CN1180369A - 含有二硫代䓬酰胺粘合促进剂的环氧粘合剂 - Google Patents
含有二硫代䓬酰胺粘合促进剂的环氧粘合剂 Download PDFInfo
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- CN1180369A CN1180369A CN96193055A CN96193055A CN1180369A CN 1180369 A CN1180369 A CN 1180369A CN 96193055 A CN96193055 A CN 96193055A CN 96193055 A CN96193055 A CN 96193055A CN 1180369 A CN1180369 A CN 1180369A
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- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
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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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
- Y10T428/31522—Next to metal
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
本发明提供了一种可固化的构件环氧粘合剂组合物,它含有(a)环氧树脂;(b)环氧树脂的固化剂;和(c)式(Ⅰ)化合物,其中,R<sup>1</sup>和R<sup>2</sup>可相同或不同,它们选自:烷基、羟基烷基、环烷基、芳基、芳烷基、或杂环基,其中环中的1—3个非碳原子可独立地选自S、N和O。
Description
发明领域
本发明涉及含有一种或多种环氧树脂和一种或多种二硫代草酰胺(DTO)的结构粘合剂组合物。
发明背景
可固化的环氧树脂结构粘合剂组合物通常被用于粘合金属部件。这种操作在汽车工业中正越来越流行,特别是随着对安静要求的不断增加,因为缝隙粘合减少或消除了吱吱声并提高了车身刚度。因为生产技术和方案,对这种粘合剂的性能要求是苛刻的。例如,金属表面通常涂有机油。此外,更多的金属部件是镀锌过的以作为防腐蚀的手段。镀锌部件的富含锌的表面是难以粘附的。
许多环氧树脂结构粘合剂/金属构件因为长时间浸水或高湿度条件而受损坏,尤其是存在溶解的盐分时。尽管这种粘合整体性的下降部分是由于许多环氧树脂的亲水性所造成的(常吸收水并导致这些树脂有些塑化),但是会导致灾难性的粘合剂粘合断裂(failure)。一种灾难性的粘合剂粘合断裂发生于所吸收的水迁移至聚合物/金属界面时,在这里它破坏氢键和酸碱作用,而已知氢键和酸碱作用对粘附性是有贡献的。已有各种较疏水的和/或高交联的环氧树脂,但是它们常很昂贵而且难以应用,并且在完全固化时常会发脆。在某些情况下,这些树脂的内聚能密度较低或过于柔软,从而缺乏内在的粘合强度。
被取代的二硫代草酰胺已知可在无碳复印纸中用作生色剂,因为当该化合物与镍螯合时会形成深蓝色。该技术描述于美国专利No.4,201,404,3,935,960,3,632,377,3,492,145,3,394,042和3,287,154。
近年来,授予了许多描述使用取代的二硫代草酰胺和其他试剂,以改善某些聚合物与干净的铜和黄铜表面的粘附性方面的专利。美国专利No.4,842,946(Foust等人)描述了在施涂于聚酰亚胺膜的底涂料(primer)溶液中使用羰基和硫代羰基化合物,以改善电沉积铜在聚酰亚胺上的粘附情况。烷基二硫代草酰胺,如二甲基二硫代草酰胺和二月桂基二硫代草酰胺被列为合适的试剂。美国专利No.4,452,291(Schemenski等人)描述了汽车轮胎结构,其中镀有黄铜和/或锌的钢绳用4种不同组合物中任何一种进行涂覆,其中一种含有任选的二硫代草酰胺。其中描述到了在被密封之前涂有黄铜的钢的表面保护更佳,而且有更好的试剂粘附性,另外在许多情况下改善了硫化的涂有黄铜的钢/橡胶复合材料之间的初粘附。美国专利No.4,572,888(Maeda等人)描述了使用硫代酰肼和硫代羧酸酰胺(carbothio acid amide),其中有几个例子中将取代的DTO加入可光聚合的组合物中,该组合物含有热塑性粘合剂聚合物和一种或多种可光聚合的烯不饱和化合物如各种丙烯酸酯单体的预溶解混合物。这些组合物被干燥并用作干的膜光阻材料,其特征是可改善对基底金属(在例子中为铜)的粘附性。
Xue,Gi等人J.Chem.Soc.Faraday Trans.,87(8),pp.1229-1232(1992)描述了将2-巯基苯并咪唑化学吸附于用化学方法清洁过的铜金属表面。这种对铜的处理方法被描述为可改善环氧树脂与铜的粘附。
尽管已经研究了在各种类型的粘合剂和涂层中各种化合物的促进粘附性能方面的作用,但是仍需要一种可提高环氧树脂粘附性的化合物。
发明概述
因此,本发明提供了一种可固化的构件环氧粘合剂组合物,它含有
(a)环氧树脂;
(b)环氧树脂的固化剂;和
(c)式I化合物
其中,R1和R2可相同或不同,它们选自:烷基、羟基烷基、环烷基、芳基、芳烷基、或杂环基,其中环中的1-3个非碳原子可独立地选自S、N和O。本发明的该化合物特别适用于粘合油腻金属。
本发明还提供了一种粘合于油腻金属的方法,它包括(i)将上述的组合物施用于油腻的金属基件,以及(ii)固化该组合物。本发明还包括一种构件,它包括用上述的组合物粘合在一起的两个钢基件。
本发明的其他特征和优点在随后的说明书中给出,而且有一些根据说明是明显的,或者可以通过实施本发明而领会。本发明的目的和其他优点可用书面描述和权利要求中特别指出的方法和物品来实现和达到。
应理解,上面的一般性描述和下面的详细描述是代表性的和阐述性的,它们用于提供如权利要求所要求的本发明的进一步的解释。
发明详述
本发明提供了可用作构件粘合剂的环氧粘合剂组合物。该粘合剂特别适用于金属基件如钢。
具体地,本发明提供了一种可固化的构件环氧粘合剂组合物,它含有(a)环氧树脂;(b)环氧树脂的固化剂;和(c)式I化合物
其中,R1和R2可相同或不同,它们选自:烷基、羟基烷基、环烷基、芳基、芳烷基、或杂环基,其中环中的1-3个非碳原子可独立地选自S、N和O。
在优选例子中,烷基有1-18个碳原子;羟基烷基有1-18个碳原子;环烷基在环状部分有4-8个碳原子;而芳烷基的烷基有1-18个碳原子。在优选例子中,芳基是苄基或取代的苄基;而芳烷基的芳基部分是苄基或取代的苄基。优选选择可溶解在粘合剂组合物中的DTO。
在一个优选例子中,粘合剂组合物含有10-50重量%环氧树脂。最好该组合物对涂有150mg/ft2油的钢表面的T-剥离粘附值,高于不含组分(c)的相同组合物的T-剥离粘附值。
在另一优选例子中,式I的R1和R2选自烷基、羟基烷基或环烷基。在另一些优选例子中,R1和R2都是环己基,或者R1和R2都是羟乙基。
如上所述,本发明包括将二硫代草酰胺用作环氧树脂涂料和粘合剂中的的粘合促进剂。已发现这些材料可增强环氧树脂组合物与钢和涂覆钢材的粘着性,如油腻的,冷轧钢、电镀锌的钢、热浸镀锌的钢、热浸镀锌退火的钢、或电镀锌退火的钢。二硫代草酰胺在双组分胺固化环氧粘合剂和单组分环氧粘合剂中,以及在单组分和双组分环氧树脂涂料中都可用作粘合促进剂。二硫代草酰胺的优选使用浓度为0.5-25phr,较佳地为0.5-8phr,更佳地为1-3phr。术语“phr”指对于每100份重量的环氧树脂而言的重量份数。二硫代草酰胺及其制备方法公开于美国专利No.3,558,341。
在一个优选例子中,二硫代草酰胺化合物是通过溶解在双组分环氧树脂制剂的促凝剂(accelerator)或凝固剂中而加入双组分环氧树脂制剂的。将促凝剂和基本(环氧树脂)组分混合在一起,施涂在基件上,然后固化。
构件粘合剂在基件之间形成强力的整合粘合层。由构件粘合剂形成的粘合层,它在室温下的粘合强度用产业中公知的方法即T剥离试验进行测量,在粘合层厚度为0.010英寸(0.25毫米)时至少为10磅/线性英寸(pli)。构件粘合强度的上限是基件粘合断裂或基件的弯曲。本发明的粘合剂组合物在粘合层厚度为0.010英寸(0.254毫米)时的室温T-剥离粘合强度至少为12pli(磅/线性英寸),更佳的组合物的粘合强度大于约20pli,而最佳的组合物的粘合强度大于25pli。
构件粘合剂粘合情况还可以用产业中熟知的重迭剪切试验测得的室温模量来表征,它至少为3兆帕斯卡(MPa)。重迭剪切强度的上限是构件粘合断裂或基件弯曲。本发明粘合剂组合物形成的粘合,其在室温下的重迭剪切强度至少为5MPa,而较佳的组合物形成的重迭剪切强度至少为7MPa,而更佳的组合物形成的重迭剪切强度至少为10MPa,而最佳的组合物形成的重迭剪切强度至少为14MPa。
构件粘合层的厚度一般大于2密耳(0.5毫米)。在实施本发明时,形成的粘合层一般大于5密耳(0.127毫米),更通常约10密耳(0.254毫米)。
可用于本发明粘合剂组合物中的环氧化物可以是任何具有至少一个可通过开环而聚合的环氧环的有机化合物。优选的是平均环氧官能度大于1,较佳地至少2,的有机化合物。环氧化物可以是单体或聚合物,可以是脂族的、环脂族的、杂环的、芳族的或它们的混合物。更佳的环氧化物是芳族的,而且具有大于1.5个环氧基/分子,更佳地大于2个环氧基/分子。
有用材料的分子量为约150-10,000,更佳地为约300-1000。有用的材料包括具有末端环氧基的线性聚合环氧化物(如聚亚氧烷基乙二醇的二环氧基甘油醚)、具有骨架环氧基的聚合环氧化物(如聚丁二烯聚环氧化物(polybutadienepolyepoxy))、和具有侧链环氧基的聚合环氧化物(如甲基丙烯酸缩水甘油酯聚合物或共聚物),以及它们的混合物。
其中:
R′是烷基、烷基醚、或芳基,较佳地为芳基,而n是2-6的整数。较佳的是芳族缩水甘油醚,如那些通过将多元酚与过量表氯醇反应而制备的种类。有用的酚的例子包括间苯二酚、邻苯二酚、对苯二酚和多核酚类其中包括p,p′-二羟基联苄基、p,p′-二羟基联苯、p,p′-二羟基二苯基砜、p,p′-二羟基二苯甲酮、2,2′-二羟基-1,1-二萘基甲烷、和下列物质的2,2’、2,3’、2,4’、3,3’及4,4’异构体:二羟基二苯基甲烷、二羟基二苯基二甲基甲烷、二羟基二苯基乙基甲基甲烷、二羟基二苯基甲基丙基甲烷、二羟基二苯基乙基苯基甲烷、二羟基二苯基丙基苯基甲烷、二羟基二苯基丁基苯基甲烷、二羟基二苯基甲苯基甲烷、二羟基二苯基甲苯基甲基甲烷、二羟基二苯基二环己基甲烷和二羟基二苯基环己烷。同样优选的是多元酚甲醛缩合产物以及聚缩水甘油醚,它们仅含有环氧基或羟基作为活性基团。
除了n=1的上述通式I的化合物,可用作本发明组合物中任选的添加剂,只要在优选例子中相对于全部环氧化合物的平均环氧官能度大于1。
有用的材料包括双酚A的和酚醛清漆树脂的二环氧甘油醚,如在“环氧树脂手册(Handbook of Epoxy Resins)”Lee和Neville,McGraw-Hill Book Co.,NewYork(1967)中所述的种类。也可使用具有柔软骨架的环氧化物。较佳的材料包括双酚A的二环氧甘油醚和双酚F的二环氧甘油醚,最佳的是双酚A的二环氧甘油醚,因为这些材料在固化后保留所需的构件粘合性能。
可用于本发明的市售环氧化物例子包括双酚A的二环氧甘油醚(如ShellChemical Co.出售的商品名为Epon 828、Epon 1001、和Eponex 1510,以及DowChemical Co.出售的DER-331、DER-332和DER-334);双酚F的二环氧甘油醚(如Dai Nippon Ink and Chemicals Inc.的EpiclonTM830);含有二缩水甘油基环氧官能度的硅氧烷树脂;耐火环氧树脂(如Dow Chemical Co.出售的DER 580,一种溴化的双酚型环氧树脂);和1,4-丁二醇二环氧甘油醚。
在本发明的一个优选例子中,基本固化剂的用量应足以使环氧粘合剂组合物固化。根据环氧粘合剂的最终用途,其用量依照所用的环氧树脂类型可以在大体化学计量和过量环氧或基本固化剂之间变动。其数量一般为约1.5-200重量份固化剂/100份使用的环氧化物总量。较佳地,基本固化剂的用量是约2.5-75重量份数固化剂/100份环氧化物。
基本固化剂含有至少一个亲核的或亲电的基团,它与环氧环反应从而使粘合剂组合物交联。合适的基本固化剂包括聚酰胺树脂、脂族胺、聚醚二胺(polyetherdiamines)、芳族胺、聚胺;聚酰氨基胺(polyamidoamines)、聚醚二胺(polyetherdiamines)、酚类化合物和硫醇树脂。伯胺的例子包括:-二-(4-氨基苯基)砜、二-(4-氨基苯基)醚和2,2-双(4-氨基苯基)丙烷、乙二胺、1,6-己二胺、己二胺的异构体、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、二(六亚甲基)三胺(bishexamethylene triamine)、N,N′-双(3-氨基丙基)-1,2-乙烷二胺、N-(3-氨基丙基)-1,3-丙烷二胺、N-(2-氨基乙基)-1,3-丙烷二胺,环己二胺的异构体、4,4′-亚甲基双环己烷胺(4,4′-methylene biscyclohexanamine)、4,4′-亚甲基双[2-甲基环己烷胺]、异佛尔酮二胺和苯基亚烷基多胺基(phenalkylene polyamine)。有用的叔胺的例子是二甲基氨基丙基胺和吡啶。
有用的芳族胺的例子包括:二-(4-氨基苯基)砜、二-(4-氨基苯基)醚、2,2-双(4-氨基苯基)丙烷、4,4′-二氨基二苯基甲烷、3,3′-二甲基-4,4′-二氨基二苯基甲烷、间苯二胺、对苯二胺、间亚二甲苯基二胺、甲苯二胺、4,4′-亚甲基二苯胺、联苯胺、4,4′-硫代二苯胺、4-亚甲基-1,3-苯基二胺、2,6-二氨基吡啶和联茴香胺。
聚醚二胺的例子包括4,9-二噁十二烷-1,12-二胺(4,9-dioxadodecane-1,12-diamine)、4,7,10-三噁十三烷-1,12-二胺、各种分子量的双(3-氨基丙基)聚四氢呋喃,它们可从Texaco Chemical Co.公司在Jeffamine商品名D230、D400、D2000和T403下购得。
合适的聚酰氨基胺是多胺与二聚酸的反应产物。二聚酸是通过使植物油或动物脂中的C18或C22脂肪酸二聚化而制备的。然后再将二聚酸与多胺通过缩合反应应,从而产生聚酰氨基胺寡聚物。这些寡聚物已由V.Brytus,Modem Paint and CoatingsVol.74,No.10,p.172(1984)描述。这些合适的聚胺可以购得或者按美国专利No.3,257,342(Kwong)进行制备。在美国专利No.3,257,342(Kwong)中公开的固化剂是末端为氨基的聚酰胺,它们是二氨基聚醚与聚羧酸的反应产物。优选的羧酸包括二聚脂肪酸或二聚的和三聚的脂肪酸的混合物。这些羧酸可从Henkle Corporation在EmpolTM商品名下购得,其中包括EmpolTM1022、EmpolTM1018、EmpolTM1014和EmpolTM1061。
聚酰氨基胺还可如下进行制备:
(1)将酸装料于反应器中,在约-28英寸Hg的低真空下加热至约75-100℃。
(2)将胺在减压下加至反应器中。
(3)加入氮气使反应器压力达到大气压。
(4)缓慢加热至约175℃,在加热过程中蒸馏反应的水。
(5)在约175-200℃,施加约-25至-40英寸Hg的真空并蒸馏约1小时。
(6)加入氮气使反应器压力达到大气压,然后排出产物。
酚化合物的例子包括:苯酚、取代烷基苯酚(壬基苯酚)、双酚如邻苯二酚和烷基取代的邻苯二酚、间苯二酚和对苯二酚。
硫醇树脂的例子包括烷基二硫醇,如乙二硫醇、壬二硫醇、季戊四醇四(3-巯基丙酸)酯、三羟甲基丙烷三(3-巯基丙酸酯)、乙二醇二巯基乙酸酯、末端为巯基的聚醚和末端为巯基的多硫化物。
还可以使用的是硼配合物,尤其是与单乙醇胺的硼配合物;咪唑如2-乙基-4-甲基咪唑;胍如四甲基胍;取代的尿素如甲苯二异氰酸尿;双氰胺;和酸酐如4-甲基四羟基苯二甲酸酐、3-甲基四羟基苯二甲酸酐和甲基降冰片烯苯二甲酸酐。可以使用一种以上固化剂的混合物。优选的用于单组分粘合剂组合物的固化剂是胺、酸酐、胍、双氰胺以及它们的混合物。
基础固化剂的具体例子是AncamideTM系列(可从Air Product and ChemicalCompany购得)和ScherexTM系列(可从Schering-Berling购得)。
还可以加入本领域中已知的促凝剂来提高环氧粘合剂的固化速度。这种促凝剂包括那些单独使用时可作为固化剂,但是与不同等级的固化剂组合时会加速环氧粘合剂组合物固化的化合物。有用的促凝剂的例子包括酚化合物、叔胺、双氰胺、咪唑、取代的咪唑、六咪唑苯二甲酸镍配合物(hexakis imidazolenickelphthalatecomplex)、取代的尿素和三氟甲基磺酸钙。
这些促凝剂可以单独使用或混合使用,以促进环氧粘合剂组合物的固化。一些有用的混合例子包括:酚化合物与叔胺、双氰胺与咪唑和/或取代的咪唑、双氰胺与取代的尿素、双氰胺与六咪唑苯二甲酸镍配合物、以及三氟甲基磺酸钙与咪唑。优选的固化剂/促凝剂组合是甲苯二异氰酸尿素与双氰胺、促凝剂的优选数量是约0.2-10phr。
环氧粘合剂组合物优选地含有颗粒离子交换腐蚀抑制添加剂。添加剂颗粒是用氧化硅或氧化铝等无机氧化物制成的,它们具有化学结合的、用于抑制腐蚀的阳离子。一种特别有用的阳离子是钙(Ca2+)。
添加剂颗粒优选其平均直径为约0.1-200微米。更佳地,颗粒的平均直径为约1-50微米。合适的添加剂颗粒包括可从W.R.Grace&Co.以商品名“Shildex”购得的钙离子交换无定形氧化硅凝胶。
环氧粘合剂组合物优选含有韧化剂(toughening agent),尤其是聚合物型韧化剂或者聚合物型韧化剂的混合物。有用的韧化剂具有在环氧树脂中基本不溶的环氧化物不相容组分以及在环氧树脂中基本溶解的环氧化物相容组分。
可用于本发明的韧化剂包括:具有橡胶相和热塑相的聚合物型化合物,如具有聚合的二烯橡胶核心和聚丙烯酸酯或聚甲基丙烯酸酯外壳的接枝共聚物;具有橡胶核心和聚丙烯酸酯或聚甲基丙烯酸酯外壳的接枝共聚物;由可自由基聚合的单体和共聚合稳定剂在环氧化物中原位聚合产生的弹性体颗粒。
有用的韧化剂的具体例子包括:具有聚合的二烯橡胶骨架或核心(它接枝于丙烯酸酯或甲基丙烯酸酯、单乙烯基芳香烃或其混合物的外壳)的接枝共聚物,比如在美国专利No.3,496,250中公开的。优选的橡胶骨架包括聚合的丁二烯或聚合的丁二烯和苯乙烯混合物。优选的、含有聚合的甲基丙烯酸酯的外壳是低级烷基(C1-C4)取代的甲基丙烯酸酯。优选的单乙烯基芳香烃是苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基二甲苯、乙基乙烯基苯、异丙基苯乙烯、氯苯乙烯、二氯苯乙烯和乙基氯苯乙烯。
其他有用的韧化剂例子是丙烯酸酯核心-外壳接枝共聚物,其中核心或骨架是玻璃化温度(Tg)低于约0℃的聚丙烯酸酯聚合物,如聚丙烯酸丁酯或聚丙烯酸异辛酯(在它们上面接枝了Tg大于25℃的聚合物(外壳)如聚甲基丙烯酸甲酯)。
可用于本发明的韧化剂的其他例子还有,Tg低于约25℃且在与组合物的其他组分混合之前已在环氧化物中原位聚合的弹性体颗粒。这些弹性体颗粒一般被称为“有机溶胶”,它们是用可自由基聚合的单体和可共聚合的、可溶于环氧化物中的聚合物稳定剂聚合而成。可自由基聚合的单体是烯不饱和单体,或者与共反应的双官能氢化合物(如二醇、二胺和烷醇胺)混合的二异氰酸酯。这些弹性体颗粒的例子公开于美国专利No.4,525,181中。
另外的韧化剂是橡胶改性的液态环氧树脂。这种树脂的一种例子是KratonTMRP6565橡胶(可从Shell Chemical Company购得)。这种改性的环氧树脂是用85重量%EponTM 828和15重量%KratonTM橡胶制备的。KratonTM橡胶在本产业中是已知的弹性体嵌段共聚物
韧化剂还可含有液态环氧化物、液态胺、聚醚二胺、聚羟基醚、聚乙烯醇缩醛类、和液态丙烯腈丁二烯聚合物、丁二烯/腈橡胶、羧化丁二烯/腈橡胶、末端为胺的丁二烯/腈橡胶、末端为羧基的丁二烯/腈橡胶、以及聚合物与环氧树脂形成的末端为胺或羧基的加合物。末端为胺和末端为羧基的丁二烯-丙烯腈橡胶可从B.F.Goodrich以商品名“HYCAR”购得,分别是ATBN和CTBN活性液态聚合物。还可以使用韧化剂的混合物以提高固化的环氧粘合剂的性能。
韧化剂的优选用量为约3-35重量份,更佳地为约5-15重量份,按每100重量份环氧树脂计。本发明的韧化剂可提高组合物固化后的强度而不会干扰固化。韧化剂可以与环氧化物反应,也可不与环氧化物反应。
在某些情况下,还可加入活性稀释剂以控制粘合剂组合物的流动性。合适的稀释剂具有至少一个活性末端部分而且优选具有饱和的或不饱和的环状骨架。优选的活性末端醚部分包括缩水甘油醚和乙烯基醚。合适的稀释剂的例子包括:间苯二酚的二缩水甘油醚、环己烷二甲醇的二缩水甘油醚、新戊二醇的二缩水甘油醚、三羟甲基丙烷二戊烯的三缩水甘油醚、和环己烷二甲醇的二乙烯基醚。可购得的活性稀释剂是来自Shell Chemical Company的“WC-68”,以及来自Allied-Signal Corp.(Morristown,NJ)的RapicureTM CHVE,一种环己烷二甲醇的二乙烯基醚。
还可以向环氧化物组合物中加入各种其他的辅助剂,以提高组合物在固化之前或之后的性能。
包括在有用的辅助剂范围内的是非反应性稀释剂;增塑剂如常规的磷酸化合物和邻苯二甲酸化合物;阻燃剂如硼酸盐、偏硼酸盐、氢氧化铝、氢氧化镁和溴化合物;提供流动控制的触变剂如发烟硅石(fumed silica);用于改善色调的颜料如氧化铁、砖灰、碳黑、和二氧化钛;填料如滑石、氧化硅、镁、硫酸钙、硅酸铍铝;粘土如膨润土;玻璃和陶瓷珠和泡;赋予X光不透性的化合物如偏硼酸钡;以及增强材料如有机纤维和无机纤维如聚酯、聚酰亚胺、玻璃纤维和陶瓷纤维的编织和非编织织物。还可以加入分散剂和湿化剂,为硅烷基,只要它们不干扰环氧粘合剂组合物的固化反应。辅助剂可以对于所需目的有效量地加入;典型地,可以使用数量为约高达50份辅助剂/制剂的总重之内。
本发明的环氧粘合剂组合物可以用多种方法配制,其中包括单组分和双组分粘合剂系统。通过提供双组分组合物,其中两种组分在使用组合物之前便被混合,可以获得有利的组合物存放期或储存时间。在某些应用中,需要选择每种组分中各成分的数量和分布以控制粘度和更好地混合双组分。例如填料可被分开,从而是每种组分中都含有部分所用的填料。
本发明的环氧粘合剂组合物可用任何方式加以固化,其中允许用足够的热来引发固化反应。固化方式可包括常规的烘箱、感应加热、红外线辐射、微波辐射、浸入液体浴中、或它们的任何组合方式。对于双组分粘合剂组合物,固化可以在室温下约24小时实现。一般,最后的固化是在约15-230℃的温度下,于约1秒-2小时内进行的。固化可以分若干个阶段进行,如感应固化30秒,然后在215℃进行烘箱固化。
固化时间取决于具体的固化过程。感应加热时间一般为约1-60秒,而烘箱固化时间为约0.1-2小时。
本发明的环氧粘合剂组合物对于将金属与金属、塑料与金属粘合在一起特别有用,尽管可用于仅粘合塑料表面。金属表面的例子包括:钢、钛、油腻的钢、铝和镁。塑料表面包括板材模塑化合物、聚乙烯、聚碳酸酯、聚酯、聚氨酯、丙烯腈丁二烯苯乙烯、和脲甲醛。环氧粘合剂可用于装配部件,如汽车、飞机、冰箱等。
下列非限制性的实施例用于进一步更详细地阐述本发明。
测试程序
T-剥离粘合测试
将符合ASTM A619/A619M-82且尺寸为25.4mm×203mm×0.8mm的两根钢条(G60 HDGS),用甲基乙基酮进行脱脂。然后,清洁后的试样块在其一个表面上用汽车牵引润滑油进行涂油。用于该测试的汽车牵引润滑油是NovamaxTechnologies,Livonia,Mi的Novamax FB27MC-1和Quaker Chemical Corporation,Detroit,MI的Quaker 61 MAL-HCL。使用的Novamax FB27MC-1涂层重量是150+/-30mg/ft2。Quaker 61 MAL-HCL的涂层重量是400+/-25mg/ft2。用下列方法将汽车牵引润滑油施涂在钢试样上。使用Eppendorf重复移液器来将已知体积的牵引润滑油排放在钢试样一侧的表面上(16微升61 MAL-HCL;0.6毫升FB27MC-1)。用已经在有关牵引润滑油中饱和过的戴着天然橡胶手套的手指,将液滴涂在试样的一侧表面上。涂以Novamax FB27MC-1(一种水基乳剂型牵引润滑油)的试样,在室温下干燥24小时,让过量的水蒸发掉。涂以Quaker 61 MAL-HCL(一种非乳化的牵引化合物)的试样,可以在施涂之后立刻使用。
当测试的环氧组合物施涂在油腻的试样表面。测试的组合物具有0.5-1.0重量%固体玻璃珠(直径0.25mm)。玻璃珠(从Cataphote Corporation,Jackson,MS获得)被用作粘合层定距物。将一个试样放置在另一试样上,其中粘合剂一侧面对面。将迭放的试样夹紧,在20℃固化24小时。粘合后的T-剥离样品再在163℃后烘烤20分钟。测试样品在20℃适应2小时,然后进行粘合强度测试。根据ASTM1876-72进行剥离强度测试,其中试样以5厘米/分钟的十字头速度拉开。测得以牛顿/厘米表示的T-剥离。断裂模式被记录为粘合剂(A),其中粘合剂从一个试样表面被扯下;粘合剂(C),其中粘合剂裂开,在每个试样上留下粘合剂;或混合型(M),其中观察到两种断裂模式。最佳的断裂模式是100%粘合剂断裂模式,其中粘合剂基本上沿中间裂开,在每个试样中留下等厚的粘合剂。实施例中所示的T-剥离粘合测试值是5次独立测试的平均值。
重迭剪切强度
该试验测量环氧粘合剂组合物在完全固化后所能达到的最终强度。
将试样(G60 HDGS)切割成尺寸25.4mm×10.2mm×0.8mm,用甲基乙基酮进行脱脂。然后,按上述的方法,用牵引润滑油对试样进行涂覆。环氧粘合剂组合物被涂在油腻的试样的一端。测试的组合物具有0.5-1.0重量%固体玻璃珠(直径0.010英寸),它们被用作粘合层定距物。将第二个试样与第一个相配对,形成半英寸的重迭部分。然后将配对的试样夹紧,在20℃固化24小时。然后测试试样再在163℃后进行20分钟固化后烘烤过程。以2英寸/分钟(5.08厘米/分钟)的速度,按剪切方式牵拉试样,从而测得测得重迭剪切强度。测得剪切强度以兆帕斯卡记录,断裂模式被记录为粘合剂(A)、粘合剂(C)或混合型(M)。最佳的断裂模式是,100%粘合剂断裂模式,其中粘合剂基本上沿中间裂开,在每个试样中留下等厚的粘合剂。实施例中所示的重迭剪切测试值是5次独立测试的平均值。
喷盐试验
根据ASTM B117-90,让样品在35℃进行5%盐水喷雾试验,并在一定的小时后尤其是250小时和500小时后进行测试。从喷盐室中取出样品,在20℃和50%相对湿度下适应24小时。然后如上所述测定重迭剪切强度。
实施例
实施例中使用的组分
EponTM828环氧树脂-双酚A的二缩水甘油醚,环氧当量为约190且平均分子量为350-400,可从Shell Chemical Company购得。
EponTM1004环氧树脂-高分子量双酚A表氯醇共聚物,平均环氧当量为875-1025,可从Shell Chemical Company购得。
EponTM1510环氧树脂-氢化形式的EponTM828,平均环氧当量为210-238,可从Shell Chemical Company购得。
MK107-环己烷二甲醇的二缩水甘油醚,环氧当量为约160,可从ShellChemical Company购得。
PY322-脂族二缩水甘油醚,环氧当量为317-357,可从Ciba GeigyCorporation购得。
ParaloidTM EXL2691共聚物-丙烯酸酯/丁二烯/苯乙烯共聚物,可从Rohm&Haas Company购得。
ParaloidTM EXL753共聚物-丙烯酸酯/丁二烯/苯乙烯共聚物,可从Rohm&Haas Company购得。
Z-640-硅烷粘合促进剂,可从Dow Chemical Company购得。
Shieldex-钙离子交换氧化硅凝胶,可从W.R.Grace Company购得。
GP7I硅石-粒径为约20-30微米的二氧化硅填料,可从Harbison-Walker Corp.购得。
CabosilTMTS-720硅石-可从Cabot Corp.购得的发烟硅石。
B37-2000玻璃泡-玻璃泡,可从Minnesota Mining&ManufacturingCompany购得。
玻璃珠-直径为0.01英寸的固态玻璃珠,可从Cataphote Corp.购得。
Cabot M120-碳黑,可从Cabot Corp.购得。
Cardolite 541-苯基亚烷基胺(phenalkyene amine),平均胺氢当量为88,可从Cardolite Corp.购得。
HycarTM1300×16-末端为氨基的丙烯腈丁二烯共聚物,平均胺氢当量为900,可从B.F.Goodrich Company购得。
AncamineTM K54-三-2,4,6(二甲基氨基甲基)苯酚,可从Air Products Corp-购得。
Amicure CG1200-微粒双氰胺催化剂,可从Air Products Corp.购得。
实施例1
如下制备含有DTO化合物的双组分胺固化环氧粘合剂。
制备促凝剂
为了制备促凝剂组合物,将43phr末端为氨基的聚酰胺(当量比为2∶1的式NH2-CH2-CH2-CH2-(-O-CH2-CH2-)2-O-CH2-CH2-CH2-NH2的二胺与二聚酸混合物(EmpolTM,从Henkel Corp.获得)的反应产物)和硝酸钙(2phr)进行混合,然后在Meyers型混合器中加热至125℃,直至获得透明均匀的溶液。将CardoliteTM541(11.9phr)和N,N′-二环己基二硫代草酰胺(2phr)加入溶液中,在125℃搅拌溶解。然后将溶液冷却到80℃,并搅拌加入HycarTM 1300×16(17.1phr)和AncamineTMK54(7.2phr)。再加入填料GP7I(1 0phr)和CabosilTMTS720(1phr)并混合分散直至获得均匀的分散液。接着对混合物进行真空除气,以去除夹带的空气。然后将促凝剂混合物包装起来供以后使用。
制备环氧基质
将ParaLoidTMEXL 2691(15phr)与EponTM828(80phr)在Meyers型混合器中混合,并搅拌加热至70℃,直至形成EXL2691在环氧树脂中的平滑的、均质的分散液。停止混合器的加热,让混合器中的内含物在加入其他成分时冷却。将MK107环氧树脂(20phr)和硅烷Z-6040(2.5phr)搅拌加入分散液中。再依照所列次序混合加入填料:ShieldxTM(5phr)、B37-2000(22phr)、GP7I(20phr)、CabosilTMTS720(2phr)、CabotTM120(0.8phr)和固态玻璃珠(3phr)。混合混合器中的内含物,直至获得均匀的分散液。接着对混合物进行真空除气,以去除夹带的气体。然后包装起来供以后使用。
为了形成用于制备测试粘合的活性粘合剂组合物,将1.8重量份环氧基质与1.0重量份数促凝剂混合。将活性组合物施涂在测试基件上,在20℃固化24小时,在163℃后固化20分钟,在20℃固化1小时,然后再在121℃固化30分钟。测试数据列于表I。
实施例2
如下制备单组分的含有DTO化合物的环氧粘合剂。将环氧树脂EponTM828(50.2phr)和EponTM1004(17.9phr)and ParaloidTM753(12.5phr)在Meyers型混合器中混合,并搅拌加热至125℃,形成均质的分散液。将另2种环氧树脂CibaTMPY322(23.5phr)和EponexTM1510(8.4phr)加入分散液中,并混合。将粘合促进剂N,N′-二羟乙基二硫代草酰胺(1.65phr)加入混合器,在125℃溶解。让让混合器冷却至30℃。再依照所列次序搅拌加入填料:ShieldexTM(4.4phr)、GP7I(37phr)、CabosilTM TS720(2.9phr)。再将混合器冷却至20℃,搅拌加入环氧催化剂AmicureTMCG1200(5.7phr)和咪唑邻苯二甲酸镍(2.3phr)。观察混合器的内含物以保证已形成均匀的分散液。接着对混合物进行真空除气,以去除夹带的气体。
通过将获得的粘合剂施涂在测试基件上,并在170℃固化40分钟而制得测试粘合件。测试数据总结于表II。
对比实施例C-1
如下制备双组分胺固化环氧粘合剂。完全按实施例1制备促凝剂,不同点在于不加入N,N′-二环己基二硫代草酰胺。完全按实施例1制备环氧基质。完全按实施例1形成活性粘合剂组合物,施涂于测试基件上,并固化。测试数据总结于表I。
对比实施例C-2
完全按实施例2制备单组分环氧粘合剂,不同点在于不加入N,N′-二环己基二硫代草酰胺。完全按实施例2将获得的粘合剂施涂于测试基件上,固化,并测试。测试数据总结于表II。
表I
金属基件:涂有150mg/ft2(干重)Novamax FB27MC-1的G60HDGS
实施例1 对比实施例1T-剥离强度 40pli 30pli%粘合断裂 100% 50%OLS强度(最初) 2700psi 2662psiOLS强度(喷盐后250小时) 2400psi 2262psi%OLS强度的保留 88% 85%OLS强度(喷盐后500小时) 2200psi 2000psi%OLS强度的保留 82% 75%
含有二硫代草酰胺化合物的双组分制剂(实施例1)具有更高的T-剥离强度,而且实施例1粘合剂的T-剥离粘合的断裂模式是100%的内聚断裂。相反,对比实施例C-1的粘合剂的粘合强度下降,而且断裂模式是混合型的-50%粘合和50%内聚。在实施例1中掺入二硫代草酰胺化合物还改善了环境耐久性。用实施例1的粘合剂粘合的测试样品,在暴露于喷盐500小时后,保留了82%最初的粘合强度。在粘合层区域,粘合没有任何基蚀(undercutting)或腐蚀的迹象。相反,用对比实施例C-1的粘合剂粘合的测试样品,仅保留75%最初的粘合强度,而且在粘合层区域的边缘存在基蚀迹象。
表II
金属基件:涂有400mg/ft2Quaker MAL-HCL牵引油70EG电镀锌的钢材
对比实施例C-2 实施例2OLS强度 2556psi 2772psi%内聚断裂 30% 80%
在实施例2中的粘合剂中加入二硫代草酰胺化合物可提高OLS强度,并且与对比实施例C-2的相应粘合剂相比,有更高百分比的内聚断裂模式。
对于本领域的技术人员而言,很明显可以在本发明的精神和范围内,对本发明进行各种修饰和改动。因此,本发明涵盖了本发明的这些修饰和改动形式,只要透明在所附的权利要求及其等价权利要求的范围之内。
Claims (10)
1.一种可固化的构件环氧粘合剂组合物,其特征在于,它含有(a)环氧树脂;(b)环氧树脂的固化剂;和(c)式I化合物
其中,R1和R2可相同或不同,它们选自:烷基、羟基烷基、环烷基、芳基、芳烷基、或杂环基,其中环中的1-3个非碳原子可独立地选自S、N和O。
2.如权利要求1所述的组合物,其特征在于,还含有促凝剂以提高组合物的固化速度。
3.如权利要求1所述的组合物,其特征在于,还含有韧化剂。
4.如权利要求1所述的组合物,其特征在于,该组合物对涂有150mg/ft2油的钢表面的T-剥离粘附值,高于否则不含组分(c)的相同组合物。
5.如权利要求1所述的组合物,其特征在于,式I的R1和R2选自:烷基、羟基烷基或环烷基。
6.如权利要求1所述的组合物,其特征在于,R1和R2都是环己基。
7.如权利要求1所述的组合物,其特征在于,R1和R2都是羟乙基。
8.如权利要求1所述的组合物,其特征在于,还含有颗粒离子交换腐蚀抑制剂。
9.一种粘合于油腻金属的方法,其特征在于,包括
(i)将权利要求1所述的组合物施用于油腻金属基件;和
(ii)固化该组合物。
10.一种构件,其特征在于,它含有两块用权利要求1所述的组合物粘合在一起的钢基件。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/420,087 US5712039A (en) | 1995-04-11 | 1995-04-11 | Epoxy adhesives with dithiooxamide adhesion promoters |
US08/420,087 | 1995-04-11 |
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CN1180369A true CN1180369A (zh) | 1998-04-29 |
CN1083871C CN1083871C (zh) | 2002-05-01 |
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CN96193055A Expired - Fee Related CN1083871C (zh) | 1995-04-11 | 1996-02-20 | 含有二硫代草酰胺粘合促进剂的环氧粘合剂 |
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Country | Link |
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US (1) | US5712039A (zh) |
EP (1) | EP0820492B1 (zh) |
JP (1) | JPH11503775A (zh) |
KR (2) | KR19980703733A (zh) |
CN (1) | CN1083871C (zh) |
AU (1) | AU4989596A (zh) |
CA (1) | CA2216420A1 (zh) |
DE (1) | DE69603951T2 (zh) |
ES (1) | ES2135218T3 (zh) |
MX (1) | MX9707571A (zh) |
WO (1) | WO1996032454A1 (zh) |
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-
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- 1996-02-20 AU AU49895/96A patent/AU4989596A/en not_active Abandoned
- 1996-02-20 DE DE69603951T patent/DE69603951T2/de not_active Expired - Fee Related
- 1996-02-20 MX MX9707571A patent/MX9707571A/es unknown
- 1996-02-20 CN CN96193055A patent/CN1083871C/zh not_active Expired - Fee Related
- 1996-02-20 WO PCT/US1996/002299 patent/WO1996032454A1/en not_active Application Discontinuation
- 1996-02-20 EP EP96906555A patent/EP0820492B1/en not_active Expired - Lifetime
- 1996-02-20 ES ES96906555T patent/ES2135218T3/es not_active Expired - Lifetime
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Cited By (4)
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CN105008449A (zh) * | 2012-12-14 | 2015-10-28 | 倍耐力轮胎股份公司 | 用于车轮的轮胎 |
CN105008449B (zh) * | 2012-12-14 | 2018-02-23 | 倍耐力轮胎股份公司 | 用于车轮的轮胎 |
CN104151220A (zh) * | 2014-08-12 | 2014-11-19 | 湖南凯米尔生物科技有限公司 | N,n’-二烷基二硫代草酰胺及其制备方法和用途 |
CN104151220B (zh) * | 2014-08-12 | 2016-11-16 | 湖南凯米尔生物科技有限公司 | N,n’‑二取代二硫代草酰胺及其制备方法和用途 |
Also Published As
Publication number | Publication date |
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JPH11503775A (ja) | 1999-03-30 |
EP0820492A1 (en) | 1998-01-28 |
DE69603951D1 (de) | 1999-09-30 |
WO1996032454A1 (en) | 1996-10-17 |
KR19987003733A (zh) | 1998-12-05 |
MX9707571A (es) | 1997-12-31 |
KR19980703733A (ko) | 1998-12-05 |
US5712039A (en) | 1998-01-27 |
CA2216420A1 (en) | 1996-10-17 |
AU4989596A (en) | 1996-10-30 |
CN1083871C (zh) | 2002-05-01 |
EP0820492B1 (en) | 1999-08-25 |
DE69603951T2 (de) | 2000-05-04 |
ES2135218T3 (es) | 1999-10-16 |
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