CN100500725C - 经ε-己内酰胺和DIPA或1,2,4-三唑混合封闭的多异氰酸酯及其制备和应用 - Google Patents
经ε-己内酰胺和DIPA或1,2,4-三唑混合封闭的多异氰酸酯及其制备和应用 Download PDFInfo
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Abstract
本发明涉及通过混合封闭的多异氰酸酯,它们的生产及其在涂层和保护层中作为交联剂成分的应用,优选用于可深拉的抗腐蚀烤漆,特别是用于卷材涂漆法。
Description
本发明涉及混合封闭的多异氰酸酯,其制备和作为涂膜和涂层交联组分的应用,优选用于可深拉和抗腐蚀烤漆,特别可用于卷材涂漆工艺(Coil-Coating-Verfahren)。
将封闭的多异氰酸酯与含OH的缩聚物或聚合物(聚酯或聚丙烯酸酯)配制成用于“单组分”烤漆的粘合剂是现有技术中已知的。采用ε-己内酰胺、二异丙基胺(DIPA)和1,2,4-三唑来封闭异氰酸酯基团也是已知的。
当今,通常是使未涂覆的金属板变形,组装起来形成车体并在电泳浴中给它们提供底漆。
另一种可能性是给金属板在制备后提供适当的底漆并临时贮存该涂覆的卷材。当采用事先涂覆的金属板生产车体时,所述涂层必须要经过金属板的每一种变形而无损坏。
本发明的目的是提供一种具有很好的可变形性和良好的抗腐蚀保护的卷材涂料。
现已发现,就以此方式生产的烤漆涂料而言,封闭剂ε-己内酰胺、DIPA和1,2,4-三唑的特定组合产生了特殊效果,即室温下的可深拉性能和由此制备的涂层老化后的抗撕裂性能。
本发明涉及混合封闭的多异氰酸酯,其含有:
A1)40-70当量%主要为直链的NCO预聚物,其NCO含量为5.0-10.0重量%,
A2)30-60当量%脂肪族涂料用多异氰酸酯,
B1)30-60当量%的ε-己内酰胺,和
B2)40-70当量%作为封闭剂的二异丙基胺或1,2,4-三唑,
其中异氰酸酯组分A1)和A2)的当量百分数之和为100当量%,封闭剂B1)和B2)的当量百分数之和为100-110当量%。
对本发明而言,重要的是将具有弹性效果的NCO预聚物(A1)和高度支化的涂料用多异氰酸酯(A2)的混合物用做多异氰酸酯组分并将ε-己内酰胺(B1)和在低温下解离的封闭剂二异丙基胺(DIPA)或1,2,4-三唑(B2)的混合物用做封闭剂。
为制备NCO预聚物组分A1),使二异氰酸酯与二羟基化合物和少量的三羟基化合物以已知方式反应。就本发明选择的NCO预聚物而言,100当量%的二异氰酸酯与40-45当量%的二羟基化合物和5-10当量%的三羟基化合物反应。本发明合适的二异氰酸酯包括例如1,6-二异氰酸根合己烷(HDI),1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI),二-(4-异氰酸根合环己基)甲烷(H12MDI或Desmodur /Bayer AG),2,6-或2,5-二-异氰酸根合降冰片烷或1,4-二-异氰酸根合甲基-环己烷和1,3-或1,4-四甲基亚二甲苯基二异氰酸酯,以及芳族二异氰酸酯例如2,4-和2,6-亚甲苯基二异氰酸酯(TDI)或4,4’-和2,4’-二异氰酸根合二苯基甲烷(MDI)。优选IPDI。
合适的二羟基化合物包括聚氨酯化学中已知的直链聚酯、聚碳酸酯和聚醚,其数均分子量为500-3000。优选的二羟基化合物是数均分子量为1700的己二酸/新戊基二醇/1,6-己二醇聚酯与以双酚A起始并具有550的数均分子量的聚环氧丙烷聚醚的混合物。此外,可以使用数均分子量为62-400的低分子量二醇如新戊基二醇或三甲基戊二醇-1,3以提高NCO预聚物的NCO含量。
如上所述,少量的三官能度羟基化合物也可以用来提高NCO预聚物的抗溶剂性能。实例包括三羟甲基丙烷或以三羟甲基丙烷起始且数均分子量为250-1000的环氧丙烷聚醚。设计NCO预聚物A1)使其具有5.0-10.0重量%的NCO含量。
组分A2)是本身已知的涂料用多异氰酸酯,其含有缩二脲基、异氰酸酯基、脲基甲酸酯基、亚氨基噁二嗪二酮(不对称的三聚体)基、氨基甲酸乙酯基和/或Uretdion基团,所述多异氰酸酯基于(环)脂肪族二异氰酸酯并具有12-25重量%的NCO含量。脂肪族和脂环族二异氰酸酯的实例包括1,6-二异氰酸根合己烷(HDI)、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI)、二-(4-异氰酸根合环己基)甲烷(H12MDI或Desmodur /Bayer AG)、2,6-和2,5-二-异氰酸根合降冰片烷、1,4-二-异氰酸根合甲基-环己烷和1,3-和1,4-四甲基亚二甲苯基二异氰酸酯。优选基于1,6-二异氰酸根合己烷、IPDI和Desmodur 并主要含有异氰脲酸酯基团的多异氰酸酯。
以这样的方式设计组分A1)+A2)的总NCO含量,即柔性NCO预聚物组分A1)占约85重量%和高官能度涂料用多异氰酸酯A2)占约15重量%。基于NCO基团的含量,改变这一比率使之有利于涂料用多异氰酸酯A2)。例如,如果总的NCO含量A1)+A2)为8.5%,则NCO预聚物A1)仅占约62%,而涂料用多异氰酸酯A2)占约38%。
ε-己内酰胺(B1)和1,2,4-三唑(B2)或二异丙基胺(B2)用做混合封闭剂。封闭剂B1:B2的比率优选为0.3-0.5:0.7-0.5,其中B1和B2之和为1.0摩尔,对应于封闭1摩尔或1 Val的NCO基团。
以如下方式生产本发明的封闭多异氰酸酯:首先,在室温下加入二异氰酸酯起始物料,例如IPDI,然后在搅拌下加入OH组分,例如聚酯、聚醚、二醇和三醇,通过加热至100-110℃引发过量的NCO基团与OH组分的反应,并且,当达到或基本达到NCO含量计算值时,使反应终止,以制备NCO预聚物(A1)。在接下来的步骤中,用溶剂,例如溶剂石脑油100或1-甲氧基丙基乙酸酯稀释制得的NCO预聚物,并加入涂料用多异氰酸酯A2),例如HDI三聚物以形成所有NCO组分A1)+A2)和为了进行混合封闭,首先用ε-己内酰胺(B1)在100-110℃进行部分封闭直至达到NCO含量计算值,然后使其余的NCO基团与1,2,4-三唑或二异丙基胺反应。
与1,2,4-三唑的反应是吸热的,需要约100℃的反应温度。相反,与二异丙基胺的反应是放热的,这样只需40℃-80℃的温度就能完成反应。当NCO基团的封闭完成后,本发明的封闭多异氰酸酯就生成了并可以用含羟基溶剂如异丁醇或丁二醇稀释至操作粘度。
本发明的混合封闭的多异氰酸酯用来在由木材、金属、玻璃、陶瓷和塑料制成的基材上形成涂层。优选用它们制备用于卷材涂料的底漆。
除了良好的抗腐蚀性能(盐雾试验)以外,可以采用例如本发明的混合封闭多异氰酸酯制备的卷材涂料底漆首先具有柔性和优越的粘附力,这可以通过该方式涂覆的金属板的无损深拉性能得到证实。因为本发明的封闭多异氰酸酯优选具有脂肪族特征,即它们只含有脂肪族多异氰酸酯,涂覆了底漆的卷材可以在进一步加工前贮存,甚至是在室外贮存而底漆不会发生所谓的粉化即光致破裂。使用以此方式涂覆了底漆的金属板,在例如汽车制造中可以省去阴极浸渍涂布(KTL)。
实施例
实施例1(根据本发明)
描述了混合封闭的多异氰酸酯。后者由0.625当量%的NCO预聚物组分A1),0.375当量%的涂料用多异氰酸酯组分A2),0.375当量%的封闭剂ε-己内酰胺(B1)和0.625当量%的1,2,4-三唑(B2)组成。
配方:
组分A1)
组分A2)
118.0克(0.6当量) 基于1,6-二异氰酸根合-己烷(HDI),NCO含
量为21.4%的含异氰脲酸酯的涂料用多异氰
酸酯,在23℃粘度为约3000mPas且官能度
为约3.5
392.0克 溶剂石脑油100
组分B1)
67.8克(0.6当量) ε-己内酰胺
组分B2)
固体含量: 计算值:70.0%
23℃粘度: 约5500mPas
封闭的NCO含量: 计算值5.1%
1当量封闭的NCO基团:计算值816.0克
在以下的涂料实施例中,所述的封闭多异氰酸酯按如下与支化的涂料用聚酯(70%溶解于1-甲氧基丙基乙酸酯-2,OH含量为1.4%,1当量OH基团=1214克Bayer AG)混合以获得NCO:OH当量比为1:1的单组分卷材涂料底漆.
粘合剂的组合
1当量的封闭的NCO基团=816克;对比量(reduzierte Menge):21.7克
方法:
在室温下向IPDI初始物料中加入液态(熔融)的OH组分。在搅拌下将内部温度逐级升至110℃。在该温度下搅拌反应混合物约4小时直至基本达到NCO含量计算值6.3%。然后依次加入HDI三聚体、溶剂石脑油100和ε-己内酰胺。使混合物在110℃反应约1小时直至达到NCO含量计算值3.3%。加入1,2,4-三唑并于110℃再继续搅拌3小时直到红外光谱分析不再检测到NCO。获得了具有上述性能的基本无色的溶液。
实施例2(根据本发明)
由0.625当量%的柔性NCO组分A1),0.375当量%的支化的NCO组分A2),0.5当量%的ε-己内酰胺(组分B1)和0.5当量%的二异丙基胺(组分B2)构成封闭多异氰酸酯。
配方:
组分A1) 659.4克(1.0当量) 实施例1)的IPDI预聚物
组分A2) 118.0克(0.6当量) 实施例1)的HDI三聚体
204.0克 溶剂石脑油100
204.0克 1-甲氧基丙-2-基乙酸酯
组分B1)90.4克(0.8当量) ε-己内酰胺
固体含量: 计算值:70.0%
23℃粘度: 约4000mPas
封闭的NCO含量: 计算值4.9%
1当量封闭的NCO基团:计算值848.0克
方法:
按实施例1所述制备IPDI预聚物。然后加入甲氧基丙基乙酸酯、HDI三聚体和ε-己内酰胺。在110℃下搅拌约1小时直至达到反应混合物的NCO含量3.1%。然后冷却至70-80℃,分多次加入二异丙基胺和溶剂石脑油100的混合物。该添加略微放热。温度保持在80℃,在加入二异丙基胺约30分钟后,没有NCO含量剩余(红外光谱分析)。获得了具有上述性能的透明、无色溶液。
实施例3(对比)
在异氰酸酯组分A1)和A2)方面该单封闭多异氰酸酯与实施例1相同;但是,只将ε-己内酰胺用做封闭剂。
该封闭多异氰酸酯的70%溶液的NCO当量为856克。
实施例4(对比)
在异氰酸酯组分A1)和A2)方面该单封闭多异氰酸酯与实施例1相同。但是,只将二异丙基胺用做封闭剂。
该封闭多异氰酸酯的70%溶液的NCO当量为839克。
实施例5(对比)
采用按照实施例1的多异氰酸酯组分A1)和A2),尝试制备只用1,2,4-三唑封闭的多异氰酸酯。该封闭多异氰酸酯的70%溶液是浑浊的。在短贮存时间后开始结晶。因此该封闭多异氰酸酯不能用做卷材涂料组合物的交联剂。
实施例6(应用例)
描述了涂料组合物的组成和性能。
A)用于钢和铝的单组分聚氨酯卷材涂料底漆组合物,不含铬酸盐(重量%)
在Scandex混合器中研磨上表所列的涂料组分并用刮刀施涂到磷酸处理过的测试钢板上(干膜厚度为约20微米)。然后将这些金属板在Aalborg炉(350℃)内烘烤38秒,这对应于最高的金属温度(PMT)232℃。
B)上述底漆的涂层性能
因为接下来这些底漆随金属板变形并进行覆盖涂覆,所以在随后的粘附力测试中采用了最特定值,通过在T-弯曲测试、在160℃老化30秒后的抗撕裂性能和深拉性能说明。
1)ECCA=欧洲卷材涂料协会
与对比涂料不同,由按照本发明封闭的多异氰酸酯制备的涂料1和2在室温下深拉能弯曲成杯形。这些杯形物即使在160℃下老化30分钟后,没有检测到涂层起皮。只有本发明的底漆能够通过这一严格的覆盖涂覆性能测试。
底漆1和2还额外经受了另外的飞石冲击实验(根据德国汽车工业协会-VDA),其中还向所述底漆上施涂了其它的普通商用整面涂料和面漆。对所述整面涂料和面漆独立地进行烘烤。所述涂层无损地经受了这两种烘烤操作,即没有起皮。
在飞石冲击对比测试中,按照本发明封闭的多异氰酸酯制备的涂料1和2的得分与常规阴极浸渍涂层相等。
Claims (3)
1.用于卷材涂料底漆的混合封闭的多异氰酸酯,其包含:
A1)40-70当量%主要为直链的NCO预聚物,其NCO含量为5.0-10.0重量%,
A2)30-60当量%脂肪族涂料用多异氰酸酯,
B1)30-60当量%的ε-己内酰胺,和
B2)40-70当量%作为封闭剂的二异丙基胺或1,2,4-三唑,其中异氰酸酯组分A1)和A2)的当量百分数之和为100%,封闭剂B1)和B2)的当量百分数之和为100-110%。
2.制备权利要求1的混合封闭的多异氰酸酯的方法,其特征在于:首先,在室温下加入二异氰酸酯,然后在搅拌下加入OH组分,例如聚酯、聚醚、二醇和三醇,通过加热至100-110℃引发过量的NCO基团与OH组分的反应,并且,当达到或略微低于NCO含量计算值时,使反应终止,以制备NCO预聚物(A1),在接下来的步骤中,用溶剂稀释得到的NCO预聚物,并加入涂料用多异氰酸酯A2)以形成所有NCO组分A1)+A2)和进行混合封闭,首先用ε-己内酰胺(B1)在100-110℃进行部分封闭直至达到NCO含量计算值,然后用1,2,4-三唑或二异丙基胺反应掉剩余量的NCO基团。
3.权利要求1的混合封闭多异氰酸酯用于制备卷材涂料底漆的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10156897.5 | 2001-11-20 | ||
DE10156897A DE10156897A1 (de) | 2001-11-20 | 2001-11-20 | Mit epsilon-Caprolactam und DIPA bzw. 1,2,4-Triazol mischblockierte Polyisocyanate, deren Herstellung und Verwendung |
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CN1589288A CN1589288A (zh) | 2005-03-02 |
CN100500725C true CN100500725C (zh) | 2009-06-17 |
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CNB028230949A Expired - Fee Related CN100500725C (zh) | 2001-11-20 | 2002-11-07 | 经ε-己内酰胺和DIPA或1,2,4-三唑混合封闭的多异氰酸酯及其制备和应用 |
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US (1) | US6723817B2 (zh) |
EP (1) | EP1448652B1 (zh) |
JP (1) | JP4217625B2 (zh) |
KR (1) | KR100923613B1 (zh) |
CN (1) | CN100500725C (zh) |
AT (1) | ATE506388T1 (zh) |
AU (1) | AU2002340507A1 (zh) |
CA (1) | CA2467546C (zh) |
DE (2) | DE10156897A1 (zh) |
ES (1) | ES2364241T3 (zh) |
HK (1) | HK1074849A1 (zh) |
WO (1) | WO2003044072A1 (zh) |
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DE10253482A1 (de) * | 2002-11-18 | 2004-06-03 | Bayer Ag | Verfestigungsstabile blockierte Polyisocyanate |
US20040249106A1 (en) * | 2003-06-03 | 2004-12-09 | Gindin Lyubov K. | Modified polyurethanes |
CA2655722C (en) | 2006-07-05 | 2012-11-27 | Valspar Sourcing, Inc. | Water-dispersible polyurethane polymer |
DE102006038941A1 (de) | 2006-08-18 | 2008-02-21 | Bayer Materialscience Ag | Wasserverdünnbare, bzw. wasserlösliche blockierte Polyisocyanate für die Herstellung von wässrigen 1K-PUR-Beschichtungen mit schneller physikalischer Antrocknung |
WO2022260180A1 (ja) * | 2021-06-11 | 2022-12-15 | 日本発條株式会社 | コーティング剤、及び、ばね |
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DE3322719A1 (de) * | 1983-06-24 | 1985-01-03 | Chemische Werke Hüls AG, 4370 Marl | Pulverfoermige ueberzugsmittel |
DE3328134C2 (de) * | 1983-08-04 | 1986-08-07 | Hüls AG, 4370 Marl | EP-Pulverlacke und Verfahren zur Herstellung matter Überzüge |
DE4240480A1 (de) * | 1992-12-02 | 1994-08-25 | Bayer Ag | Organische Polyisocyanate mit zumindest teilweise blockierten Isocyanatgruppen |
DE4339367A1 (de) | 1993-11-18 | 1995-05-24 | Bayer Ag | Blockierte Polyisocyanate |
DE4416750A1 (de) | 1994-05-13 | 1995-11-16 | Bayer Ag | Mischblockierte Polyisocyanate |
DE19516400A1 (de) | 1995-05-04 | 1996-11-07 | Bayer Ag | Blockierte Polyisocyanate und ihre Verwendung |
DE19631269A1 (de) | 1996-08-02 | 1998-02-05 | Bayer Ag | Mit 3,5-Dimethyl-1,2,4-triazol blockierte Polyisocyanate |
DE19637334A1 (de) * | 1996-09-13 | 1998-03-19 | Bayer Ag | Stabilisierte blockierte Isocyanate |
DE19738497A1 (de) | 1997-09-03 | 1999-03-04 | Bayer Ag | Amin-blockierte Polyisocyanate |
DE59903122D1 (de) * | 1998-12-07 | 2002-11-21 | Bayer Ag | Malonester/triazolmischblockiertes hdi-trimerisat/formaldehydstabilisierung |
DE19856968A1 (de) * | 1998-12-10 | 2000-06-15 | Bayer Ag | Malonester/Triazolmischblockiertes HDI-Trimerisat/Formaldehydstabilisierung |
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2001
- 2001-11-20 DE DE10156897A patent/DE10156897A1/de not_active Withdrawn
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2002
- 2002-11-07 AU AU2002340507A patent/AU2002340507A1/en not_active Abandoned
- 2002-11-07 CN CNB028230949A patent/CN100500725C/zh not_active Expired - Fee Related
- 2002-11-07 CA CA 2467546 patent/CA2467546C/en not_active Expired - Fee Related
- 2002-11-07 JP JP2003545706A patent/JP4217625B2/ja not_active Expired - Fee Related
- 2002-11-07 DE DE50215017T patent/DE50215017D1/de not_active Expired - Lifetime
- 2002-11-07 WO PCT/EP2002/012429 patent/WO2003044072A1/de active Application Filing
- 2002-11-07 EP EP20020774774 patent/EP1448652B1/de not_active Expired - Lifetime
- 2002-11-07 AT AT02774774T patent/ATE506388T1/de active
- 2002-11-07 KR KR1020047007633A patent/KR100923613B1/ko not_active IP Right Cessation
- 2002-11-07 ES ES02774774T patent/ES2364241T3/es not_active Expired - Lifetime
- 2002-11-18 US US10/298,773 patent/US6723817B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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EP1448652A1 (de) | 2004-08-25 |
US20030130468A1 (en) | 2003-07-10 |
CA2467546C (en) | 2011-05-17 |
HK1074849A1 (en) | 2005-11-25 |
CN1589288A (zh) | 2005-03-02 |
JP2005509705A (ja) | 2005-04-14 |
AU2002340507A1 (en) | 2003-06-10 |
EP1448652B1 (de) | 2011-04-20 |
US6723817B2 (en) | 2004-04-20 |
JP4217625B2 (ja) | 2009-02-04 |
KR100923613B1 (ko) | 2009-10-23 |
ATE506388T1 (de) | 2011-05-15 |
CA2467546A1 (en) | 2003-05-30 |
DE10156897A1 (de) | 2003-05-28 |
ES2364241T3 (es) | 2011-08-29 |
WO2003044072A1 (de) | 2003-05-30 |
KR20040063967A (ko) | 2004-07-15 |
DE50215017D1 (de) | 2011-06-01 |
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