CN101365764A - 用于粘接金属的粘合剂组合物 - Google Patents
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Abstract
一种特别适合与金属使用的双组分结构粘合剂组合物,其包含一种或多种乙烯基单体,优选丙烯酸酯或甲基丙烯酸酯单体,一种或多种可溶的或可分散的聚合物和炔属二醇粘合促进剂以及优选的一种或多种可聚合的酸性粘合促进剂。
Description
背景技术和优选实施方案
本发明的优选实施方案涉及双组分结构粘合剂组合物,其利用新的和独特的粘合促进剂,显示出对金属改进的粘合性以及其它重要特性。
这些粘合剂组合物是丙烯酸酯或甲基丙烯酸酯单体和聚合物的混合物,其包含至少下列组分:
A、一种或多种乙烯基单体,优选丙烯酸酯或甲基丙烯酸酯单体,
B、一种或多种可溶的或可分散的聚合物,和
C、炔属二醇粘合促进剂
优选还将一种或多种可聚合的酸性粘合促进剂加入到组合物中。
也可以将其它添加剂添加到组合物中来增强其性能。
在评价传统的酸性粘合促进剂对粘接金属基材效果的过程中,令人惊讶地发现添加炔属二醇在组合物粘接到各种金属的能力方面产生了显著的改进,即使当传统金属粘接粘合促进剂不能提供所需粘合程度时。
本发明的优选实施方案的炔属二醇粘合促进剂对应于通式:
其中R1、R2、R3和R4选自H和烷基,且其中n等于或大于0。
US专利Nos.4,650,543和3,268,593公开了一组优选的炔属二醇粘合促进剂,其全部内容在此引入作为参考。特别优选的炔属二醇粘合促进剂是其中R1、R2、R3和R4全部是H而且n=0的2-丁炔-1,4-二醇。另一个特别优选的炔属二醇粘合促进剂由Air Products andChemicals,Inc.以 104销售,是其中R1和R3是甲基、R2和R4是异丁基而且n=0的2,4,7,9-四甲基-5-癸炔-4,7-二醇。这些优选的炔属二醇的一个重要特征是其中羟基附着在靠近炔属叁键的碳原子上2-丁炔-1,4-二醇主链结构。其它特别优选的炔属二醇粘合促进剂包括其中羟基部分与炔键碳原子由一个或多个氧乙烯基(n=1或以上)隔开的乙氧基化2-丁炔-1,4-二醇,例如SURFYNOL 485,其是乙氧基化2,4,7,9四甲基-5-癸炔-4,7二醇。
通常,商业上炔属二醇作为消泡剂和表面活性剂而被销售,用于各种水性或水基的应用,例如油漆和涂料。在此以前,它们在粘合剂中的使用限于基于聚合物乳液和水相容的添加剂的水基组合物。当有机溶剂或单体是组合物中的主要液体物质时,并不推荐在有机涂料或粘合剂中使用它们。即使当在水基组合物中使用炔属醇或二醇时,它们的好处通常限于来自作为消泡剂或表面活性剂的功能的效果。因此,通过使用本发明优选实施方案的组合物在对各种金属表面的粘合方面的显著改进是令人惊讶的。
尽管不打算受约束于具体理论,对于由使用这些炔属二醇粘合促进剂而带来的有益效果的可能解释可以来源于一种或多种对于金属粘合的理论解释。这些理论包括但不限于:各种电子给体-受体、氢键合或偶极子-偶极子相互作用的现象。在这种意义上讲,炔属二醇粘合促进剂在至少两种方式上具有发挥功能的潜能,其中或者炔属部分的供电子能力或者羟基部分的氢键合能力,或两者都可以参与粘合过程。在以下事实中可以发现证据,即其中上述结构的叁键被双键替代的优选的2-丁炔,1,4-二醇的烯烃或双键类似物,即2-丁烯,1,4-二醇,不能赋予本发明以创造性改进。类似的,2-丁炔-1,4-二醇的双(乙酸酯)也不能赋予本发明以相同的创造性改进。因此,相信需要存在至少一个羟基部分和叁键以赋予所期望的改进。
虽然优选的本发明的添加剂可以作为唯一的粘合促进剂添加到组合物中,但发现了它们与其它酸性粘合促进剂组合的特别用途。酸性粘合促进剂对丙烯酸酯或甲基丙烯酸酯基的结构粘合剂对金属的粘接强度的影响的能力在本领域是已知的。传统的酸性粘合促进剂包括不饱和的单羧酸、例如丙烯酸和甲基丙烯酸,不饱和二羧酸例如马来酸和富马酸,和不饱和磷酸酯例如单-和双-甲基丙烯酰氧乙基磷酸酯。
影响丙烯酸酯甲基或丙烯酸酯结构粘合剂对金属的粘接能力的因数是复杂的和相互作用的。它们包括金属表面和酸性粘合促进剂对粘合剂组合物反应性的催化或抑制影响,以及特定金属表面对初期粘合和粘接的耐久性的影响。例如,锌和铜可或者催化或者抑制粘合剂的固化,其取决于特定的配方。关于初期粘接强度和粘接的耐久性,在铁和铝表面上氧化铁和氧化铝表现不同。
丙烯酸和甲基丙烯酸通常增强丙烯酸酯和甲基丙烯酸酯结构粘合剂粘接铁类金属的能力,而且通常加快它们的固化速率。马来酸通常增强对锌表面的粘合性,不饱和磷酸酯通常增强对无处理(unprepared)的铝和不锈钢表面的粘合性和粘接的耐久性。可以使用这些酸性粘合促进剂的组合来配制用于金属和非金属材料的特定用途以及组合的粘合剂。
本发明优选实施方案的一个基础是即使当现有技术的金属粘合促进剂已经被评价过或被掺入到某些粘合配制剂中,特定的配制剂,即使具有某些其它所期望的特性,也不能提供对一种或多种金属基材所需要程度的粘合性。在这样的配制剂中,添加优选的本发明的炔属二醇粘合促进剂可以在金属粘合性方面赋予所期望的改进。这些特定的改进包括但不限于,增加的粘接强度和所期望的内聚破坏方式增加超过不期望的粘合破坏方式,优选两者都有。内聚破坏是粘接破坏的方式,其中在测试或使用中发生粘接分离时,在粘合剂层内发生破坏,在两基材片上留下粘合剂。在粘合破坏方式中,粘合剂从基材片上干净分离,在其表面上不留下粘合剂残留物。
与优选本发明组合物相关的粘合剂组的详细信息可以在US专利3,890,407、4,182,604、4,223,115、4,536,546、4,645,810、4,714,730、4,942,201和D.J.Damico,Engineered MaterialsHandbook,Volume 3,119 ASM International,1990的主题概述中找到,它们的所有内容在此引入作为参考。
出于讨论的目的,可聚合的乙烯基、丙烯酸酯和甲基丙烯酸酯单体包括在上面引用的′604专利中所公开的那些物质;且可溶的或可分散的聚合物包括在′604和′546专利中公开的那些物质。催化剂或引发物质包括现有技术普遍认可的所有的那些物质,包括上面引用的参考文献中描述的那些物质。
本发明特别优选的组合物包含:
A、20~90%可聚合的乙烯基单体,优选丙烯酸酯或甲基丙烯酸酯单体,
B、10~60%可溶的或可分散的聚合物或聚合物的混合物,和
C、0.1~10%炔属二醇。
优选的,该组合物还包含0.5~20%可聚合的酸性粘合促进剂或其混合物。
如需要,可以添加其它添加剂来增强组合物性能。
实施例
下列实施例中使用的组分是:
组分 描述 供应商
甲基丙烯酸甲酯 单体 Lucite
甲基丙烯酸 可聚合的羧酸粘合促进剂 Lucite
Tyrin 3615 氯化聚乙烯 DuPont/Dow
Kraton D1155 热塑性SBS嵌段共聚物 Kraton Polymer
Paraloid BTA 753 MBS核-壳冲击改性剂 Rohm & Haas
磷酸酯CD-9052 可聚合的酸性粘合促进剂 Sartomer
0.05%CuAcAc溶液 MMA中的乙酰丙酮合铜溶液 实验室制备/Aldrich
Reillcat ASY-2 二氢吡啶活化剂组分 Reilly Industries
2-丁炔-1,4-二醇 本发明的粘合促进剂 BASF
2-丁炔-1,4-二醇二 对比炔属化合物 Aldrich
乙酸酯
实施例 A B C D E F
组分 对照
甲基丙烯酸甲基酯 63.4 61.4 61.4 61.4 61.4 61.4
甲基丙烯酸 2.5 2.5 2.5 2.5 2.5 2.5
Tyrin 3615 5 5 5 5 5 5
Kraton D1155 5 5 5 5 5 5
对甲苯磺酰氯 1.5 1.5 1.5 1.5 1.5 1.5
Rohm & Haas BTA-753 20 20 20 20 20 20
磷酸酯CD-9052 1.25 1.25 1.25 1.25 1.25 1.25
0.05% CuAcAc溶液 0.1 0.1 0.1 0.1 0.1 0.1
Reillcat ASY-2 1.25 1.25 1.25 1.25 1.25 1.25
2-丁炔-4-二醇 - 2 - - - -
Surfynol 485 - - - 2 - -
Surfynol 61 - - - - 2 -
2-丁炔-1,4-二醇二乙酸酯 - - - - - 2
炔属组分特点 本发明的二醇本发明的二醇本发明的二醇单OH无0
- 基
结果
根据ASTM D1002的 2112 2513 2308 2184 2048 2153
铝搭接剪切强度,psi
破坏方式 粘合 内聚/粘合 粘合 粘合 粘合 粘合
实施例A是对照实施例,而优选的本发明实施例包括实施例B-D。这些实施例,特别是实施例B和C,公开了本发明优选实施方案的组合物相比那些不包含本发明炔属二醇组分的组合物的改进的粘合性。然而,这些实施例并不限制本发明公开的范围。
Claims (6)
2.权利要求1的粘合剂组合物,其中酸性粘合促进剂选自不饱和单羧酸、例如丙烯酸和甲基丙烯酸,不饱和二羧酸、例如马来酸和富马酸,不饱和磷酸酯、例如单-和双-甲基丙烯酰氧乙基磷酸酯,及其混物。
4.权利要求3的组合物,其进一步包含0.5~20%可聚合的酸性粘合促进剂。
5.权利要求4的粘合剂组合物,其中酸性粘合促进剂选自不饱和单羧酸、例如丙烯酸和甲基丙烯酸,不饱和二羧酸、例如马来酸和富马酸,不饱和磷酸酯、例如单-和双-甲基丙烯酰氧乙基磷酸酯,及其混合物。
6.粘合地固定金属基材的方法,其包括:
a)制备权利要求1的粘合剂组合物,和
b)将该粘合剂组合物固定到金属基材。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US75331005P | 2005-12-22 | 2005-12-22 | |
US60/753,310 | 2005-12-22 | ||
US11/643,543 | 2006-12-21 | ||
US11/643,543 US20070155879A1 (en) | 2005-12-22 | 2006-12-21 | Adhesive compositions for bonding metals |
PCT/US2006/049224 WO2007076108A1 (en) | 2005-12-22 | 2006-12-22 | Adhesive compositions for bonding metals |
Publications (2)
Publication Number | Publication Date |
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CN101365764A true CN101365764A (zh) | 2009-02-11 |
CN101365764B CN101365764B (zh) | 2014-01-22 |
Family
ID=38002136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN200680052543.1A Expired - Fee Related CN101365764B (zh) | 2005-12-22 | 2006-12-22 | 用于粘接金属的粘合剂组合物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20070155879A1 (zh) |
EP (1) | EP1963450B1 (zh) |
JP (1) | JP5417849B2 (zh) |
CN (1) | CN101365764B (zh) |
AU (1) | AU2006330904A1 (zh) |
CA (1) | CA2633738C (zh) |
WO (1) | WO2007076108A1 (zh) |
Cited By (1)
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CN102753635A (zh) * | 2010-02-26 | 2012-10-24 | 斯科特巴德尔有限公司 | 基于甲基丙烯酸酯的粘合剂组合物 |
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US8921490B2 (en) * | 2009-06-30 | 2014-12-30 | Henkel US IP LLC | Ultrafast heat/room temperature adhesive composition for bonding applications |
KR101206591B1 (ko) * | 2009-08-25 | 2012-11-29 | (주)엘지하우시스 | 수성 점착제 조성물, 그 제조방법 및 점착 필름 |
WO2012047246A1 (en) * | 2010-10-06 | 2012-04-12 | Toray Plastics (America) Inc. | Barrier coating composition with organic particles |
WO2015164031A1 (en) | 2014-04-22 | 2015-10-29 | Dow Global Technologies Llc | Polyurethane-acrylate epoxy adhesive |
US20170309584A1 (en) * | 2014-10-23 | 2017-10-26 | Agency For Science, Technology And Research | Method of bonding a first substrate and a second substrate |
CN109468097A (zh) * | 2018-10-22 | 2019-03-15 | 广东星宇耐力新材料股份有限公司 | 一种铝箔xps挤塑板复合水性胶粘剂及其制备方法 |
JP7234654B2 (ja) * | 2019-01-28 | 2023-03-08 | 株式会社リコー | 電極及びその製造方法、電極素子、非水電解液蓄電素子 |
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- 2006-12-21 US US11/643,543 patent/US20070155879A1/en not_active Abandoned
- 2006-12-22 CN CN200680052543.1A patent/CN101365764B/zh not_active Expired - Fee Related
- 2006-12-22 JP JP2008547652A patent/JP5417849B2/ja not_active Expired - Fee Related
- 2006-12-22 EP EP06848132.4A patent/EP1963450B1/en not_active Not-in-force
- 2006-12-22 CA CA2633738A patent/CA2633738C/en not_active Expired - Fee Related
- 2006-12-22 AU AU2006330904A patent/AU2006330904A1/en not_active Abandoned
- 2006-12-22 WO PCT/US2006/049224 patent/WO2007076108A1/en active Application Filing
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102753635A (zh) * | 2010-02-26 | 2012-10-24 | 斯科特巴德尔有限公司 | 基于甲基丙烯酸酯的粘合剂组合物 |
CN102753635B (zh) * | 2010-02-26 | 2014-11-26 | 斯科特巴德尔有限公司 | 基于甲基丙烯酸酯的粘合剂组合物 |
Also Published As
Publication number | Publication date |
---|---|
WO2007076108A1 (en) | 2007-07-05 |
CA2633738C (en) | 2014-07-15 |
US20070155879A1 (en) | 2007-07-05 |
JP5417849B2 (ja) | 2014-02-19 |
EP1963450B1 (en) | 2014-10-22 |
JP2009521582A (ja) | 2009-06-04 |
CN101365764B (zh) | 2014-01-22 |
CA2633738A1 (en) | 2007-07-05 |
AU2006330904A1 (en) | 2007-07-05 |
EP1963450A1 (en) | 2008-09-03 |
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