint and coated steel sheet using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3559328B2 (en) |
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1994
- 1994-12-27 JP JP32492294A patent/JP3559328B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH08176419A (en) | 1996-07-09 |
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