CN1037726A - 可变色粘合剂 - Google Patents

可变色粘合剂 Download PDF

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CN1037726A
CN1037726A CN89103482A CN89103482A CN1037726A CN 1037726 A CN1037726 A CN 1037726A CN 89103482 A CN89103482 A CN 89103482A CN 89103482 A CN89103482 A CN 89103482A CN 1037726 A CN1037726 A CN 1037726A
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tackiness agent
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威廉·弗朗西斯·马威克
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Rio Tinto Alcan International Ltd
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Abstract

一种粘合剂组合物，其中包含一种单料式热固化 型粘合剂和一种具有效含量的实质上水不溶性指示 剂的混合物，所述指示剂在室温实质上不与该单料式 热固化型粘合剂的各组分(即可固化树脂、用于该树 脂的热活化的固化剂以及促进剂)发生反应，但当该 粘合剂固化时使得该组合物产生颜色变化。最好改 粘合剂是一种单料式热固化型环氧树脂粘含剂体 系。使用此种粘合剂组合物可以用肉眼观察确定该 粘合剂的固化点。

Description

本发明涉及一种可变色粘合剂。更具体讲，是涉及一种单料式热固化型粘合剂，特别是一种单料式热固化型环氧树脂粘合剂，这种粘合剂在固化过程中能改变颜色。
通常工业用的粘合剂体系是两料式体系或单料式体系。两料式体系包括含有可固化树脂的第一部分和含有用于该可固化树脂的固化剂作为第二部分。由于两料式粘合剂体系的两个部分一经混在一起就相互反应而使该树脂固化，所以它们必须分开贮存，只有在临到使用之前才能混到一起。但是，单料式粘合剂体系包含一种可固化树脂和一种适于该可固化树脂的热活化式固化剂所成的具贮存稳定性的混合物，并且平时该树脂与固化剂不发生反应，直到受热使固化剂活化后方才起反应。本发明就是涉及这类热固化型单料式粘合剂体系。
在可用于粘合剂配方中的各类型可固化合成树脂中，其中有一类具重要工业用途，就是环氧树脂类。工业中已广泛使用加热固化的环氧树脂粘合剂。它们与室温固化的两料式环氧树脂粘合剂相比，具有若干优点。热固化型环氧树脂粘合剂与那些室温固化的粘合剂不同，它们不需要把两个部分即树脂及交联剂精确混合。此外，与室温固化两料式环氧树脂粘合剂相比，热固化型环氧树脂粘合剂能使该粘合剂具有较优的耐高温环境性能。
但不利的是，热固化型环氧树脂粘合剂要求在固化时精确地输入热量，以便使接合部位达到最优性能。例如，某些热固化型环氧树脂粘合剂对于过度固化是敏感的，当工件在烘炉中时间过长或烘炉温度过高时，使接合部位的性能变差。还有一些热固化型环氧树脂粘合剂对固化不足是敏感的，从而使体系中未反应部分脆弱而不能经受苛刻环境，暴露在外的接合部位强度变弱。一般来讲，当使用大型烘炉时不难作到在固化时精确输入热量，但在应用其他加热方法特别采用红外线辐照时，就难于作到。况且红外线辐照加热方法对于某些粘结结构是非常必要的，例如极大的工件就无法置于烘炉之内，或是遇到粘结修补的情况，这时只需局部加热。本发明的目的是在事先难于控制加热的场合在环氧树脂粘合剂的热固化中能够精确地输入热量。
USP    3773706提出了在两料式粘合剂体系的可固化树脂部分加入碱性染料酚藏花红，即3，7-二氨基-5-苯基氯化吩嗪鎓。当固化剂部分与含有该染料的树脂部分加混到一起后，固化反应即可进行，并随着反应的进行，由该染料所带来的颜色也随之变化。按USP    3773706的表Ⅰ中的实例Ⅱ，向两料式环氧树脂粘合剂体系中加入该染料后，其颜色在23℃的低温即发生变化。
USP    4164492描述了在一种用于增量填充物料或模制组合物中的两料式聚酯或环氧树脂体系中使用一种染料来指示该两个部分是否已混合均匀，还指示树脂在该混合物中固化的程度。该染料（特别是偶氮苯4-偶氮-2-萘酚的甲基衍生物）是加入到该两料式体系其中之一或另一部分之中，使之具有颜色。从树脂-催化剂混合物颜色的均匀性来指示该两部分是否已彻底混匀。这种染料随着固化反应进行而失去颜色，从而提供对树脂最后完成固化和进程的指示。
USP    4160064披露了一种两料式环氧树脂封合剂，它是由第一和第二种带子所组成，第一种带含有一种可固化的环氧树脂组合物，在分开的第二种带中含有用于该可固化环氧树脂组合物的固化剂。在环氧树脂组合物中还含有一种着色剂，它使第一种带有颜色，但它与该固化剂接触后又失去它的颜色。在第一种带中由于有该着色剂，就可以保证它们用作为封合剂之前把两种带混合均匀。这两个部分一经混合在一起，这种着色剂就开始褪色，据说在混合后数分钟内完全褪色，或至少在该环氧树脂组合物固化时完全褪色。USP    4160064中所披露的染料据说若最初只加入到固化剂中，就没有使该环氧树脂封合剂具有潜在的瞬时颜色的效能。
USP    4717674提出了一种方法来测定两料式环氧树脂体系的聚合程度，该方法是在该环氧树脂上加有活性与该环氧树脂的固化剂活性相似的荧光染料作为标记。
当环氧树脂和固化剂之间进行反应时，该标记的荧光就变化，因此，借助于测定该标记的发射情况，就可以测定该树脂的固化程度。
英国专利960，276提出了使固化剂与环氧树脂混合彻底的方法。其中披露了使用一种具酸-碱指示剂性质的染料，将该染料先与环氧树脂密切混合，而当其后加入固化剂并与树脂部分密切混合后，它的颜色发生改变。
上述先有技术都是只用于两料式组合物，都未提到单料式体系。事实上，其中所披露的体系都是该染料或颜料在遇到该两料式体系中的一种或另一种（即树脂或固化剂）时因具有反应活性结果使颜色改变。这些都不能应用于单料式粘合剂体系，因为单料式必须是同时含有固化剂和树脂的在贮存中稳定的混合物。
因此，本发明是提供一种粘合剂组合物，其中包含一种单料式热固化型粘合剂和有效含量的实质上水中不溶的指示剂，而这种指示剂在室温不与该粘合剂反应，但在该粘合剂固化时具有发生颜色变化的能力。
本发明还提供一种粘接两个工件的方法，包括在准备粘接的工件表面上涂上一种粘合剂组合物，该组合物包含一种单料式热固化型粘合剂和一种实质上不溶于水的指示剂，这种指示剂在室温实质上不与该粘合剂反应，但当该粘合剂固化并向接合部位施加热量时具有使该组合物颜色变化的能力，直至该粘合剂组合物的颜色变化表示该粘合剂已完成固化为止。
本发明优于以前所用单料式体系之处在于对粘合剂固化的指示可以使粘接部位得到可靠固化而不需用其他监控系统，例如向粘接线处插入热电偶。
不讲自明的是，本发明涉及的是单料式热固化型粘合剂组合物。如前所述其中包含一种可固化的树脂组合物与一种固化剂的加混物，而该固化剂在室温不会和该可固化树脂组合物发生反应，但它在高温被活化，于是和该树脂组合物发生反应而引起固化。一般情况下，单料式热固化型粘合剂组合物还含有一种促进剂，用于加速树脂-固化剂的反应。对于单料式热固化型环氧树脂体系而言，通常使用胺类促进剂。
适用于本发明的热固化型粘合剂应是在比较低温度即能固化的，并且在室温它们实质上不与所用指示剂发生反应。应注意的是，该粘合剂的固化是由颜色变化来指示，只有不致掩盖此种颜色变化的粘合剂才是适用的。在本发明中特别优选的是使用一种单料式热固化型环氧树脂粘合剂作为该组合物中的粘合剂组分，因为这种粘合剂广泛应用于要求高粘结强度的许多工业用途。此外，由于本发明特别适用于借助向接合部位辐照红外线来进行固化的场合，使用单料式热固化型环氧树脂粘合剂是特别适宜的，因为它们是在较低温度固化，例如在160℃左右。此类单料式环氧树脂粘合剂已为人所熟知，并且除含有可固化的环氧树脂之外，还含有一种热活化的固化剂，一般是双氰胺，还有一种胺类促进剂。双氰胺在室温不溶于环氧树脂，因此是以环氧树脂中的微细分散体系形式存在。在此阶段，环氧树脂和双氰胺之间实质上不发生反应。当温度高于约120℃，该双氰胺开始溶解于环氧树脂中，在溶解之后，双氰胺就与环氧树脂一起反应使得树脂发生固化。
由于双氰胺对于环氧树脂的反应活性不高，在该组合物中包括一种胺类促进剂，用以提高反应的程度。多种适用于本发明的粘合剂均可从市场上购到，例如商品标号为DP    70-0126的单料式热固化型环氧树脂粘合剂（Stafford的Evode    Ltd出产）。无论何种情况下，都可用常规试验来确定一种热固化型环氧树脂粘合剂是否适用于本发明。
本发明中应用的指示剂是这样的物质，它在室温（25℃）与该单料式体系中任何组分（即：树脂、固化剂和促进剂）都是实质上不起反应。相反，它应当在热引致的固化过程中由颜色变化来反映该粘合剂内的反应。这些指示剂并不是直接反映温度的那些物质，因为若是直接反映温度，它就不能区别下面两种情况：一是在固化周期中将该粘合剂慢速加热并瞬间达到其固化温度;另一是迅速将粘合剂加热至固化温度并在该温度保持一些时间。暂且不考虑某些理论，可以认为在正在发生热引致的固化的环氧树脂粘合剂内所进行反应的特征表现在该粘合剂的酸度变化或是氧化还原环境的变化。不利的是，那些常规式水溶性化学指示剂并不适用于本发明，因为向单料式环氧树脂粘合剂中加入水溶性物质，对于由此粘合剂所加工的受负荷粘接部位的耐久性是十分不利的。但是，常规式化学指示剂中那些实质上不溶于水并符合上述其他要求的指示剂，可能适用于本发明。溴甲酚红紫是实质上不溶于水的，它可以在本发明中应用，但由于含有溴甲酚红紫的单料式热固化型环氧树脂粘合剂不具备长期稳定性，所以它的应用受到局限。有一类物质是水不溶性并且在pH或氧化还原环境改变时形成带颜色的衍生物，这类物质包括在压感复写纸（carbonless    copying    paper）中所用的成色剂，并在“Journal    of    the    Society    of    Dyers    and    Colourists”，105，April    1989，pp.171-172中有所描述。有一种商品名Reaktred    448（BASF，即Badische    Anilin    and    Soda    Fabrik    AG产品）的成色剂。Reaktred    448是一种荧烷（fluoran）成色剂（重氮基若丹明内酯），附图中示出其红外光谱图。在本发明中可用的氮杂若丹明内酯成色剂在西德专利申请号DE-A-2603101（BASF）中有所披露。另一可用的成色剂实例是1，2-苯并-6-二乙胺-荧烷（见“Journal    of    the    Society    of    Dyers    and    Colourists”，105，April，1989，172页    17b行）。向该组合物中加入指示剂的量当然要取决于该指示剂的初始及最终颜色（及它们的强度）。一般情况下，按该组合物总重量计，其用量是在0.1-1.5%范围。
本发明可普遍应用于将部件粘结到一起的用途，例如将金属结构的部件粘结到一起。
附图示出Reaktred 448的红外光谱图。该分析是用Perkin Elmer 783型红外分光光度计所作，并用Perkin Elmer 7500型专业计算机记录并解析其结果。图中的X-轴表示光的波数（厘米-1），用溶于1，1，2-三氯三氟乙烷中的Reaktred 448样品并于KBr盘上抹涂后使光线通过。Y-轴表示入射光透过该样品的百分率。
实例1
制备按本发明的粘合剂组合物，在机械式混合器中，将单料式热固化型环氧树脂粘合剂DP-0126（Stafford的Evode    Ltd出产）与占全部组合物1.5%（重量）的成色剂Reaktred    448（BASF产品）混合到一起。此混合物的性质如下示。
在25℃，8星期后对
粘合剂粘度的影响    初始颜色    颜色Ⅰ    颜色Ⅱ    颜色Ⅲ
稍变稠厚    橙    橙    黄    黄
其中：颜色Ⅰ是在120℃，30分钟后
颜色Ⅱ是在160℃，30分钟后
颜色Ⅲ是在180℃，30分钟后
在120℃，30分钟后，该环氧树脂粘合剂的反应未完全;但是，在160℃，加热30分钟后该组合物颜色变化，并且将该组合物加热至180℃并无另外的颜色变化，表示该粘合剂在160℃加热30分钟后已基本上固化完全。从这些结果明显看到，Reaktred    448是适用于加入到环氧树脂粘合剂中的指示剂，它在固化完全之前颜色不变，并且它对该粘合剂无不利效应。
实例2
制备下述按本发明的粘合剂组合物：
组合物A：DP    70-0126（Evode    Ltd.，产品）
+1%（重量）Reaktred    448（BASF产品）
组合物B：DO-0126（Evode    Ltd.，产品）
+1%（重量）溴甲酚红紫（5，5′-二溴-邻-甲酚磺基酞，即5，5′-dibromo-o-cresolsulphonephthalein）
通过研磨将该成色组分混入该膏状粘合剂中。两者均未与该粘合剂立即发生反应。将厚度1，6毫米的5251铝合金板先经预处理，预处理时使用“Accomet    C”（Albright    and    Wilson公司产品）免冲洗铬酸盐预处理剂，然后用这些粘合剂制成标准式搭接粘接。于180℃将粘接件固化15分钟，这是这种粘合剂规定的固化程序。将粘接件暴露于中性盐雾中历时20星期，对每种混合物所粘接的同样三件在张力测试仪上拉断测定盐雾试验前后的强度下降。还应用未加成色组分的DP    70-0126进行了试验。所得结果如下：
平均初始强度    暴露20星期后的
粘合剂组合物    （兆帕）    平均强度（兆帕）
DP    70-0126    17.1    16.1（保留94%）
A    16.1    15.6（保留97%）
B    17.3    16.4（保留95%）
实例3
在电动研钵中将100克Epoxyweld    7168（Evode    Ltd.的单料式热固化型环氧树脂组合物专利产品）和1克Reaktred    448混合1小时，成为混合物并将之重新包装。在室温（25℃）贮存3个月之后，分析该混合物，发现其粘度未增高，并且该树脂的固化物的异色异构特性（变色为由粉红至黄）也未下降。

Claims (9)

1、一种粘合剂组合物，其中包含一种单料式热固化型粘合剂和一种具有效含量的实质上水不溶性指示剂的混合物，所述指示剂在室温实质上不与该单料式热固化型粘合剂的各组分发生反应，但当该粘合剂固化时使得该组合物产生颜色变化。
2、权利要求1的组合物，其中该单料式热固化型粘合剂是一种环氧树脂粘合剂。
3、权利要求2的组合物，其中该粘合剂可在温度约160℃进行固化。
4、权利要求2的组合物，其中该水不溶性指示剂是Reaktred  448。
5、一种用粘合剂粘结两个工件的方法，该方法包括以下步骤：（1）将工件的准备粘接的表面上涂以一种粘合剂组合物，该组合物包含一种单料式热固化型粘合剂和一种具有效含量的实质上水不溶性指示剂的混合物，该指示剂在室温实质上不与该单料式热固化型粘合剂的各组分发生反应，但当该粘合剂固化时使得该组合物产生颜色变化;（2）将粘接部位加热，直至该粘合剂颜色变化指示该粘合剂的固化为止。
6、权利要求5的方法，其中该单料式热固化型粘合剂是一种环氧树脂粘合剂。
7、权利要求6的方法，其中该粘合剂是在温度约160℃发生固化。
8、权利要求6的方法，其中该水不溶性指示剂是Reaktred  448。
9、权利要求5的方法，其中是以红外线辐照方式将粘接部位加热。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365047C (zh) * 1999-05-05 2008-01-30 达普产品公司 随时可用的含干燥指示剂的接缝/修补产品
WO2009059511A1 (en) * 2007-11-08 2009-05-14 Wuhan Keda Marble Protective Materials Co., Ltd. A red and green dry adhesive, a method producing the same
CN107001894A (zh) * 2014-11-18 2017-08-01 3M创新有限公司 变色粘合剂组合物
CN109642139A (zh) * 2016-07-08 2019-04-16 施敏打硬株式会社 通过加热固化而颜色发生变化的结构用粘接剂组合物
CN109722192A (zh) * 2017-10-27 2019-05-07 正一龙华特殊材料(深圳)有限公司 变色指示热固胶水及变色指示热固导电胶
CN113166593A (zh) * 2018-12-23 2021-07-23 3M创新有限公司 固化时发生视觉变化的两部分粘合剂组合物

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4001417A1 (de) * 1990-01-19 1991-07-25 Beiersdorf Ag Zaehelastifizierter, zweikomponentiger epoxidharzklebstoff
JPH07123179B2 (ja) * 1990-10-05 1995-12-25 信越ポリマー株式会社 異方導電接着剤による回路基板の接続構造
US7278590B1 (en) 1992-02-24 2007-10-09 Homax Products, Inc. Systems and methods for applying texture material to ceiling surfaces
US6883688B1 (en) 1992-02-24 2005-04-26 Homax Products, Inc. Aerosol spray texturing systems and methods
US8028864B2 (en) 1992-02-24 2011-10-04 Homax Products, Inc. Actuator systems and methods for aerosol wall texturing
US6152335A (en) 1993-03-12 2000-11-28 Homax Products, Inc. Aerosol spray texture apparatus for a particulate containing material
US5807918A (en) * 1996-03-26 1998-09-15 Patch Rubber Company Color changeable aqueous adhesive systems
DE19751953A1 (de) 1997-11-24 1999-05-27 Henkel Kgaa Funktionelle Farbstoffe als Indikator in aerob härtenden Zusammensetzungen
US6017983A (en) * 1998-01-29 2000-01-25 Alpha Metals, Inc. Color indicator for completion of polymerization for thermosets
US6331080B1 (en) * 1998-07-15 2001-12-18 3M Innovative Properties Company Optical fiber connector using colored photocurable adhesive
JP4531957B2 (ja) * 2000-09-08 2010-08-25 古河電気工業株式会社 光ファイバと光コネクタの接続固定硬化確認方法
DK1424973T3 (da) * 2001-04-23 2010-06-14 Euro Celtique Sa Bortskaffelsessystem til transdermal doseringsform
KR101407131B1 (ko) * 2002-06-10 2014-06-19 유로-셀티크 소시에떼 아노뉨 경피 전달 장치에 포함된 활성 성분의 오용을 방지하는 경피 전달 장치의 처리 시스템
JP3852395B2 (ja) * 2002-11-06 2006-11-29 東亞合成株式会社 ２−シアノアクリレート用硬化判定剤及び硬化判定方法
US7500621B2 (en) 2003-04-10 2009-03-10 Homax Products, Inc. Systems and methods for securing aerosol systems
US7273896B2 (en) * 2003-04-10 2007-09-25 Angiotech Pharmaceuticals (Us), Inc. Compositions and methods of using a transient colorant
EP1711147B1 (en) 2004-01-27 2011-01-19 Coloplast A/S An absorbing article with zones of different surface properties
US20050161531A1 (en) 2004-01-28 2005-07-28 Greer Lester R.Jr. Texture material for covering a repaired portion of a textured surface
US7677420B1 (en) 2004-07-02 2010-03-16 Homax Products, Inc. Aerosol spray texture apparatus for a particulate containing material
US7487893B1 (en) 2004-10-08 2009-02-10 Homax Products, Inc. Aerosol systems and methods for dispensing texture material
US8344056B1 (en) 2007-04-04 2013-01-01 Homax Products, Inc. Aerosol dispensing systems, methods, and compositions for repairing interior structure surfaces
US8469292B1 (en) 2007-04-04 2013-06-25 Homax Products, Inc. Spray texture material compositions and dispensing systems and methods
US9382060B1 (en) 2007-04-05 2016-07-05 Homax Products, Inc. Spray texture material compositions, systems, and methods with accelerated dry times
US8580349B1 (en) 2007-04-05 2013-11-12 Homax Products, Inc. Pigmented spray texture material compositions, systems, and methods
DE202007005742U1 (de) * 2007-04-20 2007-08-23 Sto Ag Reaktionsharz und Abdichtungssystem für Stahlbetonoberflächen mit einem Reaktionsharz
US20090165942A1 (en) * 2007-12-26 2009-07-02 National Starch And Chemical Investment Holding Corporation Insulation and Method of Installing
DE102008013170A1 (de) * 2008-03-07 2009-09-10 Wobben, Aloys Verfahren zum Einstellen eines Mischungsverhältnisses von zwei oder mehr Komponenten
EP2588512B1 (en) 2010-06-29 2015-03-11 3M Innovative Properties Company Color indicating epoxy resins and methods thereof
DE102011013645A1 (de) * 2011-03-11 2012-09-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Epoxidharzsystem mit visueller Kontrolle des Aushärtezustandes
US9156042B2 (en) 2011-07-29 2015-10-13 Homax Products, Inc. Systems and methods for dispensing texture material using dual flow adjustment
US9248457B2 (en) 2011-07-29 2016-02-02 Homax Products, Inc. Systems and methods for dispensing texture material using dual flow adjustment
US9156602B1 (en) 2012-05-17 2015-10-13 Homax Products, Inc. Actuators for dispensers for texture material
US9435120B2 (en) 2013-03-13 2016-09-06 Homax Products, Inc. Acoustic ceiling popcorn texture materials, systems, and methods
US9372177B2 (en) * 2013-03-15 2016-06-21 The Boeing Company Method and system for detecting exposure of composites to high-temperature
US9776785B2 (en) 2013-08-19 2017-10-03 Ppg Architectural Finishes, Inc. Ceiling texture materials, systems, and methods
US9970833B2 (en) 2014-04-23 2018-05-15 The Boeing Company Witness material and method for monitoring the environmental history of an object
USD787326S1 (en) 2014-12-09 2017-05-23 Ppg Architectural Finishes, Inc. Cap with actuator
US10160887B1 (en) * 2017-07-25 2018-12-25 W.F. Taylor Llc Cure signaling adhesive
JP7265242B2 (ja) * 2018-12-10 2023-04-26 国立研究開発法人宇宙航空研究開発機構 樹脂組成物、硬化不良予知方法、接合体の製造方法、接着キット、及び硬化不良検出装置

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA703098A (en) * 1965-02-02 B. B. Chemical Co. Of Canada Method of bonding with adhesive and adhesive containing an indicator
NL262511A (zh) * 1960-03-17
US3770547A (en) * 1971-05-14 1973-11-06 Sloane Mfg Co R & G Color bond surveillance system
US3773706A (en) * 1971-11-26 1973-11-20 Ubm Armonk Method for indicating stage of cure of crosslinked resins and compositions resulting therefrom
DE2445715A1 (de) * 1974-09-25 1976-04-08 Pelikan Werke Wagner Guenther Klebstoff mit indikatorfarbstoff
JPS5741514B2 (zh) * 1974-10-24 1982-09-03
DE2603101A1 (de) * 1976-01-28 1977-08-04 Basf Ag Azarhodaminlactone, deren herstellung und deren verwendung als farbbilder fuer kopierverfahren
US4164492A (en) * 1978-03-14 1979-08-14 Alco Standard Corporation Novel catalyst for curing polyester resins and method for determining the degree of cure in polyester and epoxy resin systems
US4343885A (en) * 1978-05-09 1982-08-10 Dynachem Corporation Phototropic photosensitive compositions containing fluoran colorformer
JPS5993772A (ja) * 1982-11-18 1984-05-30 Dainippon Printing Co Ltd 電子線硬化型ラミネ−ト用着色接着剤
GB2149468B (en) * 1983-11-08 1988-10-12 Raychem Ltd Device for connecting elongate objects
JPS61211016A (ja) * 1985-03-18 1986-09-19 Fujikura Ltd フレキシブルプリント基板と補強板との接合方法
DE3703887A1 (de) * 1987-02-09 1988-08-18 Beitz Wolfgang Herstellung von klebstoff-formelementen fuer schrauben-, welle/nabe- und linienhafte formschlussverbindungen
US4920091A (en) * 1987-12-25 1990-04-24 Fuji Photo Film Co., Ltd. Recording material
ATE123502T1 (de) * 1988-07-09 1995-06-15 Ciba Geigy Ag Härtbare epoxydharzzusammensetzungen.

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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WO2009059511A1 (en) * 2007-11-08 2009-05-14 Wuhan Keda Marble Protective Materials Co., Ltd. A red and green dry adhesive, a method producing the same
CN101157836B (zh) * 2007-11-08 2010-05-19 武汉市科达云石护理材料有限公司 红绿干贴胶及其制备工艺
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CN113166593B (zh) * 2018-12-23 2022-05-03 3M创新有限公司 固化时发生视觉变化的两部分粘合剂组合物

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KR900018317A (ko) 1990-12-21
EP0342965B1 (en) 1993-12-01
ATE97937T1 (de) 1993-12-15
EP0342965A1 (en) 1989-11-23
BR8902272A (pt) 1990-01-09
NO891955D0 (no) 1989-05-16
JPH0224380A (ja) 1990-01-26
CA1340560C (en) 1999-05-25
US5425824A (en) 1995-06-20
DE68911030D1 (de) 1994-01-13
AU3495789A (en) 1989-11-23
MX170247B (es) 1993-08-12
DE68911030T2 (de) 1994-04-07
MY105208A (en) 1994-08-30

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