CN101243116B - 包含具有衍生自脂肪族异氰酸酯单元的聚氨酯的聚酯-聚氨酯杂化树脂模塑组合物 - Google Patents
包含具有衍生自脂肪族异氰酸酯单元的聚氨酯的聚酯-聚氨酯杂化树脂模塑组合物 Download PDFInfo
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及一种杂化树脂组合物，该组合物包含：包含脂肪族多官能异氰酸酯化合物和自由基聚合引发剂的组合物A；和包含烯属不饱和的基本上无水的聚酯多元醇和聚氨酯催化剂的组合物B。该组合物A可以含有非干扰性溶剂例如苯乙烯，且该组合物B通常具有5或更小的酸值(基于固体物)。对于户外用途，该组合物B优选不含叔氢、醚二醇和对苯二甲酸残基。
Description
本发明涉及杂化树脂。一方面，本发明涉及包含聚酯树脂和聚氨酯树脂的杂化树脂，同时另一方面，本发明涉及其中该聚氨酯包含衍生自脂肪族异氰酸酯单元的杂化树脂。再一方面，本发明涉及由这种杂化树脂制成的涂层。
聚酯-聚氨酯杂化树脂是本领域已知的热固性塑料成型组合物(例如USP5153261)。这些树脂通常比聚酯更坚韧，比聚氨酯更坚固、更刚性且更便宜。这种树脂通常是包含以羟基作为端基的不饱和聚酯多元醇、烯属不饱和单体(例如苯乙烯)和多异氰酸酯的那些树脂。它们容易适应许多目前用于聚氨酯和不饱和聚酯工业的常用热固性模塑技术。可从Cook Composites andPolymers得到的Xycon
杂化树脂是这些树脂的代表。
杂化树脂是包含A部分和B部分的双组分或两部分体系。A部分含有多异氰酸酯和聚酯催化剂，同时B部分含有以羟基作为端基的不饱和聚酯多元醇/不饱和单体溶液，任选地具有聚氨酯催化剂和/或填料。一旦将A部分与B部分在适当的条件下混合在一起，便形成分子链的互穿网络。该混合的聚酯组分提供扩链作用，同时多异氰酸酯组分提供交联作用。结果得到与任一单独的组分相比，表现出改善的韧性和热性质的模制品或涂层。
凝胶涂层通常用作复合模塑制品的外侧或外部表面层，因为它们赋予制品以光滑、耐用的外表。不饱和聚酯树脂被广泛用作船舶和有纹理的大理石的凝胶涂层，因为它们便宜、容易操作、并且在室温下固化。而且，这些树脂提供坚固、柔韧、耐磨且抗冲击的表面。然而，在某些产生压力的应用(例如螺旋桨桨片)中，需要对这些涂覆性能进行改善。这些应用需要具有以下特征的涂层，其具有优良的防潮性、韧性(例如抗裂性)和类似的将保护下面的层压物(laminate)不受环境力损坏的性质。
在一个实施方式中，本发明涉及包含下列物质的杂化树脂组合物：
A.包含脂肪族多官能异氰酸酯化合物和自由基聚合引发剂的组合物A；和
B.包含烯属不饱和的基本上无水的聚酯多元醇和聚氨酯催化剂的组合物B。
该杂化树脂组合物包含约10-50重量％的组合物A，约50-90重量％的组合物B。NCO基团与OH基团的摩尔比为0.3-2.0，优选为0.5-1.5。组合物A中的脂肪族多官能异氰酸酯具有5-50％、优选10-35％的NCO含量。组合物A可以含有非干扰性的溶剂，例如苯乙烯，组合物B通常具有10或更小，优选5或更小的酸值(基于固体物)和基于固体物的约120-170，优选130-160的羟基数。对于户外用途，组合物B优选不含有在叔碳上的氢、醚二醇(ether glycol)和对苯二甲酸残基。
在另一实施方式中，本发明涉及由该杂化树脂制成的凝胶涂层，在再一实施方式中，本发明涉及包含由该杂化树脂制备的凝胶涂层的制品。
用在该杂化树脂的组合物A中的烯属不饱和单体可以为任何能够通过乙烯基加成聚合使该不饱和聚酯多元醇交联的烯属不饱和单体。有用的烯属不饱和单体的实例为苯乙烯，邻、间、对-甲基苯乙烯，丙烯酸甲酯，甲基丙烯酸甲酯，叔丁基苯乙烯，二乙烯基苯，邻苯二甲酸二烯丙酯，氰尿酸三烯丙酯以及两种或多种不饱和单体的混合物。优选的单体是苯乙烯，因为它提供经济的单体。
该不饱和聚酯多元醇具有至少一个二羧基烯烃部分，并优选为α，β-烯属不饱和二羧酸化合物的低聚物，该低聚物通过饱和二羧酸或多羧酸或饱和二羧酸酐或多羧酸酐以及不饱和二羧酸或多羧酸或不饱和二羧酸酐或多羧酸酐中的一种或多种与二醇或多元醇的缩合反应获得。该不饱和聚酯多元醇还可以由不饱和二羧酸或多羧酸或不饱和二羧酸酐或多羧酸酐与二醇和/或多元醇制得。用于本发明的多元醇具有小于5并且优选小于约2的酸价或酸值。此外，用于本发明的多元醇具有约250-约1000、优选约250-约500的当量重量。合适的饱和二羧酸或多羧酸的实例包括间苯二甲酸、邻苯二甲酸、对苯二甲酸、己二酸、琥珀酸、癸二酸、以及两种或多种这些化合物的混合物，优选间苯二甲酸。典型的不饱和羧酸或羧酸酐包括马来酸、富马酸、柠康酸、氯代马来酸、烯丙基琥珀酸、衣康酸、中康酸、它们的酸酐、以及两种或多种这样的化合物的混合物，优选马来酸酐。在本发明中有用的多元醇的实例包括新戊二醇、乙二醇、二甘醇、三甘醇、丙二醇、一缩二丙二醇、1，4-丁二醇、聚乙二醇、丙三醇、甘露糖醇、1，2-丙二醇、季戊四醇、1，6-己二醇、1，3-丁二醇、以及两种或多种这样的化合物的混合物。对于户外用途，组合物B优选不含有叔氢、醚二醇和对苯二甲酸残基。
组合物B应当基本上无水。“基本上无水”的意思是组合物B的水含量足够低以避免不可接受的发泡程度。优选地，基于组合物B的总重量，组合物B包含不超过约2000ppm，优选不超过1000ppm的水。
该通常被称为脂肪族多异氰酸酯的脂肪族异氰酸酯化合物必须具有至少两个官能团并能够与该聚酯多元醇反应。适合的异氰酸酯化合物的实例包括2，2，4-三甲基-六亚甲基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、以及它们的缩二脲和环状三聚体形式。优选地，该脂肪族异氰酸酯化合物为六亚甲基二异氰酸酯，更优选为六亚甲基二异氰酸酯的二聚体或三聚体形式。
在一个实施方式中，该脂肪族异氰酸酯化合物可以用多元醇(例如二醇)改性以提供聚合体形式以易于处理。通常，基于该异氰酸酯官能团的总原子量和该脂肪族异氰酸酯化合物的总分子量，该异氰酸酯的含量范围为约5％-约50％，更优选为约10％-约35％。
对制备本发明的杂化树脂组合物有用的自由基聚合催化剂为乙烯基聚合催化剂，例如过氧化物、过硫化物、过硼酸盐、过碳酸盐和偶氮化合物或任何其它能够催化该聚酯多元醇和/或该烯属不饱和单体的乙烯基聚合的合适催化剂。一些这样的催化剂的说明性实例为过氧化苯甲酰(BPO)、过氧苯甲酸叔丁酯(TBPB)、2，2’-偶氮-二-异丁腈、过氧化二苯甲酰、过氧化月桂酰、过氧化二叔丁基、过氧化碳酸二异丙酯、以及过氧-2-乙基己酸叔丁酯。还可以将促进剂与乙烯基聚合过氧化物催化剂结合使用，以控制自由基引发速率。常用的过氧化苯甲酰促进剂为N，N-二乙基苯胺。
在制备本发明的杂化树脂时有益于催化聚氨酯的形成的催化剂包括：(a)叔胺，例如N，N-二甲基环己胺；(b)叔膦，例如三烷基膦；(c)强碱，例如碱金属和碱土金属的氢氧化物、醇盐和酚盐；(d)强酸的酸性金属盐，例如氯化铁；以及(e)有机金属化合物，例如二月桂酸二丁基锡、羧酸铋和锆螯合物2，4-戊二酮。其它通常使用的用于制备聚氨酯的催化剂可参见USP 4280979。
本发明的杂化树脂可以通过基于通常用在不饱和聚酯和聚氨酯工业中的液态反应模塑或压缩模塑技术的方法制备。液态模塑是将杂化树脂直接注射或倾注到模具中(封闭式模塑法)或模具上(敞开式模塑法)。在液态注射封闭式模塑中，将在单体溶液(多元醇)中的多异氰酸酯和以羟基作为端基的聚酯分别加料到混料头的腔中，所述两种组合物在该混料头中混合。一旦混合，即刻发生杂化反应，由此反应速率取决于所使用的催化剂。将该杂化的液态蒸气注入到模具的两个部分(mold halves)之间，在其中继续进行该杂化树脂体系的各种组分之间的反应。在固化足够的时间(通常为1-120分钟，优选2-60分钟)以后，从模具取下该部件。该部件可用作模制品或者可以进一步在烘箱中进行后期退火。常用的液态封闭式模塑技术包括树脂传递模塑(RTM)、反应注射成型(RIM)和结构性反应注射成型法(S-RIM)。
本发明的再一目标是获得能固化的树脂组合物，其包含至少一种如本发明所定义的杂化树脂，其可以用于通过固化而制备例如凝胶涂层(或阻隔涂层)的涂层或复合模塑制品。因此，本发明的树脂可以用于基于SMC、BMC、DMC的复合模塑制品或用于例如凝胶涂层(或阻隔涂层)的涂层。
所述涂层可以应用于复合模塑基底，该基底由本发明的树脂或其它树脂，包括UPR或乙烯基酯或任何其它的热固性树脂制成。
液态注射敞开式模塑具有同样的步骤，除了将该杂化树脂喷射到模具上以外，其中该模制品的一侧被暴露在大气中。该模塑方法通常被称为“喷射成型法”。直接倾倒的液态模塑包括手动混合该多元醇和多异氰酸酯，然后将该杂化液体倾注到其中发生固化的模具中或该模具上。注射与倾注之间的主要差别在于混合时间、混合强度和注射压力。在这两种液态模塑技术中，所述多元醇和/或多异氰酸酯均可以含有纤维材料、填料和/或其它添加剂，但在凝胶涂层应用中，该树脂通常不含任何纤维材料和填料。
杂化树脂对于压缩模塑也是可改善的(amendable)。通常的压缩模塑技术包括片状、块状或团状模塑料，其分别称为SMC、BMC和DMC。不管所使用的模塑技术如何，本发明的杂化树脂均具有改善的收缩控制、表面外观和冲击强度的优点，而没有显著地损失热性质。
本发明的凝胶涂层相对于油漆层更厚，但通常厚度仍小于半毫米。为了使该厚度的液体层停留在不在水平方向上的模具表面上，该树脂应当是触变性的。换句话说，在通过例如喷涂、刷涂或辊涂这样的方法的涂敷过程中，该粘度相对低，但是一旦该涂覆步骤结束，其便足够粘滞以抵抗重力。适宜的触变剂可以选自(热解)硅石、脂肪酸酰胺、粘土，其重量含量为相对于组合物B的重量的0.2-5％。
在其中通常使用该杂化树脂的模塑工艺中，通常两种或多种成型元件共同限定模具腔。否则可以提供单一的复杂形状的腔室。将本发明的杂化树脂涂覆在整个模具表面的至少部分上。该模具接触表面可以由任何常规材料例如玻璃、增强聚酯、环氧树脂、钢、铝或其他金属形成。
在一个说明性实施例中，该杂化树脂的组合物A包含异氰酸酯或在非干扰性溶剂例如苯乙烯中的异氰酸酯溶液。由于其相对于芳香族二异氰酸酯的抗变黄或抗其它变色性，脂肪族异氰酸酯例如2，2，4-三甲基-六亚甲基二异氰酸酯尤其适用于户外用途。
组合物B包含不饱和聚酯树脂、润湿剂、流平助剂、包装促进剂(promotion package)、填料、聚氨酯催化剂、粘度调节剂和颜料。一个典型的配方(以重量份计)包含以下成分：
组分描述 重量份
不饱和聚酯多元醇 873.43
黑色颜料分散体 1.12
黄色氧化铁颜料分散体 1.80
白色颜料分散体 92.83
脱气剂 2.5
粘土(季铵处理的) 12.48
滑石 12.48
辛酸钴溶液 0.87
二月桂酸二丁基锡 1.25
硅流体200cSt-鱼眼消除剂 1.25
由以上配方明显可见，本发明的杂化树脂可以含有一种或多种添加剂，例如填料、颜料、加工助剂、固化助剂、抗氧剂、UV-抑制剂、催化促进剂等。这些添加剂可以包括在组合物A与组合物B的任意一个中，或者同时包含在组合物A和组合物B中，尽管包含在组合物B中更为典型。
以下实施例进一步说明本发明。在这些实施例中，所有的粘度测量均在粘度计在设定的速度下运行约2分钟后进行。
实施例1不饱和聚酯树脂的制备(对比)
在装备有搅拌器、冷凝器、温度计和用于引入氮气的导管的4升烧瓶中添加740g二甘醇、456g丙二醇、1060g间苯二甲酸。在210℃下加热该混合物约10小时直到酸值降至10mg KOH/g。在温度降至150℃后，将624g马来酸酐添加到该混合物中。在210℃下再继续进行该反应6小时至酸值为30-50mg KOH/g。将该产物与1460g被阻聚的苯乙烯共混以形成4000g的清澈树脂溶液(树脂A)。在63％的固含量下，树脂溶液的粘度为约1000mPa.s(cP)。树脂粘度通过布鲁克菲尔德粘度计在25℃下用20rpm的RVT 2号转子进行测量。
实施例2常规凝胶涂层的制备(对比)
然后通过共混以下成分制备凝胶涂层组合物：
| 成分 | 重量百分比 |
| 树脂A | 53.2 |
| 二氧化钛 | 15.0 |
| 热解硅石 | 1.5 |
| 单体 | 19.4 |
| 滑石 | 10.5 |
| 12％的钴 | 0.2 |
| 乙二醇 | 0.2 |
所得凝胶涂层具有19000mPa.s(cP)的布鲁克菲尔德粘度(在77℃下，4rpm)和6.0-7.0的触变指数(RVF 4号转子，2/20rpm)。使用1.8％的过氧化甲乙酮(MEKP)以固化凝胶涂层。凝胶化时间为约15分钟，并且固化时间为约60分钟。以下列出该固化凝胶涂层的风化特性，该特性通过QUV-A，ASTMG154使用在60℃下标准地暴露于UV 8小时、随后在50℃下缩合4小时的方法进行测量。
| 小时 | 总的颜色变化，ΔE | ％光泽保持率 |
| 050010001500 | 0.001.525.825.73 | 100998612 |
实施例3以OH作为端基的不饱和聚酯树脂的制备
在装备有搅拌器、冷凝器、温度计和用于引入氮气的导管的4升烧瓶中添加1380g新戊二醇、202g丙二醇、994g间苯二甲酸。在210℃下加热该混合物约10小时直到酸值降至10mg KOH/g。在温度降至150℃后，将587g马来酸酐添加到该混合物中。在210℃下继续进行该反应直到酸值小于5mgKOH/g且OH值为130-150mg KOH/g。将该产物与1160g被阻聚的苯乙烯共混以形成4000g的清澈树脂溶液(树脂B)。在71％的固含量下，树脂溶液的粘度为700mPa.s(cP)。
实施例4聚酯-聚氨酯杂化凝胶涂层的制备
然后通过将以下形成组合物B的成分共混制备双组分凝胶涂层组合物：
| 成分 | 重量百分比 |
| 树脂B二氧化钛热解硅石单体滑石12％的钴二月桂酸二丁基锡乙二醇促进剂 | 42.624.52.019.910.10.20.30.30.1 |
所得凝胶涂层具有15000mPa.s(cP)的布鲁克菲尔德粘度(在77℃下，4rpm)和5.0-6.0的触变指数。该组合物A含有脂肪族二异氰酸酯和过氧化甲乙酮(MEKP)。该组合物A和组合物B以20/80的比例混合以固化该聚酯-聚氨酯杂化凝胶涂层。凝胶化时间为约15分钟，并且固化时间为约60分钟。以下列出通过QUV-A测量的该凝胶涂层的风化特性。
| 小时 | 总的颜色变化，ΔE | ％光泽保持率 |
| 050010001500 | 0.000.600.650.78 | 100100100100 |
实施例5比较水煮(boil)100小时的层压物
用实施例2和4的凝胶涂层样品制备涂覆有凝胶的(gel-coated)层压物。该层压物具有两种不同厚度的凝胶涂层。凝胶涂层的厚的部分(TK)具有约0.762mm(30密耳)的固化凝胶涂层厚度，并且凝胶涂层的薄的部分(TN)具有约0.381mm(15密耳)的固化凝胶涂层厚度。将这些板浸渍在沸腾的去离子水中100小时，将该性能分为0至5五个不同的等级。0等级表示没有变化，5等级表示极端的变化。结果表明，与常规的凝胶涂层相比，该聚酯-聚氨酯杂化凝胶涂层具有好得多的抗水性。
| 煮100小时 | 实施例2 | 实施例4 |
| 气泡(TK/TN) | 2.7/2.7 | 0/0 |
| 颜色变化(TK/TN) | 1.4/1.4 | 0.64/0.64 |
| 纤维突起(prom.)变化(TK/TN) | 0.8/1.8 | 0.66/0.66 |
| 裂纹(TK/TN) | 0.8/1.0 | 0/0 |
| 光泽损失(TK/TN) | 0.3/0.3 | 0/0 |
| 总的级别(TK/TN) | 6.0/7.2 | 1.30/1.30 |
实施例6比较铸件在不同温度下的机械性质
将所述凝胶涂层样品制成铸件，根据以下ASTM标准D-638测量铸件的抗张性能。抗张性能在环境温度、-10℃和-30℃下测量。结果表明，与传统的凝胶涂层相比，该聚酯-聚氨酯杂化凝胶涂层具有好得多的低温抗张伸长率的保持。
| 实施例2-23℃ | 实施例2-10℃ | 实施例2-30℃ | |
| 抗张强度(MPa) | 49±3 | 50±4 | 41±7 |
| 抗张模量(MPa) | 2299±134 | 3013±134 | 3107±180 |
| 伸长率(％) | 2.6±0.2 | 2.2±0.2 | 1.5±0.3 |
| 实施例423℃ | 实施例4-10℃ | 实施例4-30℃ | |
| 抗张强度(MPa) | 44±4 | 49±3 | 50±6 |
| 抗张模量(MPa) | 2038±85 | 2441±113 | 2713±149 |
| 伸长率(％) | 2.9±0.4 | 2.4±0.2 | 2.2±0.3 |
实施例7反向冲击强度的比较
涂覆有凝胶的层压物的反向冲击强度根据以下ASTM标准D-3029测量。对每个样品进行共9次试验，报道其平均值。结果表明，与常规凝胶涂层相比，该聚酯-聚氨酯杂化凝胶涂层具有好得多的反向冲击强度。
| 反向冲击试验 | 实施例2 | 实施例4 |
| 平均裂纹数标准偏差 | 14.81.169 | 5.70.951 |
| 平均裂纹长度cm(英寸)标准偏差cm(英寸) | 3.18(1.25)0.00 | 2.24(0.88)0.086(0.034) |
| 平均凝胶涂层厚度mm(密耳)标准偏差mm(密耳) | 0.58(23.0)0.008(0.3) | 0.51(20.0)0.0 |
| 平均总厚度cm(英寸)标准偏差cm(英寸) | 1.04(0.41)0.030(0.012) | 0.79(0.31)0.23(0.09) |
尽管以上已经以相当多的细节描述了本发明，但该细节是为了说明性目的，而不应被认为是对描述于所附权利要求中的本发明的精神和范围的限制。以上引用的所有美国专利和被允许的专利申请在此引入作为参考。
Claims (23)
1.一种凝胶涂层，其中该凝胶涂层通过对能固化的树脂组合物进行固化而制得，其中，该能固化的树脂组合物包含至少一种杂化树脂，该杂化树脂包含：
A.包含脂肪族多官能异氰酸酯化合物和自由基聚合引发剂以及任选的非干扰性溶剂的组合物A；和
B.包含烯属不饱和的基本上无水的聚酯多元醇和聚氨酯催化剂的组合物B。
2.权利要求1的凝胶涂层，其中所述异氰酸酯化合物为下列物质中的至少一种：2，2，4-三甲基-六亚甲基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、以及它们的缩二脲和环状三聚体衍生物。
3.权利要求1或2的凝胶涂层，其中所述异氰酸酯化合物为六亚甲基二异氰酸酯和/或其衍生物。
4.权利要求3的凝胶涂层，其中所述异氰酸酯为六亚甲基二异氰酸酯环状三聚体衍生物。
5.权利要求1或2的凝胶涂层，其中所述聚酯多元醇包含至少一个二羧基烯烃部分。
6.权利要求1或2的凝胶涂层，其中所述聚酯多元醇包含α，β-烯属不饱和二羧酸化合物的低聚物，该α，β-烯属不饱和二羧酸化合物的低聚物通过饱和二羧酸或多羧酸或饱和二羧酸酐或多羧酸酐以及不饱和二羧酸或多羧酸或不饱和二羧酸酐或多羧酸酐中的一种或多种与二醇或多元醇的缩合反应获得。
7.权利要求1或2的凝胶涂层，其中所述自由基聚合引发剂为过氧化物、过硫化物、过硼酸盐、过碳酸盐和偶氮化合物中的至少一种。
8.权利要求1或2的凝胶涂层，其中所述聚氨酯催化剂为叔胺、叔膦、强碱、酸性金属盐和有机金属化合物中的至少一种。
9.权利要求1或2的凝胶涂层，其中基于该组合物B的总重量，所述组合物B包含小于2000ppm的水。
10.权利要求9的凝胶涂层，其中基于该组合物B的总重量，所述组合物B包含小于1000ppm的水。
11.权利要求1的凝胶涂层，其中该组合物B优选不含叔氢、醚二醇和对苯二甲酸残基。
12.一种凝胶涂层，其中该凝胶涂层通过对能固化的树脂组合物进行固化而制备，其中，该能固化的树脂组合物包含至少一种杂化树脂，该杂化树脂包含：
-10-50重量％的如权利要求1或2所定义的组合物A，
-50-90重量％的如权利要求1或2所定义的组合物B。
13.权利要求1或2的凝胶涂层，其中所述组合物B的酸值为10或更小，且基于固体物的羟基数为120-170。
14.权利要求13的凝胶涂层，其中所述羟基数为130-160。
15.权利要求1或2的凝胶涂层，其中组合物A中的所述脂肪族多官能异氰酸酯具有5％-50％的NCO含量。
16.权利要求15的凝胶涂层，其中所述异氰酸酯具有10％-35％的NCO含量。
17.权利要求1的凝胶涂层，其中所述脂肪族多异氰酸酯具有至少两个官能团，并且能够与组合物B的所述聚酯多元醇反应。
18.权利要求1的凝胶涂层，其中所述杂化树脂具有触变性。
19.权利要求18的凝胶涂层，其中通过以组合物B的重量的0.2％-5％的重量含量添加选自硅石、脂肪酸酰胺、粘土的触变剂，使得所述杂化树脂具有触变性。
20.权利要求1的凝胶涂层，其中该凝胶涂层涂覆在复合模塑基底上，该基底是由权利要求1所定义的凝胶涂层的杂化树脂或由不饱和聚酯树脂或由乙烯基酯或由任何其它热固性树脂制备的。
21.权利要求1或2的凝胶涂层，其中在所述杂化树脂中的NCO基团与OH基团的摩尔比为0.3～2.0。
22.权利要求21的凝胶涂层，其中所述摩尔比为0.5～1.5。
23.包含权利要求1-22中任一项的凝胶涂层的制品。
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| JP2003171429A (ja) * | 2001-12-04 | 2003-06-20 | Hitachi Chem Co Ltd | 不飽和ポリエステル樹脂組成物及びこの製造法、並びにこれを用いた熱硬化性成形材料及びプラスチック成形品 |
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- 2006-08-21 WO PCT/EP2006/008199 patent/WO2007022932A2/en active Application Filing
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4107101A (en) * | 1974-06-05 | 1978-08-15 | Bayer Aktiengesellschaft | Process for the production of crosslinked, urethane-containing plastics |
| US5142015A (en) * | 1989-10-25 | 1992-08-25 | Bayer Aktiengesellschaft | Unsaturated urethanized polyester resins, a process for their production and their use for the production of coatings |
| US5159044A (en) * | 1990-11-20 | 1992-10-27 | Amoco Corporation | Sheet molding compounds having improved viscosity |
| US5821296A (en) * | 1996-04-22 | 1998-10-13 | Aristech Chemical Corporation | Polyurethane-polyester hybrid resin system having improved stability |
| CN1513009A (zh) * | 2001-06-01 | 2004-07-14 | ŵ�����˹ɷ�����˾ | 包含多异氰酸酯和由多元醇、多元羧酸和一元羧酸制备的聚酯低聚物的涂料组合物 |
| WO2003099898A1 (en) * | 2002-05-17 | 2003-12-04 | University Of Maine System Board Of Trustees | Methods for strengthening wood products and modified unsaturated polyester resins therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101318682B1 (ko) | 2013-10-16 |
| ATE432305T1 (de) | 2009-06-15 |
| BRPI0615711A2 (pt) | 2011-05-24 |
| DK1917286T3 (da) | 2009-09-14 |
| EP1917286B1 (en) | 2009-05-27 |
| WO2007022932A3 (en) | 2007-05-03 |
| MY141205A (en) | 2010-03-31 |
| ES2327449T3 (es) | 2009-10-29 |
| SI1917286T1 (sl) | 2009-10-31 |
| PL1917286T3 (pl) | 2009-10-30 |
| PT1917286E (pt) | 2009-08-24 |
| AU2006284121B2 (en) | 2011-12-15 |
| WO2007022932A2 (en) | 2007-03-01 |
| CA2620015C (en) | 2014-05-06 |
| JP2009506146A (ja) | 2009-02-12 |
| DE602006007014D1 (de) | 2009-07-09 |
| BRPI0615711B1 (pt) | 2021-10-13 |
| ZA200801005B (en) | 2008-11-26 |
| JP5435695B2 (ja) | 2014-03-05 |
| KR20080039456A (ko) | 2008-05-07 |
| EP1917286A2 (en) | 2008-05-07 |
| MX2008002450A (es) | 2008-04-03 |
| CN101243116A (zh) | 2008-08-13 |
| CA2620015A1 (en) | 2007-03-01 |
| AU2006284121A1 (en) | 2007-03-01 |
| US20070049686A1 (en) | 2007-03-01 |
| US8742054B2 (en) | 2014-06-03 |
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