CN1494562A - 单组分聚氨酯烘烤漆及其应用 - Google Patents
单组分聚氨酯烘烤漆及其应用 Download PDFInfo
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Abstract
本发明涉及1K聚氨酯漆，其中的多异氰酸酯交联剂用CH－酸酯，特别是用丙二酸酯封端。此漆具有低的烘烤温度。这种烤漆特别用来给塑料零件上漆。
Description
本发明涉及单组分聚氨酯烘烤漆，其多异氰酸酯交联剂具有CH-酸酯的封端，特别具有丙二酸酯的封端。
如在下面的出版物所显示：Petersen，Liebigs Ann.Chem.562，(1949)205和DE-A 30 010 60，用CH-酸酯，特别是丙二酸酯给多异氰酸酯封端属于先有技术。
使用由丙二酸酯封端的多异氰酸酯和聚合的OH组分(聚酯、聚丙烯酸酯等)能够混合储存稳定的“单组分漆”。在涂布以后，这样的漆，甚至在100℃的烘烤温度，比如在100℃烘烤30min的条件下都固化。而对于其他的异氰酸酯封端剂，比如丁酮肟、1，2，4-三唑、二异丙胺或3，5-二甲基吡唑，这样低的烘烤温度是几乎不能实现的。
然而，当比如热塑性塑料，如用于汽车零件，象保险杠、方向盘的毂盖或车内的装潢要喷漆时，低的烘烤温度又是必要的。目前，要求是用单组分漆涂布聚丙烯零件，因此要求甚至低于100℃的烘烤温度。
用比如二月桂酸二丁基锡(DBTL)催化，使用如上所述的传统封端剂加工单组分聚氨酯烤漆是已知的(比如在Farbe & Lack 7/96，102ndyear，page51-58，Vincentz Verlag/Hannover)。
用比如丙二酸酯封端的多异氰酸酯来催化单组分烤漆迄今还未为人所知。
因此，本发明的目的就是找到一种催化剂(Katalyse)，使用这种催化剂可以使基于用CH-酸酯封端的多异氰酸酯的单组分聚氨酯烤漆甚至在低于100℃的烘烤温度下固化。
使用按照本发明的含有钛化合物的单组分聚氨酯烤漆已经实现了这个目的。
因此，本发明提供了溶剂基的或者用水稀释的单组分聚氨酯烤漆，它由如下组分组成：
i)用CH-酸酯，特别是用丙二酸酯封端的多异氰酸酯，和
ii)含羟基的聚合物，
iii)任选的添加剂和加入的成分，
其特征在于，基于组分i)和ii)的和，含有0.5～4.0wt％的四价钛化合物。
本发明的基础是四价钛有机化合物作为催化剂的存在，该化合物使得自CH-酸酯，优选丙二酸酯封端的多异氰酸酯和有机多羟基化合物并作为单组分可加工的聚氨酯漆混合物，即使在90℃的烘烤温度/30min下也有足够的交联，其中85℃的烘烤温度/30min也是可以实现的。
按照本发明将要使用的钛(IV)催化剂与处于溶解形式的上述漆的粘料组分混合。这样的单组分聚氨酯漆粘料是储存稳定的，可以经过配合作为最终的产品，例如用于下面的漆的应用中：填料或底漆、金属底漆、清漆、含颜料的面漆或水稀释的软手感漆。它们可以任选含有传统的添加剂和加入的成分，比如颜料、流动助剂等。
按照本发明考虑将作为钛催化剂使用的有比如原钛酸四正丁酯、钛酸四乙酯、钛酸四甲酯、四(2-乙基己酸)钛、三异丙氧化氯化钛和三氯化环戊二烯基钛，以及任何所需的这些钛(IV)化合物的混合物。特别优选的是钛酸四正丁酯。
基于漆粘料组分的固体含量，钛(IV)催化剂的用量为0.5～4.0wt％，优选1.5～2.5wt％。
按照本发明的单组分聚氨酯烤漆可用来涂布各式各样材料的底材，比如用来涂布金属、玻璃、矿物、陶瓷、木材、纸张、塑料，比如聚碳酸酯、聚甲基丙烯酸甲酯、聚酰胺、聚丙烯等的底材。
在下面的实施例中，借助于催化的清漆，以及和其他基于铋、锡和锆的催化剂的对比来说明本发明。已经显示出，使用钛酸四丁酯，可以把不使用催化剂的漆在100℃下完全固化，降低到至少90℃，甚至于可降低到85℃。因此用这样的单组分漆给聚丙烯塑料零件上漆也是可以做到的。
实施例
原料组分
实施例1
清漆组分的制备和表征
a)用丙二酸酯封端的多异氰酸酯交联剂
批 g 克当量
DesmodurW，三聚，乙酸丁二醇酯(BDGA) 246.0 1.0
中的80％，NCO含量：测量值17.1％1)
丙二酸二乙酯(DEM) 160.0 1.0
甲醇钠的30％甲醇溶液 3.5 -
3，5，5-三甲基-3-氨甲基环己胺(IPDA) 8.5 0.1
低聚甲醛(Pafo) 3.0 0.1
Tinuvin770DF2) 3.7 -
异丁醇(IB) 78.9 -
N-甲基吡咯烷酮(NMP) 78.9 -
磷酸二丁酯(DBP) 11.0 -
被封端的NCO基团 593.5 1.0
固体，计算： 大约65％
在23℃的粘度 大约7000mPa
pH值： 6.3
清澈溶液，Hazen色度： 大约50Apha
1克当量封端的NCO基团 594.0g
1)三聚：将DesmodurW放入容器中，在搅拌和通过细氮气流下加热到80℃。加入3～5mL的5％Triton B溶液(在正丁醇/NMP中)反应开始，在每种情况下反应温度一降低到85～90℃以下时，就要对反应进行催化，以这样的方法，使初始的NCO含量32.06％降低到大约21.0％，这相当于存在的NCO基团中35％被转化。用BDGA稀释混合物，让其冷却。淡黄色的三聚DesmodurW溶液，其NCO含量为17.1％，相当于246g的NCO当量，按照下面进行进一步加工。
2)购自Ciba Speciality Chemicals公司，CH-4002 Basel
实施
在搅拌下，将DEM和部分量的3.0g甲醇钠溶液在50℃下放入容器中。在其中分批加入上述DesmodurW三聚产物。在添加以后，温度升至70～75℃，继续搅拌大约5br，直至NCO含量降低到大约0.5％。然后用NMP稀释该混合物，用IPDA结合仍然保留的NCO基团。
在温度大约为50℃的此反应溶液中加入Pafo、0.3g甲醇钠溶液和IB(半量)的清澈溶液，在50℃下继续进行2hr的搅拌。
然后加入Tinuvin770 DF、DBP和IB(剩下的量)的溶液，在50℃下继续进行大约2hr的搅拌。
得到储存稳定的用丙二酸酯封端的多异氰酸酯的溶液，此溶液具有在开始时提到的特征。
b)用于上述用丙二酸酯封端的交联剂的反应物是含羟基的聚丙烯酸酯DesmophenA 655(Bayer AG，羟基含量3％，供给形式的OH当量567g，醋酸丁酯/二甲苯3∶1中的65％)。
实施例2(按照本发明)
叙述清漆的制备和在各种催化剂的影响下该清漆的固化。
a)清漆的组成
重量份
按照实施例1a的交联剂 32.7(0.055克当量封端的
NCO)
DesmophenA 665(见1b) 31.2(0.055克当量OH)
Baysilone OL17，在二甲苯中10％1) 0.4
Tinuvin1130，在二甲苯中10％2) 4.1
Tinuvin292，在二甲苯中10％2) 4.1
醋酸丁酯，醋酸1-甲氧基-2-丙酯 27.5
(MPA)
清漆组分 100.0
1)购自Bayer AG，51368 Leverkusen
2)购自Ciba Speciality Chemicals公司，CH-4002 Basel
为了进行进一步的测试，将上述清漆与各自的催化剂混合，各自的催化剂基于粘料的固体计，量为1％和2％，即每100g清漆为0.41g和0.82g。借助于刮刀制备120μm的湿膜。在如下条件下，在烘箱中烘烤。
实施例3(按照本发明)
描述了汽车镜框涂漆
用商品洗涤溶液清洗购自Audi公司的未涂漆镜框(材料是ABS)，然后用脱盐水再洗涤并干燥。借助于使用Sata公司喷枪的喷涂涂布列于下面的清漆体系。使用的喷嘴直径1.4mm，喷涂压力2.5bar。
1.填料涂布
均匀地涂布购自Du Pont公司(Wuppertal)的商品双组分聚氨酯填料，漆膜厚度30～40μm，然后在80℃下干燥30min。
2.底漆涂布
然后涂布显色和显效果的清漆体系(也是购自Du Pont公司的金属底漆，银色)，漆膜厚度12～15μm，在80℃下干燥5min。
3.清漆涂布
作为第三道和最后一道漆层，涂布具有如下漆组成的如在实施例2中所述的清漆：
重量份
如实施例1a的交联剂 32.7
DesmophenA 665(见实施例1b) 31.2
Baysilone OL17，在二甲苯中的10％ 0.4
Tinuvin1130，在二甲苯中的10％ 4.1
Tinuvin292，在二甲苯中的10％ 4.1
醋酸丁酯/MPA 1∶1 26.7
原钛酸四正丁酯
0.8
100.0
将该清漆涂布为膜厚40～50μm的漆膜，然后在80℃下干燥30min，得到的清亮的高光泽的漆膜表面具有良好的固化和良好的漆性能。
b)催化剂筛选
借助于符合汽车工业要求的摆锤硬度(Pendelhrte)(DIN 53157)和耐溶剂性测试来测试清漆的固化。在此方法中，用比如棉絮将数滴各种溶剂连续涂在漆膜上。让其作用1min以后，抹去溶剂，对漆膜进行评价。评分0意味着漆膜完全没有损坏。在最差的评分5的情况下，漆膜从底材上分离。用CieLab法测量漆膜变黄。大约1.0的b值可看作是仍然可接受的。当已经烘烤过的漆是再次烘烤过度时，形成Δb值，它不可以超过10。
正如在下页的概括中所看到的，用如下的催化剂测试了8个清漆：
1.没有催化剂的盲值；
2.(2-乙基己酸)3铋，得自King Industries；
3.原钛酸四正丁酯(TBT)；
4.二月桂酸二丁基锡(DBTL)；
5.(2-乙基己酸)4Zr；
6.(2-乙基己酸)4钛；
7.三异丙氧化氯化钛；
8.三氯化环戊二烯基钛。
正如所看到的，钛酸四丁酯(TBT)是唯一一种即使在80℃/30min固化情况下就开始起作用的被测催化剂。在使用2％的TBT时，膜硬度和耐溶剂性都比0值还好。在90℃/30min固化的情况下，这个趋势就更加明显。评分为0025的耐溶剂性在188s的良好漆膜硬度下表明交联是良好可用的，用0值和用其他催化剂催化的漆膜都不能做到如此。再有，90℃/30min固化显示出，四价钛催化剂比其他催化剂更具有优点。
在160℃/30min的过度烘烤条件下，对钛(IV)催化剂而言有比较高的泛黄值，Δb＝2.5～3.1，这必须被看作是这样的结果，即塑料不会经受住那样的温度而不变形。
用于下页的清漆的催化剂研究
| 催化剂 | 1 | 2(比较) | 3(本发明的) | 4(比较) | 5(比较) | 6(比较) | 7 | 8 | |||||||
| 无 | K-Kat3481)(2-乙基己酸)3铋 | 原钛酸四正丁酯(TBT) | 二月桂酸二丁基锡(DBTL) | (2-乙基己酸)4锆 | (2-乙基己酸)4钛 | 三异丙氧化氯化钛 | 三氯化环戊二烯基钛 | ||||||||
| 催化剂量(计算的固/固) | 1％ | 2％ | 1％ | 2％ | 1％ | 2％ | 1％ | 2％ | 1％ | 2％ | 1％ | 2％ | 1％ | 2％ | |
| 干燥30min/80℃摆锤硬度(s)耐溶剂性作用时间1min二甲苯/MPA/乙酸乙酯/丙酮0＝良好，5＝差泛黄(b值) | 9955550.6 | 7155550.6 | 3244550.6 | 10155550.6 | 14444550.6 | 8755550.6 | 11055550.6 | 9255550.7 | 10855550.6 | 11355550.9 | 9755551.0 | 9255551.3 | 7855552.2 | 9555551.4 | 10455553.0 |
| 30min/90℃摆锤硬度(s)耐溶剂性作用时间1min二甲苯/MPA/乙酸乙酯/丙酮0＝良好，5＝差泛黄(b值) | 19533550.6 | 15022550.6 | 9022450.6 | 161334 50.6 | 18800250.6 | 16034550.6 | 17123450.6 | 15323450.6 | 19323450.6 | 19923451.0 | 17912451.0 | 19223451.4 | 17412452.5 | 18633551.7 | 19223453.3 |
| 30min/100℃摆锤硬度(s)耐溶剂性作用时间1min二甲苯/MPA/乙酸乙酯/丙酮0＝良好，5＝差泛黄(b值)泛黄30min，100℃+30min，160℃(Δb值) | 20600140.60.1 | 18800250.60.1 | 14700240.60.1 | 19500241.12.5 | 20200021.83.1 | 18001240.60.2 | 19200130.60.3 | 21100120.60.4 | 21400120.70.2 | 21100121.01.3 | 20200021.12.4 | 21100021.52.2 | 20300122.93.7 | 18800131.91.2 | 21100123.11.8 |
1)King Industries Specialty Chemicals，Kattensingel 7，2801 Gouda，Holland
Claims (4)
1.溶剂基或水稀释的单组分聚氨酯烤漆，它由如下组分组成：
i)用CH-酸酯，特别是用丙二酸酯封端的多异氰酸酯，和
ii)含羟基的聚合物，
iii)任选的添加剂和加入的成分，
其特征在于，其基于组分i)和ii)的和含有0.5～4.0wt％的四价钛化合物。
2.如权利要求1的单组分聚氨酯烤漆，其特征在于，该组分i)含有用丙二酸酯封端的多异氰酸酯。
3.如权利要求1的单组分聚氨酯烤漆，其特征在于，该四价钛化合物是钛酸四正丁酯。
4.如权利要求1的烤漆在给得自塑料、金属、木材、纸张、陶瓷、矿物、玻璃的基材上漆的应用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10109228A DE10109228A1 (de) | 2001-02-26 | 2001-02-26 | 1K-Polyurethaneinbrennlacke und deren Verwendung |
| DE10109228.8 | 2001-02-26 |
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| Publication Number | Publication Date |
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| CN1494562A true CN1494562A (zh) | 2004-05-05 |
Family
ID=7675544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028055845A Pending CN1494562A (zh) | 2001-02-26 | 2002-02-14 | 单组分聚氨酯烘烤漆及其应用 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6919417B2 (zh) |
| EP (1) | EP1366101A1 (zh) |
| JP (1) | JP2004528415A (zh) |
| KR (1) | KR20040030510A (zh) |
| CN (1) | CN1494562A (zh) |
| CA (1) | CA2439077A1 (zh) |
| DE (1) | DE10109228A1 (zh) |
| MX (1) | MXPA03007596A (zh) |
| PL (1) | PL363290A1 (zh) |
| WO (1) | WO2002068494A1 (zh) |
| ZA (1) | ZA200306565B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI417310B (zh) * | 2010-02-08 | 2013-12-01 | Asahi Kasei Chemicals Corp | Block polyisocyanate compositions and coating compositions comprising the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10308105A1 (de) * | 2003-02-26 | 2004-09-09 | Bayer Aktiengesellschaft | Polyurethan-Beschichtungssysteme |
| DE10336883A1 (de) * | 2003-08-08 | 2005-03-10 | Basf Ag | Kunststoff, insbesondere Polyurethan enthaltend ein sterisch gehindertes, verestertes Amin |
| US20050287349A1 (en) * | 2004-06-23 | 2005-12-29 | Yu Poli C | Method for coating coils |
| JP5562267B2 (ja) * | 2010-02-08 | 2014-07-30 | 旭化成ケミカルズ株式会社 | ブロックポリイソシアネート組成物及びこれを含む塗料組成物 |
| JP5572567B2 (ja) * | 2010-02-08 | 2014-08-13 | 旭化成ケミカルズ株式会社 | ブロックポリイソシアネート組成物を製造する方法 |
| JP5562271B2 (ja) * | 2010-06-04 | 2014-07-30 | 旭化成ケミカルズ株式会社 | ブロックポリイソシアネート組成物の製造方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3046409A1 (de) * | 1980-12-10 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | Beschichtungsmittel und ein verfahren zur herstellung von ueberzuegen |
| JPS5924771A (ja) * | 1982-08-02 | 1984-02-08 | Semedain Kk | 一液型室温硬化性シ−ラント組成物 |
| US4727099A (en) * | 1986-08-15 | 1988-02-23 | E. I. Du Pont De Nemours And Company | Coating composition containing a reactive urethane component, a hydroxyl containing acrylic polymer having pendent ester groups and a metallic alkylate catalyst |
| US4727100A (en) * | 1986-08-15 | 1988-02-23 | E. I. Du Pont De Nemours And Company | Coating composition containing a reactive urethane component an acrylic fatty acid drying oil resin and a metallic alkylate |
| KR100331585B1 (ko) * | 1993-04-29 | 2002-12-06 | 가부시키가이샤 구라레 | 열가소성 폴리우레탄 함유 조성물, 이의 제조방법, 이를 포함하는 성형품 및 탄성섬유 및 이들의 제조방법 |
| US6103849A (en) * | 1994-06-27 | 2000-08-15 | Bayer Corporation | Storage stable, heat curable polyurethane compositions |
| DE19813352A1 (de) * | 1998-03-26 | 1999-09-30 | Bayer Ag | Malonesterblockierte Polyisocyanate mit Formaldehyd gegen Thermovergilbung |
-
2001
- 2001-02-26 DE DE10109228A patent/DE10109228A1/de not_active Withdrawn
-
2002
- 2002-02-14 WO PCT/EP2002/001536 patent/WO2002068494A1/de active Application Filing
- 2002-02-14 JP JP2002568003A patent/JP2004528415A/ja active Pending
- 2002-02-14 CA CA 2439077 patent/CA2439077A1/en not_active Abandoned
- 2002-02-14 EP EP02719832A patent/EP1366101A1/de not_active Withdrawn
- 2002-02-14 MX MXPA03007596A patent/MXPA03007596A/es active IP Right Grant
- 2002-02-14 PL PL02363290A patent/PL363290A1/xx not_active Application Discontinuation
- 2002-02-14 CN CNA028055845A patent/CN1494562A/zh active Pending
- 2002-02-14 KR KR10-2003-7011138A patent/KR20040030510A/ko not_active Application Discontinuation
- 2002-02-20 US US10/079,661 patent/US6919417B2/en not_active Expired - Fee Related
-
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- 2003-08-22 ZA ZA200306565A patent/ZA200306565B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI417310B (zh) * | 2010-02-08 | 2013-12-01 | Asahi Kasei Chemicals Corp | Block polyisocyanate compositions and coating compositions comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| US6919417B2 (en) | 2005-07-19 |
| CA2439077A1 (en) | 2002-09-06 |
| US20030055158A1 (en) | 2003-03-20 |
| KR20040030510A (ko) | 2004-04-09 |
| ZA200306565B (en) | 2004-08-23 |
| MXPA03007596A (es) | 2003-12-11 |
| WO2002068494A1 (de) | 2002-09-06 |
| DE10109228A1 (de) | 2002-09-05 |
| JP2004528415A (ja) | 2004-09-16 |
| PL363290A1 (en) | 2004-11-15 |
| EP1366101A1 (de) | 2003-12-03 |
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