CN1328307C - 热活化的环氧粘合剂及其在结构泡沫嵌件中的用途 - Google Patents

热活化的环氧粘合剂及其在结构泡沫嵌件中的用途 Download PDF

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CN1328307C
CN1328307C CNB200380107780XA CN200380107780A CN1328307C CN 1328307 C CN1328307 C CN 1328307C CN B200380107780X A CNB200380107780X A CN B200380107780XA CN 200380107780 A CN200380107780 A CN 200380107780A CN 1328307 C CN1328307 C CN 1328307C
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Abstract

描述了用于结构泡沫嵌件的可膨胀粘合剂，该结构泡沫嵌件用于加强车辆。粘合剂的特征为包含如聚甲基丙烯酸甲酯的粘度增加剂，它导致具有不寻常小的空隙和不寻常高的杨氏模量的固化的粘合剂。

Description

热活化的环氧粘合剂及其在结构泡沫嵌件中的用途
本发明涉及热活化的环氧粘合剂及其在泡沫嵌件中的用途，该泡沫嵌件结合到金属体。开发结构泡沫嵌件(SFI)以加强机动车辆中的结构，在***位置增加车辆的强度和刚度。开发声学泡沫嵌件(AFI)以降低噪声和振动对车辆通过的影响。例如，将由未固化可膨胀环氧粘合剂涂敷的SFI固定到汽车的B-柱腔。通常将AFI放入汽车的中空部件用于防止噪声和振动在整个中空腔中传播的目的。AFI可包括由可膨胀粘合剂涂敷的泡沫。然后将汽车体进行电沉积涂敷(e-涂敷)和烘烤，因此环氧粘合剂通过热活化而膨胀以在泡沫嵌件和金属片之间形成结合。然而，与现有技术的可膨胀粘合剂相关的一个问题是在它们膨胀之前它们交联的倾向。此过早的交联导致车辆基质的无效浸湿和伴随的更弱结合。另外，解决过早交联的问题-例如，通过降低或消除催化剂-产生另一个问题，即形成具有可接受粘合的固化的膨胀的聚合物，代价是大的空隙(＞2000μm的数均直径)，它的形成降低耐用性和导致机械性能的降低。
因此泡沫嵌件领域的进步是提供用于嵌件的可膨胀粘合剂，该粘合剂在交联发生之前能有效地浸湿基质，因此产生最优的化学粘合和提高耐用性，但该粘合剂产生小空隙，因此导致提高的机械性能。
本发明的粘合剂可膨胀直到350％。为保证填充空腔，膨胀受空腔中的可利用空间限制。本发明的粘合剂产生均衡压力，该均衡压力有助于在空腔中排列部件。
本发明通过提供一种可膨胀粘合剂解决本领域的需求，该可膨胀粘合剂包括a)固化的单组分环氧树脂；b)粘度增加剂；和c)不大于25重量份的无机填料，基于100份环氧树脂，其中粘合剂当膨胀时包含数均或重均直径小于1000μm的空隙。
在第二方面，本发明是一种结构泡沫嵌件，该结构泡沫嵌件包括a)膨胀的聚合物，和b)接触膨胀的聚合物的可膨胀粘合剂，该可膨胀粘合剂包含i)单组分环氧树脂；ii)聚合物粘度增加剂；iii)发泡剂；iv)催化剂；和v)固化剂，其中可膨胀粘合剂在100％膨胀下的杨氏模量为至少500mPa，优选在150％膨胀下为600mPa。
在第三方面，本发明是一种加强的车辆框架，该车辆框架包括a)膨胀的聚合物，和b)粘合膨胀的聚合物和车辆框架的膨胀的粘合剂，该膨胀的粘合剂包含i)单组分固化的环氧树脂；和ii)聚合物粘度增加剂，其中膨胀的粘合剂在100％膨胀下的杨氏模量为至少500mPa。
在第四方面，本发明是一种制备泡沫嵌件的方法，该方法包括如下步骤：a)在足以胶凝化可膨胀粘合剂而没有交联的条件下接触可膨胀粘合剂与膨胀的聚合物；b)在车辆框架中放置膨胀的聚合物与胶凝化的可膨胀粘合剂；c)热活化可膨胀粘合剂以产生膨胀的粘合剂，该膨胀的粘合剂在膨胀的聚合物和车辆框架之间形成结合；d)固化膨胀的粘合剂，其中可膨胀粘合剂包含i)单组分环氧树脂；ii)聚合物粘度增加剂；iii)发泡剂；iv)催化剂；和v)固化剂，和其中膨胀的粘合剂包含数均直径为＜1000μm的空隙。
在第五方面，本发明是膨胀的粘合剂，该膨胀的粘合剂包括a)固化的单组分环氧树脂；b)粘度增加剂；和c)不大于25重量份的无机填料，基于100份环氧树脂，其中膨胀的粘合剂包含数均直径为＜1000μm的空隙。
本发明通过提供含有粘合剂的泡沫嵌件解决本领域中的的问题，该粘合剂在交联发生之前有效浸湿基质，因此产生优异的化学粘合和提高耐用性，但该粘合剂产生降低的泡孔结构，因此导致提高的机械性能。本发明的粘合剂可膨胀直到350％。为保证填充空腔，膨胀受空腔中的可利用空间限制。本发明的粘合剂产生均衡压力，该均衡压力有助于在空腔中排列部件。
用于制备泡沫嵌件的膨胀的聚合物(也称为硬质泡沫)的杨氏模量为优选至少200mPa，更优选至少350mPa；Tg为优选至少50℃，和更优选至少80℃；和密度小于1g/cm3，更优选小于0.7g/cm3和优选至少0.0016g/cm3和更优选至少0.08g/cm3，甚至更优选至少0.3g/cm3。膨胀的聚合物可以是当膨胀时具有尺寸稳定性的任何膨胀的聚合物和提供结构整体性或声学密封性能的聚合物。膨胀的聚合物的优选例子包括发泡聚氨酯、发泡聚苯乙烯、发泡聚烯烃、和发泡的2份环氧物质。更优选的膨胀的聚合物是发泡聚氨酯。设计膨胀的聚合物的尺寸在每个尺寸中比它要***的空腔小3-6mm。
单份粘合剂包括膨胀和粘合到膨胀泡沫和从其制备车辆空腔内部的材料的任何单份粘合剂。用于涂敷可膨胀聚合物的可膨胀粘合剂使用单组分环氧树脂配制剂制备。优选的环氧树脂包括双酚A和双酚F的二缩水甘油醚，以及双酚A和双酚F的二缩水甘油醚的低聚物，单独或以结合的方式。更优选，环氧树脂是双酚A的二缩水甘油醚和双酚A二缩水甘油醚的低聚物的混合物。环氧树脂优选构成用于制备可膨胀粘合剂的总材料的40wt％到80wt％。
聚合物粘度增加剂是增加用于制备可膨胀粘合剂的共混物的粘度、以控制由发泡剂产生的气体的释放和聚结的聚合物。粘度增加剂优选作为细粉末(体积平均＜200μm)使用和Tg优选为至少70℃，更优选至少100℃。聚合物粘度增加剂的例子包括聚丁酸乙烯酯、苯氧基树脂、聚苯乙烯、聚碳酸酯和聚合丙烯酸酯和甲基丙烯酸酯和聚乙烯醇缩甲醛。更优选的粘度增加剂的例子包括聚合丙烯酸酯和甲基丙烯酸酯，更优选聚甲基丙烯酸甲酯(PMMA)，最优选羧酸官能化的PMMA，如市售的DegalanTM4944F PMMA(购自Rohm America)。使用有效量的聚合物粘度增加剂以控制气体从发泡剂的释放以降低在获得的固化树脂中的泡孔尺寸。聚合物粘度增加剂的浓度是优选至少2，更优选至少5，和最优选至少10wt％；和优选不大于40wt％，更优选不大于30wt％，和最优选不大于20wt％，基于用于制备可膨胀粘合剂的总材料。
环氧树脂的聚合由有效量的聚合促进催化剂、优选0.1wt％-2wt％的催化剂催化，基于用于制备可膨胀粘合剂的总材料。合适的催化剂包括，但不限于脲和咪唑。优选催化剂的例子是Acclerine CEL2191(1-(2-(2-羟基苯并酰氨基)乙基)-2-(2-羟苯基-2-咪唑啉，它具有如下化学结构：
Figure C20038010778000061
此催化剂的制备由Bagga在U.S.专利4,997,951中描述，该描述在此引入作为参考。
在有效量的发泡剂存在下将环氧树脂膨胀到所需体积以达到所需的泡沫结构和密度，优选发泡剂的量为0.5wt％-10wt％，更优选0.5-3wt％，和最优选1-2wt％，基于用于制备可膨胀粘合剂的总材料。优选的发泡剂可热活化至少100℃，更优选至少120℃，和优选不大于160℃。合适发泡剂的例子包括由Fukui在U.S.6,040,350，第4栏，25-30行描述的那些，该部分在此引入作为参考。优选市售发泡剂的例子是Celogen AZTM120偶氮二甲酰胺(均来自Crompton)。
可膨胀粘合剂可进一步包括已知的流变控制剂如煅烧的二氧化硅。表面活性剂也可用于可膨胀粘合剂，如硅烷或钛酸酯基表面活性剂。
将环氧树脂采用有效量的固化剂、优选2-10wt％固化剂固化，基于用于制备可膨胀粘合剂的总材料。合适固化剂的例子包括由Fukui在第4栏，66-67行和第5栏，1-9行描述的那些，该部分在此引入作为参考。
优选的固化剂包括双氰胺如AMICURE CG-1200(购自AirProducts)。
足够数量的固化剂用于形成所需的泡沫结构和提供尺寸稳定性，优选2wt％或更高，甚至更优选3wt％或更高，和最优选4wt％或更大，和优选10wt％或更小，甚至更优选8wt％或更小和最优选6wt％或更小。
可膨胀粘合剂也可包括任何填料，可以使用具有足够小粒度的填料。填料可以是有机或无机的。优选的有机填料是聚乙烯、聚丙烯、聚氨酯、橡胶和聚乙烯醇缩丁醛。优选的无机填料是碳酸钙、滑石、二氧化硅、正硅酸钙铝、中空玻璃球等。更优选的有机填料是聚烯烃聚合纤维，如聚乙烯共聚物。更优选的无机填料包括碳酸钙。填料的数量优选不大于25重量份，更优选不大于15重量份，和最优选不大于10重量份，基于100重量份的用于制备可膨胀粘合剂的环氧树脂。
优选的可膨胀粘合剂由如下方式制备：在大于环境温度的温度下，优选30℃-50℃下结合和混合环氧树脂、发泡剂、催化剂、固化剂、粘度增加剂、和非必要地填料15分钟到2小时。在真空中除去带入的空气和然后将可膨胀粘合剂注入围绕和符合膨胀的聚合物的形状的热模具(100℃-130℃)，以达到在膨胀的聚合物上从1mm到4mm的粘合剂可变设计的厚度。将获得的泡沫嵌件附加在汽车结构的空腔中以在泡沫嵌件和金属基材之间产生1mm到4mm的间隙。然后将金属结构e-涂敷，及残余的e-涂层液体通过在泡沫嵌件和金属之间的间隙逸出。最终，将e-涂层和可膨胀粘合剂在合适的固化温度、优选150℃-200℃下固化。
优选的固化(膨胀)的粘合剂在100％膨胀下的杨氏模量为至少500mPa，更优选至少700mPa，和最优选至少1000mPa。另外，优选的固化的粘合剂含有令人惊奇地小的空隙，空隙的数均直径优选小于1000μm，更优选小于500μm，和最优选小于100μm。因此，泡沫嵌件对汽车结构的粘合坚固和持久。
如下实施例仅用于说明性目的和不希望以任何方式限制本发明。除非另外说明，所有的百分比是wt％。
实施例-具有受控粘合剂孔度的结构泡沫嵌件的制备
将密度为0.64g/cm3和杨氏模量为400mPa的硬质聚氨酯泡沫制成所需的形状。可膨胀粘合剂由如下方式制备：通过在40℃下向容器中混合加入DER 331环氧树脂(40％)、DER 337环氧树脂(25％)、CELOGEN AZ 120发泡剂(1.5％)、CaCO3填料(O.45％)、炭黑(0.9％)、ACCELERINE CEL 2191催化剂(1％，从Celerity LLC获得)、AMICURECG1200双氰胺、DEGALAN 4944F PMMA(12.1％)、MICROTHENEFE-532聚乙烯共聚物(10％)、和CABOSIL TS-720(4.1％)1小时。然后通过在真空下混合30分钟除去带入的空气。将共混物注入围绕和符合聚氨酯泡沫嵌件的形状的热模具(120℃)，使得可膨胀粘合剂基本覆盖嵌件以对于膨胀的粘合剂最终机械性能中的设计方差获得2-3mm的可变设计的厚度。粘合剂在热模具中停留4分钟，其后将模具在10分钟时间内冷却到室温和取出。将获得的泡沫嵌件在汽车结构的空腔中附加以在SFI和金属基材之间产生2-mm间隙。将金属结构在环境温度下e-涂敷，及残余液体通过SFI和金属之间的间隙脱出。将结构在烘箱中在180℃下加热40分钟以固化e-涂层和膨胀和固化粘合剂。固化的粘合剂在100％膨胀下的杨氏模量为1033mPa。

Claims (10)

1.一种包括单组分环氧树脂配制剂的可膨胀粘合剂，包括a)环氧树脂；b)2-40重量％的粘度增加剂，其包含Tg至少为100℃的羧酸官能化的聚甲基丙烯酸甲酯；c)填料；d)固化剂和e)催化剂，包括脲或咪唑，和f)发泡剂，其中粘合剂在至少100％膨胀下的杨氏模量为至少500mPa，当膨胀时包含数均直径小于1000μm的空隙。
2.根据权利要求1所述的可膨胀粘合剂，其中基于粘合剂组合物，固化剂的量为2-10wt％，催化剂的量为0.1-2wt％.
3.根据权利要求1或2所述的可膨胀粘合剂，其中催化剂为1-(2-(2-羟基苯并酰氨基)乙基)-2-(2-羟苯基-2-咪唑啉)。
4.根据权利要求1所述的可膨胀粘合剂，其中填料为聚乙烯、聚丙烯、聚氨酯、橡胶或聚乙烯醇缩丁醛。
5.一种膨胀的粘合剂，包括膨胀的根据权利要求1-4任一所述的粘合剂。
6.根据权利要求5所述的膨胀的粘合剂，其中空隙的数均直径小于500μm。
7.一种泡沫嵌件，包括a)膨胀的聚合物，和b)接触膨胀的聚合物的可膨胀粘合剂，该可膨胀粘合剂为根据权利要求1-4任一所述的粘合剂。
8.根据权利要求7所述的泡沫嵌件，其中膨胀的聚合物是硬质聚氨酯泡沫。
9.一种加强的车辆框架，包括a)膨胀的聚合物，和b)根据权利要求5所述的膨胀的粘合剂。
10.一种制备结构泡沫嵌件的方法，包括如下步骤：a)在足以胶凝化可膨胀粘合剂而没有交联的条件下接触根据权利要求1所述的可膨胀粘合剂与膨胀的聚合物；b)在车辆框架中放置膨胀的聚合物与胶凝化的可膨胀粘合剂；c)热活化可膨胀粘合剂以产生膨胀的粘合剂，该膨胀的粘合剂在膨胀的聚合物和车辆框架之间形成结合，和d)固化膨胀的粘合剂。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108473662A (zh) * 2016-01-19 2018-08-31 陶氏环球技术有限责任公司 具有高伸长率和优异的热稳定性的单组分环氧改性聚氨酯和/或聚脲粘合剂以及使用其的装配工艺
US11583098B2 (en) * 2018-11-26 2023-02-21 L&P Swiss Holding Gmbh Pocket spring core

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6787579B2 (en) * 2001-05-02 2004-09-07 L&L Products, Inc. Two-component (epoxy/amine) structural foam-in-place material
US20030050352A1 (en) * 2001-09-04 2003-03-13 Symyx Technologies, Inc. Foamed Polymer System employing blowing agent performance enhancer
US7041355B2 (en) * 2001-11-29 2006-05-09 Dow Global Technologies Inc. Structural reinforcement parts for automotive assembly
EP1456286B1 (en) * 2001-12-21 2012-06-13 Henkel AG & Co. KGaA Expandable epoxy resin-based systems modified with thermoplastic polymers
KR100931762B1 (ko) * 2002-04-15 2009-12-14 다우 글로벌 테크놀로지스 인크. 발포체 제품 및 이를 사용한 발포체 충전 차량 중공 부재 형성 방법
JP4938445B2 (ja) * 2003-03-05 2012-05-23 ダウ グローバル テクノロジーズ エルエルシー 構造用強化物品及びその製造方法
US7199165B2 (en) * 2003-06-26 2007-04-03 L & L Products, Inc. Expandable material
US20050159531A1 (en) * 2004-01-20 2005-07-21 L&L Products, Inc. Adhesive material and use therefor
US20050230027A1 (en) * 2004-04-15 2005-10-20 L&L Products, Inc. Activatable material and method of forming and using same
US7360552B2 (en) 2004-04-23 2008-04-22 Dow Global Technologies Inc. Injectable structural adhesive
US20050241756A1 (en) * 2004-04-28 2005-11-03 L&L Products, Inc. Adhesive material and structures formed therewith
US8070994B2 (en) 2004-06-18 2011-12-06 Zephyros, Inc. Panel structure
MX2008000040A (es) * 2005-07-01 2008-04-04 Sika Technology Ag Material termicamente expansible solido.
US20070110951A1 (en) * 2005-07-20 2007-05-17 Frank Hoefflin Thermally expansible material substantially free of tackifier
US20070034099A1 (en) * 2005-08-10 2007-02-15 Lexmark International, Inc. Seals for an image forming apparatus
US7561820B2 (en) * 2005-08-10 2009-07-14 Lexmark International, Inc. Seals for an image forming apparatus
US7520560B2 (en) * 2005-08-12 2009-04-21 Ford Global Technologies, Llc Method of bonding and sealing automotive structural component joints
US8475694B2 (en) 2005-10-25 2013-07-02 Zephyros, Inc. Shaped expandable material
DE102007038659A1 (de) 2007-08-15 2009-02-19 Henkel Ag & Co. Kgaa Expandierbares, extrudiertes Formteil und Verfahren zu seiner Herstellung
EP1946995A1 (de) 2006-12-22 2008-07-23 Sika Technology AG Verstärkungssystem zur Verstärkung eines Hohlraumes eines Bauelements
JP5143135B2 (ja) * 2007-07-19 2013-02-13 旭化成ケミカルズ株式会社 酸化剤とアミン系化合物の反応物を含有する解体性接着剤
US8116657B2 (en) * 2007-12-18 2012-02-14 Lexmark International, Inc. Upper seal for inhibiting doctor blade toner leakage
US8099012B2 (en) 2007-12-18 2012-01-17 Lexmark International, Inc. Developer roll lip seal
GB0806434D0 (en) 2008-04-09 2008-05-14 Zephyros Inc Improvements in or relating to structural adhesives
US20100028651A1 (en) * 2008-07-29 2010-02-04 Golden Michael R Toughened expandable epoxy resins for stiffening and energy dissipation in automotive cavities
GB0916205D0 (en) 2009-09-15 2009-10-28 Zephyros Inc Improvements in or relating to cavity filling
GB0917123D0 (en) * 2009-09-30 2009-11-11 Rolls Royce Plc A method of securing a liner panel to a casing
US8525526B2 (en) * 2009-11-13 2013-09-03 Hubbell Incorporated High voltage test terminal having a shock-absorbing insulator
CN103153604B (zh) 2010-03-04 2016-04-13 泽菲罗斯公司 结构复合层压板
GB201016530D0 (en) 2010-09-30 2010-11-17 Zephyros Inc Improvements in or relating to adhesives
GB201105762D0 (en) * 2011-04-05 2011-05-18 Zephyros Inc Adhesive activation by an alternative current at low frequency
CN102982360A (zh) * 2011-07-12 2013-03-20 埃尔瓦有限公司 生态环境影响量化值标识符
JP2013091774A (ja) * 2011-10-05 2013-05-16 Canon Inc エポキシ樹脂組成物
CN105722933A (zh) 2013-07-26 2016-06-29 泽费罗斯股份有限公司 热固性粘合膜的改进或涉及它的改进
JP6237084B2 (ja) * 2013-10-07 2017-11-29 Jsr株式会社 硬化性組成物、硬化膜及びその形成方法、並びに塩基発生剤
US9675853B2 (en) * 2014-05-13 2017-06-13 Parsons Xtreme Golf, LLC Golf club heads and methods to manufacture golf club heads
WO2015160468A1 (en) * 2014-04-14 2015-10-22 Dow Global Technologies Llc Epoxy resin compositions for pre-gel ovens
GB201417985D0 (en) 2014-10-10 2014-11-26 Zephyros Inc Improvements in or relating to structural adhesives
US9764769B2 (en) 2015-02-09 2017-09-19 Honda Motor Co., Ltd. Vehicle frame structural member assembly and method
WO2017187602A1 (ja) * 2016-04-28 2017-11-02 日産自動車株式会社 部材接合方法
US11377532B2 (en) 2016-07-20 2022-07-05 Sika Technology Ag Approach to heat expandable materials
US11142254B2 (en) 2017-08-07 2021-10-12 Sika Technology Ag System of a sealed and reinforced structural element
CN111542579B (zh) 2017-10-18 2022-10-21 Ddp特种电子材料美国公司 胶粘剂组合物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1342182A (zh) * 1999-03-03 2002-03-27 汉克尔特罗森公司 热固化、热膨胀性的模制件
WO2002031077A2 (en) * 2000-10-10 2002-04-18 Henkel Kommanditgesellschaft Auf Aktien Two component thermosettable compositions useful for producing structural reinforcing adhesives

Family Cites Families (116)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2866744A (en) 1954-05-12 1958-12-30 Exxon Research Engineering Co Method of reforming hydrocarbons used in platinum catalyst in a plurality of separate reaction zones
US3581681A (en) * 1969-03-10 1971-06-01 Irving M Newton Pallet
US3755212A (en) * 1971-05-13 1973-08-28 Dow Chemical Co Air blown polyurethane foams
US3821130A (en) * 1972-04-26 1974-06-28 Dow Chemical Co Air frothed polyurethane foams
US3849146A (en) 1973-01-02 1974-11-19 Xerox Corp Direct-print light-developable silver halide emulsion containing cyclic dioxide or selenone as sensitizer
US3859162A (en) * 1973-05-11 1975-01-07 Minnesota Mining & Mfg Pre-preg materials, chemically integral composite foam structures prepared therefrom, and methods of preparation
US4019301A (en) * 1974-07-15 1977-04-26 Fox Douglas L Corrosion-resistant encasement for structural members
US4017117A (en) * 1975-10-08 1977-04-12 The Budd Company Roof hinged door in an automobile
US4390645A (en) * 1979-11-23 1983-06-28 The Dow Chemical Company Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom
JPS57151354A (en) * 1981-03-16 1982-09-18 Nissan Motor Reinforcing material and reinforcing panel
US4769391A (en) * 1985-12-19 1988-09-06 Essex Composite Systems Reinforcement insert for a structural member and method of making and using the same
US4751249A (en) * 1985-12-19 1988-06-14 Mpa Diversified Products Inc. Reinforcement insert for a structural member and method of making and using the same
US4898630A (en) * 1987-11-18 1990-02-06 Toyota Jidosha Kabushiki Thermosetting highly foaming sealer and method of using it
US4813690A (en) * 1987-11-24 1989-03-21 L & L Products, Inc. Sealing member
JP2519493B2 (ja) * 1987-12-21 1996-07-31 トヨタ自動車株式会社 熱硬化型発泡シ―ル材
JPH01166939A (ja) * 1987-12-23 1989-06-30 Toyota Motor Corp 熱硬化型発泡シール材
JPH0788175B2 (ja) * 1988-12-28 1995-09-27 日産自動車株式会社 車体構造部材への樹脂注入強化方法および注入樹脂のせき止め構造
GB8906198D0 (en) * 1989-03-17 1989-05-04 Ciba Geigy Ag Compounds
US5213391A (en) * 1990-10-25 1993-05-25 Nissan Motor Co., Ltd. Body skeleton element of vehicle and manufacturing method thereof
JPH0772233B2 (ja) * 1991-02-19 1995-08-02 日本ゼオン株式会社 エポキシ樹脂系発泡性組成物
US5218792A (en) * 1991-03-15 1993-06-15 Fleetwood Enterprises, Inc. Motor home or trailer body constructions
JPH04323288A (ja) * 1991-04-23 1992-11-12 Asahi Chem Ind Co Ltd 接着剤組成物
US5076632A (en) 1991-05-06 1991-12-31 Chrysler Corporation Composite windshield framing structure for a convertible automobile
US5344208A (en) * 1991-12-09 1994-09-06 Chrysler Corporation Reinforcement assembly for vehicle panels
JP3259389B2 (ja) * 1992-12-10 2002-02-25 日本ゼオン株式会社 パネル補強用シート材料及びそれを用いた車輌外板パネル
US5266133A (en) 1993-02-17 1993-11-30 Sika Corporation Dry expansible sealant and baffle composition and product
US5545022A (en) * 1994-02-10 1996-08-13 Shape Corporation Apparatus for manufacturing a vehicle bumper
EP0676315B1 (en) * 1994-04-11 1998-07-29 Ford Motor Company Limited Energy absorbing vehicle pillar structure
US6168226B1 (en) * 1994-05-19 2001-01-02 Henkel Corporation Composite laminate automotive structures
US5884960A (en) * 1994-05-19 1999-03-23 Henkel Corporation Reinforced door beam
US5533781A (en) * 1994-06-20 1996-07-09 O'gara-Hess & Eisenhardt Armoring Co., Inc. Armoring assembly
JPH0812946A (ja) * 1994-06-28 1996-01-16 Taoka Chem Co Ltd 改質されたα−シアノアクリレート系接着剤組成物
DE4439221C2 (de) * 1994-11-03 1997-10-16 Katzbach Kunststoffwerk Gmbh Verkleidungsteil, insbesondere Türverkleidungsträger, für ein Kraftfahrzeug
US5506025A (en) * 1995-01-09 1996-04-09 Sika Corporation Expandable baffle apparatus
US5660428A (en) * 1995-01-11 1997-08-26 Xcorp, Inc. Recyclable, low-cost, collision-resistant automobile chassis and body
US6165588A (en) * 1998-09-02 2000-12-26 Henkel Corporation Reinforcement of hollow sections using extrusions and a polymer binding layer
GB9523649D0 (en) * 1995-11-18 1996-01-17 White Peter D B Hot melt reactive resin compositions
US6196619B1 (en) * 1995-12-22 2001-03-06 Joalto Design, Inc. Vehicle closure panel having an intrusion beam as primary structure
US5985435A (en) 1996-01-23 1999-11-16 L & L Products, Inc. Magnetized hot melt adhesive articles
JP3409561B2 (ja) * 1996-02-19 2003-05-26 東海ゴム工業株式会社 車両用構造体の製造方法
JP2990057B2 (ja) * 1996-03-13 1999-12-13 アイシン軽金属株式会社 車体側部のエネルギー吸収構造
US5720510A (en) * 1996-03-28 1998-02-24 Ford Global Technologies, Inc. Energy absorbing vehicle pillar structure
US6341467B1 (en) * 1996-05-10 2002-01-29 Henkel Corporation Internal reinforcement for hollow structural elements
CZ357598A3 (cs) * 1996-05-10 1999-06-16 Henkel Kommanditgesellschaft Auf Aktien Vnitřní zesílení dutých konstrukčních prvků
US6092862A (en) * 1996-05-14 2000-07-25 Isuzu Motors Limited Floor structure for truck's load-carrying platform
JPH09316169A (ja) * 1996-05-28 1997-12-09 Nissan Motor Co Ltd 車体補強用エポキシ樹脂系組成物およびその組成物を用いた車体の補強方法
US5725272A (en) * 1996-06-27 1998-03-10 Sika Corporation Drain assembly for acoustic baffle system
US5888600A (en) * 1996-07-03 1999-03-30 Henkel Corporation Reinforced channel-shaped structural member
US6270600B1 (en) * 1996-07-03 2001-08-07 Henkel Corporation Reinforced channel-shaped structural member methods
US5648401A (en) * 1996-10-09 1997-07-15 L & L Products, Inc. Foamed articles and methods for making same
US5806919A (en) * 1996-11-04 1998-09-15 General Motors Corporation Low density-high density insert reinforced structural joints
DE19648164C2 (de) 1996-11-21 2000-01-27 Karmann Gmbh W Karosserieteil, insbesondere Profilrahmenträger
US6099948A (en) * 1997-05-08 2000-08-08 Henkel Corporation Encapsulation of pre-expanded elastomeric foam with a thermoplastic
US6237304B1 (en) * 1997-07-18 2001-05-29 Henkel Corporation Laminate structural bulkhead
US6096403A (en) * 1997-07-21 2000-08-01 Henkel Corporation Reinforced structural members
US6233826B1 (en) * 1997-07-21 2001-05-22 Henkel Corp Method for reinforcing structural members
US6451231B1 (en) * 1997-08-21 2002-09-17 Henkel Corporation Method of forming a high performance structural foam for stiffening parts
JPH1160900A (ja) * 1997-08-26 1999-03-05 Nissan Motor Co Ltd 車体補強用エポキシ樹脂系組成物および車体の補強方法
US6068424A (en) 1998-02-04 2000-05-30 Henkel Corporation Three dimensional composite joint reinforcement for an automotive vehicle
US6003274A (en) 1998-02-13 1999-12-21 Henkel Corporation Lightweight laminate reinforcing web
JPH11263865A (ja) * 1998-03-18 1999-09-28 Parker Corp 発泡性補強材組成物および車体の補強方法
US5817860A (en) * 1998-03-20 1998-10-06 Essex Specialty Products, Inc. Polyurethane prepolymer compositions, foams made therefrom and methods of making each thereof
US6062624A (en) * 1998-04-21 2000-05-16 Lear Corporation Sealing acoustical baffle and method therefor
US6050579A (en) * 1998-04-21 2000-04-18 Aeroquip Corporation Automotive running board
US6079180A (en) * 1998-05-22 2000-06-27 Henkel Corporation Laminate bulkhead with flared edges
DE19830453A1 (de) 1998-07-08 2000-01-13 Lurgi Zimmer Ag Verfahren und Vorrichtung zum Transport von Dampf durch mindestens einen runden Spinndüsenschacht
DE29812483U1 (de) * 1998-07-16 1998-10-01 Filtertek, S.A., Plailly Filter für Flüssigkeiten
US6247287B1 (en) * 1998-08-05 2001-06-19 Neo-Ex Lab, Inc. Structure and method for closing and reinforcing hollow structural members
US6103784A (en) * 1998-08-27 2000-08-15 Henkel Corporation Corrosion resistant structural foam
ZA991856B (en) * 1998-08-27 1999-09-22 Henkel Corp Storage-stable compositions useful for the production of structural foams.
US6376564B1 (en) * 1998-08-27 2002-04-23 Henkel Corporation Storage-stable compositions useful for the production of structural foams
US6272809B1 (en) * 1998-09-09 2001-08-14 Henkel Corporation Three dimensional laminate beam structure
US6387470B1 (en) * 1998-11-05 2002-05-14 Sika Corporation Sound deadening and structural reinforcement compositions and methods of using the same
JP3386730B2 (ja) * 1998-11-30 2003-03-17 株式会社ネオックスラボ 中空構造物における遮断・補強具
US6164716A (en) 1998-12-18 2000-12-26 Daimlerchrysler Corporation Energy dissipating body panel assembly
US6276105B1 (en) * 1999-01-11 2001-08-21 Henkel Corporation Laminate reinforced beam with tapered polymer layer
US6092864A (en) * 1999-01-25 2000-07-25 Henkel Corporation Oven cured structural foam with designed-in sag positioning
US6189953B1 (en) * 1999-01-25 2001-02-20 Henkel Corporation Reinforced structural assembly
US6149227A (en) 1999-01-25 2000-11-21 Henkel Corporation Reinforced structural assembly
US6131897A (en) 1999-03-16 2000-10-17 L & L Products, Inc. Structural reinforcements
US6150428A (en) * 1999-09-28 2000-11-21 Sika Corporation Expansion temperature tolerant dry expandable sealant and baffle product and method of preparing same
US6668457B1 (en) * 1999-12-10 2003-12-30 L&L Products, Inc. Heat-activated structural foam reinforced hydroform
JP3428545B2 (ja) 2000-01-07 2003-07-22 本田技研工業株式会社 車体補強構造
US6199940B1 (en) * 2000-01-31 2001-03-13 Sika Corporation Tubular structural reinforcing member with thermally expansible foaming material
US6305136B1 (en) 2000-01-31 2001-10-23 Sika Corporation Reinforcing member with beam shaped carrier and thermally expansible reinforcing material
AU2001231087A1 (en) * 2000-01-31 2001-08-07 Sika Corporation Structural reinforcing member with ribbed thermally expansible foaming material
US6253524B1 (en) * 2000-01-31 2001-07-03 Sika Corporation Reinforcing member with thermally expansible structural reinforcing material and directional shelf
US6475577B1 (en) 2000-02-07 2002-11-05 Sika Corporation Reinforcing member with intersecting support legs
US6467834B1 (en) 2000-02-11 2002-10-22 L&L Products Structural reinforcement system for automotive vehicles
US6423755B1 (en) * 2000-02-25 2002-07-23 Essex Specialty Products, Inc Rigid polyurethane foams
US6422575B1 (en) * 2000-03-14 2002-07-23 L&L Products, Inc. Expandable pre-formed plug
US6296298B1 (en) 2000-03-14 2001-10-02 L&L Products, Inc. Structural reinforcement member for wheel well
US6482486B1 (en) 2000-03-14 2002-11-19 L&L Products Heat activated reinforcing sleeve
JP2002012167A (ja) * 2000-04-26 2002-01-15 Neoex Lab Inc 中空構造物の補強構造とその補強具
US6413611B1 (en) * 2000-05-01 2002-07-02 Sika Corporation Baffle and reinforcement assembly
US6494525B1 (en) 2000-09-15 2002-12-17 Sika Corporation Side impact reinforcement
JP2002176137A (ja) * 2000-09-28 2002-06-21 Toshiba Corp 積層型半導体デバイス
US6419305B1 (en) * 2000-09-29 2002-07-16 L&L Products, Inc. Automotive pillar reinforcement system
US6561571B1 (en) * 2000-09-29 2003-05-13 L&L Products, Inc. Structurally enhanced attachment of a reinforcing member
US6471285B1 (en) 2000-09-29 2002-10-29 L&L Products, Inc. Hydroform structural reinforcement system
US6451876B1 (en) * 2000-10-10 2002-09-17 Henkel Corporation Two component thermosettable compositions useful for producing structural reinforcing adhesives
US6378933B1 (en) * 2000-11-06 2002-04-30 Daimlerchrysler Corporation Reinforced vehicle framing
US6719870B2 (en) * 2000-12-15 2004-04-13 The Boeing Company Fastenerless internal support for hollow structures
US6824860B2 (en) * 2001-01-16 2004-11-30 Avc Holdings Inc. Thermoplastic composite reinforced thermoform and blow-molded article
US6546693B2 (en) * 2001-04-11 2003-04-15 Henkel Corporation Reinforced structural assembly
US20030018095A1 (en) * 2001-04-27 2003-01-23 Agarwal Rajat K. Thermosettable compositions useful for producing structural adhesive foams
US6787579B2 (en) * 2001-05-02 2004-09-07 L&L Products, Inc. Two-component (epoxy/amine) structural foam-in-place material
US6502821B2 (en) * 2001-05-16 2003-01-07 L&L Products, Inc. Automotive body panel damping system
US20030001469A1 (en) * 2001-06-06 2003-01-02 L&L Products, Inc. Structural reinforcement and method of use therefor
GB0114684D0 (en) * 2001-06-15 2001-08-08 Dow Chemical Co Automobile assembly
US7041355B2 (en) * 2001-11-29 2006-05-09 Dow Global Technologies Inc. Structural reinforcement parts for automotive assembly
US6739641B2 (en) * 2001-12-04 2004-05-25 The Dow Chemical Company Composite spare wheel well
EP1456286B1 (en) * 2001-12-21 2012-06-13 Henkel AG & Co. KGaA Expandable epoxy resin-based systems modified with thermoplastic polymers
DE10163253A1 (de) * 2001-12-21 2003-07-10 Henkel Teroson Gmbh Hitzehärtbarer, thermisch expandierender Formkörper
US20030127844A1 (en) * 2002-01-07 2003-07-10 Visteon Global Technologies, Inc. Suspension subframe assembly
BR0307185B1 (pt) * 2002-01-22 2013-04-30 mÉtodo para reforÇar um corpo estrutural veicular e corpo estrutural veicular reforÇado.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1342182A (zh) * 1999-03-03 2002-03-27 汉克尔特罗森公司 热固化、热膨胀性的模制件
WO2002031077A2 (en) * 2000-10-10 2002-04-18 Henkel Kommanditgesellschaft Auf Aktien Two component thermosettable compositions useful for producing structural reinforcing adhesives

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108473662A (zh) * 2016-01-19 2018-08-31 陶氏环球技术有限责任公司 具有高伸长率和优异的热稳定性的单组分环氧改性聚氨酯和/或聚脲粘合剂以及使用其的装配工艺
CN108473662B (zh) * 2016-01-19 2021-12-21 陶氏环球技术有限责任公司 具有高伸长率和优异的热稳定性的单组分环氧改性聚氨酯和/或聚脲粘合剂以及使用其的装配工艺
US11583098B2 (en) * 2018-11-26 2023-02-21 L&P Swiss Holding Gmbh Pocket spring core

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MXPA05007040A (es) 2005-09-12
AU2003301081A1 (en) 2004-07-29
EP1578851B1 (en) 2006-11-08
DE60309604T2 (de) 2007-09-13
BR0317202A (pt) 2005-11-01
JP2006512456A (ja) 2006-04-13
WO2004060984A1 (en) 2004-07-22
CA2509629A1 (en) 2004-07-22
EP1578851A1 (en) 2005-09-28
US20040131839A1 (en) 2004-07-08
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KR20050092021A (ko) 2005-09-16
US7084210B2 (en) 2006-08-01

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