CN1064054C - 含有三个氨基甲酸酯官能基的交联剂 - Google Patents
含有三个氨基甲酸酯官能基的交联剂 Download PDFInfo
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- CN1064054C CN1064054C CN94105379A CN94105379A CN1064054C CN 1064054 C CN1064054 C CN 1064054C CN 94105379 A CN94105379 A CN 94105379A CN 94105379 A CN94105379 A CN 94105379A CN 1064054 C CN1064054 C CN 1064054C
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3831—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
- C08G18/3853—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring containing cyanurate and/or isocyanurate groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明涉及可固化组合物，特别是可固化的丙烯酸类涂层组合物，该组合物包括(a)一种具有多个能与氨基甲酸酯反应官能基团的化合物；(b)一种下式的化合物。该组合物提供了耐溶剂性、耐盐性和耐各种环境侵蚀的性能。
Description
本发明涉及可固化的组合物，具体说是可固化的涂层组合物，特别是丙烯酸类组合物。
用于涂层和／或模塑的以三异氰脲酸酯为主要成分的聚氨酯组合物在先有技术中是公知的。该组合物提供了许多有用的性能，如耐溶剂性、耐盐性和耐其它各种环境侵蚀的性能。
然而这类聚氨酯也确有一些缺点。这类聚氨酯的主要组成构件是三异氰脲酸酯。三异氰脲酸酯价格昂贵且难于运输。因为三异氰脲酸酯上面的NCO基团是高度活泼的，所以要想把它们用在单组分涂层组合物中就必须用化学方法将此NCO保护起来。使用化学保护基团会进一步增加了物料费用，会导致在固化时固化速度增加，会在组合物中引入具有潜在副作用(如发黄)的额外组分，另外，需要在约150℃的高温下进行热固化。如果不用化学方法保护NCO基团，就必须用三异氰脲酸酯作为双组分组合物的一个组分。对于这样的组合物，必须将高度活泼的三异氰脲酸酯和周围的环境隔离开，也要和该组合物的其它组分隔离开，直至涂到基底上或进行模塑，这就进一步增加了工艺过程的费用和复杂性。
因此，长期以来人们希望生产出一种组合物，它能显示出具有如上所述的极佳综合性能的固化三异氰脲酸酯组合物所具有的优点，而并不一定使用异氰酸酯基作为固化反应的官能基团。
按照本发明，提出了一种可固化的组合物，它包括：(a)一种具有多个能和氨基甲酸酯反应的官能基的组分，(b)按照式(Ⅰ)的一种组分
其中：
Z代表一个氰脲环核或者一个多元醇残基，
L1、L2和L3分别各代表一个二价交联基团，或者一个共价键，
R1、R2和R3分别各代表氢、烷基、环烷基或芳基。
在实施本发明时使用的组分(a)具有能与(b)组分中氨基甲酸酯基团反应的基团。这样的活泼基团包括在氨基塑料交联剂或其它组分(如酚甲醛加合物、异氰酸酯基、硅氧烷基和酸酐基)上的活性的羟甲基或甲基烷氧基。组分(a)的例子包括三聚氰胺-甲醛树脂(包括单体的或聚合物三聚氰胺树脂，以及部分或全部烷基化的三聚氰胺树脂)、脲醛树脂(比如羟甲基脲树酯像脲甲醛树酯、烷氧基脲树脂像丁基化脲甲醛树酯)、聚酸酐(如聚琥珀酸酐、马来酸酐共聚物)和聚硅氧烷(如三甲氧基硅氧烷)。像三聚氰胺-甲醛树酯或脲-甲醛树酯之类的氨基塑料树脂是特别好的。在氨基塑料树脂中一个或者几个氨基氮被氨基甲酸酯基团取代，在低于150℃的固化温度的方法中使用甚至更好。这在题为《氨基甲酸酯去官能化的氨基塑料用于聚合物固化》的美国专利申请系列号No 07／965，510中有所叙述。
在实施本发明时使用的组分(b)具有(Ⅰ)的结构，
其中：
Z代表一个氰脲环核或一个多元醇残基，
L1、L2和L3分别各代表一个二价交联基团，或者一个共价键，以及
R1、R2和R3分别各代表氢、烷基、环烷基或者芳基。
可以使用不同的合成路线来制造按照式(Ⅰ)的化合物。
在本发明的推荐实例中，Z代表一个氰脲环。这样的化合物可以用下式表示：
(a)一个具有多个和氨基甲酸酯反应的官能基团的组分，
(b)按照式(Ⅱ)的组分
式中：
L1、L2和L3分别各代表一个交联基团，以及
R1、R2和R3分别各代表氢、烷基、环烷基。
当Z代表一个氰脲环时，二异氰酸酯首先可能与含有与异氰酸酯反应的基团和氨基甲酸酯基团(如氨基甲酸羟烷基酯，像氨基甲酸羟丙基酯或氨基甲酸羟丁基的化合物反应，然后进行三聚化而形成异氰脲酸酯。在另一种情况下，二异氰酸酯首先可能与含有与异氰酸酯反应的基团和在形成三异氰脲酸酯之后能形成氨基甲酸酯基团的化合物反应。例如，一种二异氰酸酯能够和一种OH官能环碳酸酯(如甘油和CO2的反应产物)反应、三聚形成异氰脲酸酯，碳酸环酯基与氨反应形成氨基甲酸酯官能基。
在另一个实例中，一个已经形成的，具有多个NCO基团的三异氰脲酸可以同含有可同异氰酸酯反应的基团和氨基甲酸酯基团(如氨基甲酸羟丙基酯或氨基甲酸羟丁基酯等氨基甲酸羟烷基酯)的化合物反应。在另一种情况下，异氰脲酸酯可以同那些在同异氰脲酸酯反应完成后能够形成氨基甲酸酯基团的取代基加合。例如，异氰脲酸酯能够与具有羟基和碳酸环酯基(如甘油与CO2反应的产物)的化合物反应，碳酸环酯基然后与氨反应形成氨基甲酸酯基团。
另一种合成方法是让具有多个非NCO官能基团的异氰脲酸酯和含有至少一个氨基甲酸酯基团和至少一个可与非NCO官能基反应的基团的化合物反应。非NCO官能基团的例子包括羧基、环氧基、羟基、氨基。例如，通过一个三聚的二异氰酸酯与过量的二元醇(用来控制交联的量)反应或者通过氰脲酸与环氧乙烷反应所形成的含羟基三异氰脲酸酸可以与羟甲基丙烯酰胺(OH-CH2-NH-CO-CH=CH2)反应，然后不饱合反应点与过氧化物反应形成环氧基团。然后此环氧基与CO2反应形成与氨反应能转变为氨基甲酸酯基团的碳酸环酯基。在另一种情况下，一个通过三聚的二异氰酸酯和羟基官能羧酸反应或者氰脲酸与环氧乙烷反应，然后再与甲基六氢苯二甲酸酐反应而形成的酸官能三异氰脲酸酯可以同醋酸酐反应生成酐官能的三异氰脲酸酯，它能进一步与羟基氨基甲酸酯反应。
在美国专利申请系列号07／937，612中叙述了具有非NCO基团的异氰脲酸酯或氰脲环化合物，其内容在本说明书中引作参考。
上述的二异氰酸酯、含NCO官能团的异氰脲酸酯、含非NCO官能团的异氰脲酸酯和氰脲环化合物和含有氨基甲酸酯基团或者能转变为氨基甲酸酯的基团以及能与含NCO-或非NCO-基发生反应的基团相加合。能够加合到二异氰酸酯或异氰脲酸酯的NCO-基团上的含有氨基甲酸酯基团化合物最好是氨基甲酸羟烷基酯，如氨基甲酸羟丙基酯或氨基甲酸羟丁基酯。含有能转变为氨基甲醇酯的基团和能与NCO反应的基团的化合物包括与氨反应能转变为氨基甲酸酯的含羟基碳酸环酯化合物(比如甘油和CO2的反应产物)、先与CO2反应再与氨反应就能转变为氨基甲酸酯的单缩水甘油醚(如Cardura E)、先与CO2反应再与氨反应就能转变为氨基甲酸酯的单缩水甘油基酯(如羧酸和环氧氯丙烷的反应产物)、分子中醇基能与NCO反应，而双键和过氧化物反应能转变为氨基甲酸酯的烯丙基醇，以及分子中酯基能与NCO反应而乙烯基先与过氧化物，再与CO2，再与氨反应可转变为氨基甲酸酯的乙烯基酯。
上式中二价交链基团L1、L2和L3的组成可以由所选的氰脲环化合物或多异氰酸酯的种类加以控制。二价交联基L1、L2和L3分别各自可为脂肪族的(如六亚甲基)、环脂族的，(如二异氰酸异佛尔酮基酯或或芳香族的(如二异氰酸四亚甲基亚二甲苯基残基)，它们最好不超过20个碳原子，并且具有与含有氨基甲酸酯基团的取代基相结合的氨基甲酸酯、脲或酯的端基。如果希望能抗日光降解，最好所有的二价交联基团都是脂肪族或脂环族。在一个推荐的实例中，每一个L基团独立地代表通式为-A-NH-COO-D-的基团，其中A和D各代表如下所述的二价交联。
在上式中，R1、R2和R3各自独立地代表氢、最好为1-6个碳原子的烷基或最多不超过6碳原子环的环烷基。应该明白，所谓烷基和环烷基应包括取代的烷基或环烷基，比如卤素取代的烷基或环烷基。在一个推荐的实例中，R1、R2和R3都是H，由于伯胺基甲酸酯的活性高于仲胺基甲酸酯，这就使得在选择组分(a)时有更大的灵活性，该组分(a)在固化期间与氨基甲酸酯基团反应。不过应该避免对固化材料的性能有负面影响的取代基。例如，据认为醚键容易受水解的影响，因此应避免将其放在会使醚键出现在交联网架中的位置上。
虽然在本发明中可以使用由氰脲酸得到的异氰脲酸酯，但最好是由一种或者几种二异氰酸酯(如二异氰酸六亚甲基酯或二异氰酸异佛尔酮基酯)缩合而形成的异氰脲酸酯。推荐的异氰脲酸酯的例子包括二异氰酸六亚甲基酯的异氰脲酸酯和二异氰酸异佛尔酮基酯的异氰脲酸酯。如果并不特别要求耐光牢度，可以使用如二异氰酸2，4-甲苯酯的芳香族二异氰酸酯。
在本发明的一个推荐实例中，由三聚的二异氰酸酯得到组合(b)，它具有如式(Ⅲ)的结构：
式中：
A1、A2和A3各独立地代表一个二价交联基，
D1、D2和D3各独立地代表一个二价交联基。
在这个式中，每个A都是一个二价交联基，一般是由用来形成异氰脲酸酯的二异氰酸酯的核得来的，它既可以是脂肪族的(如六亚甲基)、脂环族的(如二异氰酸异佛尔酮基酯或者也可以是芳香基团，它们最好不多于20个碳原子。每个D都是一个二价交联基团，最好不多于20个碳原子，一般由如上所述的具有氨基甲酸酯基团或者可转变为氨基甲酸酯基团的化合物得来。
在本发明的另一个实例中，Z是一种多元醇(最好是一种三元醇，如三羟甲基丙烷，即TMP或者甘油)的残基。
这类化合物可以通过多元醇与二异氰酸酯(如二异氰酸六亚甲基酯或者二异氰酸异佛尔酮基酯)反应形式三个NCO加合物，这在电沉积涂层组合物领域内是众所周知的。任何已叙述过的有关二异氰酸酯的三NCO官能异氰脲酸酯三聚体的技术都可用于制造三官能氨基甲酸酯化合物。对这些化合物，上(Ⅰ)式中的L1、L2和L3都应是交联基团，如式(Ⅲ)中所显示出的-A-CO2-NH-D-，它们来源于制备三官能NCO加合物时使用的二异氰酸酯和含有氨基甲酸酯基的化合物。例如，TMP和二异氰酸六亚甲基酯的三NCO官能加合物能够和羟基氨基甲酸酯(如氨基甲酸羧丙酯)反应生成三官能氨基甲酸酯化合物。
另外，如果要形成按照式(Ⅰ)的仲胺基甲酸酯，式中的R1、R2和R3不是氢的话，那么多元醇可以和单异氰酸酯化合物(如异氰酸丁酯)反应。在这种情况下，L1、L2和L3将代表一个共价键。
按照式(Ⅰ)、式(Ⅱ)和式(Ⅲ)的化合物分子量以300-3000为好，最好为450-1800。每个氨基甲酸酯官能基团的当量重为100-1000，最好为150-600。在按照本发明所用的涂层组合物中可任意选择地使用溶剂。虽然本发明的配方可以用比如基本为固体粉末或者分散液的形式来使用，但往常希望以基本为液态的形式使用本发明的配方，这样同时可使用溶剂。使用的溶剂的量最好能有效地使组分(a)和组分(b)都溶解。一般说来，溶剂可以是任何有机溶剂和／或水。溶剂为极性脂肪族或者极性芳香族溶剂更好。溶剂最好为酮、酯、醋酸酯、对质子惰性的酰胺、质子惰性砜、质子惰性胺和水。可用溶剂的例子包括甲乙酮、甲基异丁基酮、醋酸正戊酯、乙二醇丁基醚醋酸酯、丙二醇单乙醚醋酸酯、
二甲苯、N甲基吡啶烷酮和混合芳烃。
涂层组合物中溶剂的量可以为0．1-99％(重量)，10-60％(重)更好，而约30-约50％(重量)最好。
可以用许多先有技术中任一种公知的技术将上述涂层组合物涂在制品上。这比如可包括：喷涂、浸涂、辊涂和幕式淋涂等。对汽车本体表盘以喷涂为最好。
在一个推荐实例中，本发明的组合物作为有色+透明复合涂层的一部分，在加有颜料的底涂层之上作为透明涂层组合物。这种复合涂层由于色泽在底部而表面有一种液体光泽而广为流行。这在汽车领域受到特别广泛的认可。
由于这种复合涂层的加有颜料的底涂层组合物在先有技术中是公知的，在此无需仔细说明。在底涂层组合物中使用的，在先有技术中为公知的聚合物包括丙烯酸类、乙烯基类、聚氨酯类、聚碳酸酯类、聚酯类、醇酸类和聚硅氧烷类聚合物。推荐的聚合物包括丙烯酸类和聚氨酯类。底涂层聚合物最好是可交联的，因此含有一种或多种可交联的官能基。这样的基团包括：例如羟基、异氰酸酯基、胺基、环氧基、丙烯酸酯基、乙烯基、硅烷基和乙酰乙酸酯基。这些基团可以用如下方式加以保护，即在希望的固化条件下(一般是高温)对于交联反应不表现出保护，而是可使用的。有用的可交联基团包括羟基、环氧基、酸基、酸酐、硅烷和乙酸乙酸酯。推荐的可交联官能基包括羟基官能基和胺官能基。
底涂层聚合物可以是可自交联的，也可以需要另外的可与该聚合物官能基反应的交联剂。例如，当聚合物含有羟官能基时，交联剂可以是一种氨基塑料树脂、异氰酸酯和保护的异氰酸酯(包括异氰脲酸酯)以及酸或者酸酐官能交联剂。
在用上述的按照本发明的各层涂在制品上以后，把被涂的制品放在使各涂层能固化的条件之下。虽然可使用各种固化方法，最好还是热固化。一般说来，把涂好的制品放在主要由辐射热源产生的高温下就可进行热固化。固化温度将根据在交联剂中使用的特定保护基团的不同，然而一般是在82-144℃之间，最好是在110-133℃之间。固化时间将根据保护剂和物理参数(如涂层厚度)而变化，然而典型的固化时间15-60分钟。
用如下实例进一步叙述本发明。实例1具有氨基甲酸酯官能基的三异氰脲酸酯
在一个氮气保护下的反应釜中加入1047．0克T1890(从Piscataway，NY 的Hulls America公司购得的二异氰酸异佛尔酮基酯、4．2克二月桂酸二丁基锡和356．7克丙二醇单乙醚醋酸酯溶剂。控制反应混合物温度直至达约80℃的恒温，慢慢加入381．1克氨基甲酸羟丙基酯。维持反应直至实际上所有NCO被消耗为止。这时，向混合物中再加入溶剂(337．88克丙二醇单乙醚醋酸酯和25．0克正丁醇)。
实例2
涂层实例
制备有如下配方的透明涂层组合物：
成分 重量份
实例1的产物 56，70
部分去官能化的三聚氰胺树 14．19
脂*在二甲苯中的分散液
(非挥发份51．9％)
Tinuvin 348 B 6．84
Tinuvin 123 0．42
十二烷基苯磺酸分散液 0．84
(非挥发份33．0％)
混合溶剂(Exxate 800和丁醇) 26．61
*系列号07／965．510美国专利申请书中所叙述的三聚氰胺甲醛树脂，通过将氨基甲酸酯基团加合到三聚氰胺上使其中三个反应点不同异氰脲酸酯的氨基甲酸酯基团发生反应。此化合物有如下结构式：
将此组合物涂敷到预先涂过一层未烘烤过的高固体份含溶剂丙烯酸／三聚氰胺含颜料底涂料的金属测试板上。在打过底的金属测试板上涂底涂料时，共涂两道，中间间隔1分钟让第一层涂层迅速干燥。在涂过第二层涂料后，底涂层迅速干燥，然后就涂此透明涂层组合物。透明涂层以两层平滑涂层的方式涂敷，两次涂敷之间瞬干。涂过的底基进行短时间干燥，然后再在140℃下烘烤固化30分钟。
然后，将此板在苛刻的产生侵蚀条件下在户外曝晒架上放置四周。按通用电机侵蚀评价尺度计，用本发明涂层(实例2)涂敷的测试板其耐侵蚀等级为最好的1级。与此相比较，用羟基官能团丙烯酸类聚合物和烷基化三聚氰胺甲醛树脂作为透明涂层的现有技术所涂敷的测试板，其通用电机侵蚀评价尺度的侵蚀等级为10。这表现出按照本发明的涂层组合物有较好的耐侵蚀性能。
用推荐的实例作为参考详细地对本发明进行了叙述。然而应该明白只要在本发明的精神和范围之内，可以进行各种变化和改变。
Claims (11)
1．一种涂层组合物，其特征在于，它包括：(a)一种具有多个能与氨基甲酸甲酯反应官能基团的化合物，该化合物选自三聚氰胺-甲醛树脂，脲醛树脂、聚酸酐和聚硅氧烷，其中的三聚氰胺-甲醛树脂包括全部或部分烷基化的三聚氰胺树脂，和(b)一种按照下式的化合物：
式中
L1、L2和L3各独立地代表一个交联基团，以及
R1、R2和R3各独立地代表氢、烷基或环烷基。
2．按照权利要求1的一种涂层组合物，其特征在于，R1，R2和R3各独立地代表氢。
3．按照权利要求1的一种涂层组合物，其特征在于，R1，R2和R3各独立地代表1-6个碳原子的烷基或不超过6个碳原子环的环烷基。
4．按照权利要求1的一种涂层组合物，其特征在于，L1、L2和L3各包括一种氨基甲酸酯键。
5．按照权利要求1、2或3的一种涂层组合物，其特征在于，组分(a)选自其上具有羟甲基或甲基烷氧基的氨基塑料树脂，聚硅氧烷和聚酸酐。
6．按照权利要求1、2、3或4的一种涂层组合物，其特征在于，组分(a)是三聚氰胺甲醛树脂，包括单体或聚合物三聚氰胺树脂，以及部分或全部烷基化的三聚氰胺树脂。
7．按照权利要求5的一种涂层组合物，其特征在于，该氨基塑料树脂中一个或几个氨基氮被氨基甲酸酯基团取代。
8．按照权利要求1的一种涂层组合物，其特征在于，组分(b)具有如下结构式
其中，A1、A2和A3各独立地代表一种二价交联基团，以及
D1、D2和D3各独立地代表一种二价交联基团。
9．一种有色且透明的复合涂层，其特征在于，它包括一种着色的底层涂层和一层透明涂层，所述透明涂层来源于按照权利要求1、2或4的涂层组合物。
10．一种按照权利要求9的有色且透明的复合涂层，其特征在于，组分(b)具有如下结构式：
式中，
A1、A2和A3各独立地代表一个二价交链基团，以及
D1、D2和D3各独立地代表一个二价交链基团。
11．一种可固化的组合物，其特征在于，它包括：
(a)一种具有多个能与氨基甲酸甲酯反应官能基团的化合物，该化合物选自三聚氰胺-甲醛树脂，脲醛树脂、聚酸酐和聚硅氧烷，其中的三聚氰胺-甲醛树脂包括全部或部分烷基化的三聚氰胺树脂，和(b)一种按照下式的化合物：式中L1、L2和L3各独立地代表一个交联基团，以及R1、R2和R3各独立地代表氢、烷基或环烷基。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US056,514 | 1987-06-01 | ||
| US08/056,514 US5336566A (en) | 1993-04-30 | 1993-04-30 | Tri-carbamate-functional crosslinking agents |
| US056514 | 1993-04-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1112148A CN1112148A (zh) | 1995-11-22 |
| CN1064054C true CN1064054C (zh) | 2001-04-04 |
Family
ID=22004909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94105379A Expired - Lifetime CN1064054C (zh) | 1993-04-30 | 1994-04-29 | 含有三个氨基甲酸酯官能基的交联剂 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5336566A (zh) |
| EP (1) | EP0622387B1 (zh) |
| JP (1) | JP3506764B2 (zh) |
| KR (1) | KR100326622B1 (zh) |
| CN (1) | CN1064054C (zh) |
| AU (1) | AU683046B2 (zh) |
| BR (1) | BR9401645A (zh) |
| CA (1) | CA2122534C (zh) |
| DE (1) | DE69411221T2 (zh) |
| ES (1) | ES2120535T3 (zh) |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU6072994A (en) | 1994-11-03 |
| JP3506764B2 (ja) | 2004-03-15 |
| DE69411221T2 (de) | 1999-02-18 |
| EP0622387A1 (en) | 1994-11-02 |
| KR100326622B1 (ko) | 2002-09-05 |
| EP0622387B1 (en) | 1998-06-24 |
| CN1112148A (zh) | 1995-11-22 |
| CA2122534C (en) | 2003-03-11 |
| BR9401645A (pt) | 1995-03-07 |
| ES2120535T3 (es) | 1998-11-01 |
| CA2122534A1 (en) | 1994-10-31 |
| US5336566A (en) | 1994-08-09 |
| DE69411221D1 (de) | 1998-07-30 |
| AU683046B2 (en) | 1997-10-30 |
| JPH0726059A (ja) | 1995-01-27 |
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