CN101802124A - 反应性热熔粘合剂 - Google Patents

反应性热熔粘合剂 Download PDF

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CN101802124A
CN101802124A CN200880106906A CN200880106906A CN101802124A CN 101802124 A CN101802124 A CN 101802124A CN 200880106906 A CN200880106906 A CN 200880106906A CN 200880106906 A CN200880106906 A CN 200880106906A CN 101802124 A CN101802124 A CN 101802124A
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C·W·保罗
孙武
D·J·谷德
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Henkel AG and Co KGaA
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Abstract

本发明公开了使用硅烷官能的液体聚合物制备高初始强度的反应性热熔粘合剂。使用硅烷反应性聚合物,或者另选,非硅烷反应性聚合物,连同相容性增粘剂,配制所述粘合剂。

Description

反应性热熔粘合剂
技术领域
本发明涉及热熔粘合剂,尤其具有改进的性能的反应性热熔粘合剂。
背景技术
热熔粘合剂在室温下为固体,但当施加热量时,熔融成液态或流体态,它们以这种形式施加到基材上。一旦冷却,则粘合剂回到其固体形式。冷却粘合剂时形成的硬相赋予最终的粘合剂以所有的内聚性(强度、韧度、蠕变和耐热性)。同样以熔融形式施加的可固化热熔粘合剂冷却以凝固,随后通过化学交联反应固化。热熔可固化粘合剂与常规的液体固化粘合剂相比的优点是:(1)在固化之前,当冷却时,它们能提供“初始强度”,和(2)它们提供非常低交联密度的粘合剂,因此提供高水平的挠性和韧度。
大多数反应性热熔体是湿气固化性聚氨酯粘合剂。这些粘合剂主要由异氰酸酯封端的聚氨酯预聚物组成,所述异氰酸酯封端的聚氨酯预聚物与表面或环境湿气反应,以便扩链,形成新的聚氨酯/脲聚合物。常规通过使二元醇与二异氰酸酯反应,获得聚氨酯预聚物。通过湿气从大气或基材中扩散到粘合剂内并随后反应而获得固化。湿气与残留的异氰酸酯的反应形成氨基甲酸,该氨基甲酸不稳定,分解成胺和二氧化碳。胺快速地与异氰酸酯反应,形成脲。最终的粘合剂产品是主要通过氢键键合、脲基和氨基甲酸酯基保持在一起的轻度交联的物质。
硅烷基湿气固化性粘合剂与异氰酸酯基粘合剂相比具有数个优点。这些优点包括:1)在粘合层内没有气泡形成,这是因为固化反应的副产物不是气体(通常释放甲醇或乙醇,而不是CO2),2)在交联之后,挠性增加,这是因为硅氧烷键比脲键更加挠性,所述脲键彼此强烈地氢键键合,3)没有有害的异氰酸酯蒸气,和4)通过与表面羟基反应,改进的与玻璃和其他表面的粘合作用。已经基于许多固体聚合物开发了结合入硅烷交联基团的热熔粘合剂。硅烷反应性基团接枝到聚烯烃(H.G.Wey,Munich Adhesives and Processing Seminar 1997)、不饱和苯乙烯类嵌段共聚物(WO 91/06580)、聚氨酯(US 6749943)和乙烯-乙酸乙烯酯共聚物(GB 2197326)上获得的商业成功有限,这可能是由于当连接到固体聚合物上时,硅烷基团不能足够快速地缩合。另外,硅烷醇基团与酯基的酯交换反应具有有限的催化剂选择(US6749943)。
发明内容
需要基于硅烷固化的改进的热熔粘合剂。本发明解决了这一需求。
发明概述
本发明提供湿气可固化的反应性热熔粘合剂组合物,它提供不含异氰酸酯的湿气固化且具有改进的安全和处理性能。
本发明的一个方面涉及热熔粘合剂组合物,它包括一种或多种液体硅烷官能的聚合物和一种或多种含硅烷反应性基团的聚合物。该组合物可任选地含有其他成分,例如增粘剂、蜡、常规低分子量硅烷偶联剂、干燥剂、催化剂、颜料和/或无机填料。
本发明的另一方面涉及含液体硅烷官能的聚合物和一种或多种非硅烷反应性的聚合物和另外的增粘剂树脂的热熔粘合剂组合物。
本发明再一实施方案涉及将材料粘结在一起的方法,该方法包括将液体形式的本发明反应性热熔粘合剂组合物施加到第一基材上,使第二基材与施加到第一基材上的所述组合物接触,和将所施加的组合物置于允许该组合物冷却并固化成不可逆的固体形式的条件下,所述条件包括湿气。
本发明再一方面涉及制造制品,它包括经湿气固化的本发明的粘合剂。这些制品包括至少第一和第二基材,其中第一基材用已经湿气固化的本发明粘合剂粘结到第二基材上。所述基材可以相同或不同。在一个实施方案中,第一或第二基材中至少一个是玻璃。
附图说明
图1示出了样品2a的粘合剂的动态机械分析。
发明详述
本文引用的所有文献的公开内容通过参考以其全文引入。
所有百分比是粘合剂组合物的重量百分比,除非另有说明。
现已发现,可使用与硅烷反应性聚合物结合的液体硅烷官能的聚合物,制备安全和容易处理的反应性热熔粘合剂。这两种聚合物的接枝改进了它们在熔体相下的相容性,同时增加最终粘合剂的初始强度和固化强度。
还发现,使用增粘剂树脂,硅烷官能的液体聚合物可与非反应性的聚合物结合,以增容该共混物。
本发明的反应性热熔组合物可用于粘结由很多种基材(材料)组成的制品,所述基材包括,但不限于木材、金属、玻璃和纺织品。同样,这些粘合剂尤其用于例如粘结到外部表面、层压、塑料粘结、型材包裹和粘结到木材之类的应用中。其他非限定性用途包括纺织品粘结应用(地毯和衣服),在鞋袜(鞋子)制造中使用,在窗户制造中用作镶玻璃/背衬垫(backbedding)配混料(compound),在门,包括入户门、车库门等的制造中使用,在建筑板条制造中使用,在粘结车辆外部的组件中使用等。
本发明的粘合剂是挠性的且与表面基材强烈地反应,从而使得它们尤其当安全问题是重要的考虑因素,例如在容易发生飓风的区域内为了改进的门窗(fenestration)构造时可用作镶玻璃/背衬垫配混料。此处使用术语“镶玻璃配混料”是指本领域中常规称为背衬垫配混料且起到将玻璃窗格牢固地保持在窗框或框格内的作用的物质。门窗是建筑物,即墙壁或屋顶、机动车或类似物的开口以供接收并保持玻璃窗格定位用于保留在所述中心开口内。门窗构造或产品是门、窗户或天窗组件,它适配在建筑物开口内并用于密闭该开口。包括机动车挡风玻璃和类似物。
使用一种或多种液体硅烷官能的聚合物(聚合物A)和或者硅烷反应性聚合物(聚合物B1)或非硅烷反应性聚合物(聚合物B2),制备本发明的组合物。
硅烷官能聚合物包括用下式表示的硅烷基团或甲硅烷基:
X-Si(CxH2x+1)n(OCyH2y+1)3-n
其中n=0、1或2;
x和y独立地为1-12的整数,和
X是诸如亚乙基之类的基团,它将硅烷连接到聚合物主链上。
硅烷基团通过水而水解成硅烷醇基团,该硅烷醇基团可彼此缩合或者与粘附表面上的反应性物质缩合。硅烷基团的数量优选多于每分子至少一个(以生成完全固化的网络),更优选每分子至少两个。最优选硅烷官能聚合物是遥爪聚合物,其中大多数或所有末端是硅烷官能的。相对于每个硅烷端基,甲硅烷基醚基的数量,3-n,优选为2或3(n=1或0)。
硅烷官能的聚合物的主链可以具有各种结构,例如聚烯烃、聚丙烯酸酯或聚氨酯(例如获自Bayer的Baycoll 2458),但优选聚醚或最优选丙烯酸酯改性的聚醚(例如如美国公开申请2002/0084030A1中所述制备),例如可获自Kaneka Corporation的MAX 951。该聚合物在室温下为液体,从而在施加到基材上之后,在凝固的粘合剂内提供硅烷端基更加快速的反应,并辅助反应性位点的迁移,由此增加与一个或两个基材的表面的共价反应的潜力。
在配方内,硅烷官能的聚合物的用量取决于其分子量和官能度,但典型地为20-80wt%,优选30-60wt%,和最优选35-55wt%。
第二聚合物(B)提供给冷却的热熔粘合剂以初始强度(未固化强度)。B可以是硅烷反应性聚合物(B1)或非反应性的(B2)。硅烷反应性基团包括羧酸、胺、硫醇和羟基。优选羧酸。基团数量应当足以使得显著量,至少5%的聚合物通过硅烷基团接枝。接枝提供在施加粘合剂之前和在与湿气的任何反应之前熔体相内的相容性。在粘结与冷却之后,常常优选相分离的形态,因为这将粘合剂的韧度最大化。通过两个玻璃化转变温度(Tg)的存在和有时还通过冷却时不透明性的增加来证明相分离的形态。当使用B1时,接枝的聚合物确保冷却时微细的相分离和坚韧的粘合剂。理想的是,在施加和冷却之后,硅烷反应性聚合物分离成固相,但通过接枝的聚合物连接到固化的硅烷聚合物相上。在配方内固体聚合物B的用量取决于许多因素,其中包括聚合物的玻璃化转变温度和分子量,但通常为5-70%,优选10-50%,和最优选20-40%。
优选含酸和羟基的反应性固体丙烯酸类共聚物,其中获自INEOSAcrylics的Elvacite 2903是实例。这一材料的酸值为5.2和羟值为9.5。
任选地,具有B1的粘合剂还含有0-70%增粘剂,优选5-50%,和最优选20-40%。增粘剂的选择取决于硅烷官能和硅烷反应性聚合物的主链。增粘剂的选择包括天然和石油衍生的材料及其组合,如在C.W.Paul,“Hot Melt Adhesives”,Adhesion Science and Engineering-2,Surfaces,Chemistry and Applications,编者为M.Chaudhury和A.V.Pocius,Elsevier,纽约,2002,第718页中所述。增粘剂起到降低粘合剂的熔体粘度的作用且还可起到将在熔体内A和B聚合物增容的作用,从而有效地充当固体溶剂。优选的材料包括松香酯,芳族C9烃树脂,脂族改性的芳族C9烃树脂,酚类改性的萜烯树脂,酚类改性的芳族树脂,和纯的单体树脂。这些增粘剂的溶度参数>8.4(cal/cm3)0.5和优选>8.6(cal/cm3)0.5。最优选氢化松香酯,例如可获自Arakawa Chemical Co.的KB-100,和α-甲基苯乙烯树脂,例如可获自Eastman Chemical Co.的Kristalex 3100。
含非反应性聚合物B2的粘合剂组合物要求10-50%增粘剂,以获得充足的熔体相容性和初始强度。优选20-40%的增粘剂。
粘合剂进一步包括催化剂以促进硅烷基团的固化。催化剂的类型可包括常规的催化剂,例如链烷酸锡,例如二月桂酸二丁锡,和烷醇钛,例如可获自Dupont的Tyzor GBA。在US 2002/0084030中公开了适合于将硅烷基团固化的催化剂(也称为促进剂)的更广泛的列举。催化剂的含量为0.05-5wt%,优选0.2-3%,和最优选0.5-2%。
粘合剂任选地包括湿气清除剂以延长其有效期,例如乙烯基三甲氧基硅烷。所使用的含量可以是0-3%和优选0.5-2%。
粘合剂任选地包括促进向被粘物上粘结的粘合促进剂或偶联剂。在Michel J.Owen,“Coupling agents:chemical bonding atinterfaces”,Adhesion Science and Engineering-2,Surfaces,Chemistry and Applications,编者为M.Chaudhury和A.V.Pocius,Elsevier,纽约,2002,第403页中描述了实例。优选有机硅烷,它可将硅烷官能的聚合物连接到表面上,例如是氨基和环氧基硅烷。最优选环氧丙氧丙基三甲氧基硅烷。含量为0.01-10%,优选0.1-5%和最优选0.2-3%。粘合促进剂与湿气的反应性若大于硅烷官能的聚合物,则也可充当湿气清除剂。
硅烷官能的聚合物和硅烷反应性聚合物的接枝反应在熔体状态下发生,在粘合剂施加之前。反应与混合同时在高于100℃,但优选在低于160℃的温度下发生。
热熔粘合剂要求足够低的粘度以便容易施加和基材良好浸湿。优选在施加温度下的粘度低于100,000cP,更优选小于25,000cP,和最优选小于15,000cP。通过配方(formula)的热稳定性和基材的热敏性,决定施加温度。优选温度低于170℃,更优选低于150℃,和最优选低于140℃。
在施加之后,为了将制品粘合在一起,将反应性热熔粘合剂组合物置于允许它凝固并固化成具有不可逆固体形式的组合物的条件下。当液态熔体置于室温下时,发生凝固(硬化成初始或未固化状态)。在环境湿气存在下,发生固化,即扩链,成具有不可逆固体形式的组合物。
本文所使用的“不可逆固体形式”是指其中在粘合剂内硅烷官能的聚合物已经与湿气和本身反应,而产生不可溶硅氧烷连接的材料的固体形式。
通过下述非限定性实施例,进一步举例阐述本发明。
具体实施方式
实施例
实施例1
这一实施例证明硅烷官能的液体聚合物与硅烷反应性丙烯酸类聚合物的接枝效果。
通过两种不同的方法,制备62.5份硅烷官能的液体聚合物(MAX951,可商购于Kaneka)和37.5份含甲基丙烯酸甲酯和甲基丙烯酸正丁酯且具有变化量硅烷反应性酸基的固体丙烯酸类共聚物的共混物。
方法1(溶剂共混):在室温下,在溶剂(甲苯)内混合所述两种聚合物,直到完全溶解,然后让溶剂蒸发。
方法2(熔体共混):在300°F下混合这两种聚合物1小时。
然后判断样品的相容性并将它们呈现不透明时的最高温度记录为浊点。表1中示出了结果。
表1
Figure GPA00001050021800071
如表1所示,发现通过在室温下溶剂共混(方法1)制备的所有样品不相容。当蒸发溶剂时,明显可见两个清晰地不同的相。一个相对应于液体硅烷官能的聚合物相,另一相对应于固体丙烯酸类共聚物。相反,通过在300°F下热熔共混(方法2)制备的样品产生含丙烯酸单体的丙烯酸类共聚物的相容共混物。具有较大丙烯酸含量的丙烯酸类共聚物具有较低的浊点,这证明相容性增加。
在THF溶剂中进行对固体丙烯酸类聚合物和共混物的凝胶渗透色谱(GPC)。如表1所示,含酸的丙烯酸类聚合物具有略微更高的z-均分子量,但共混物仅仅在存在酸的情况下具有增加的Mz。在最高的酸含量(酸#为13.5,相当于约2wt%的甲基丙烯酸)下,Mz几乎加倍。另外,共混物的粘度随酸含量急剧增加。数据表明,当加热时,在丙烯酸类上的酸基与硅烷官能的聚合物反应,形成较高分子量的接枝物质,其将共混物增容。
实施例2
这一实施例比较了本发明的配方与可商购的窗户镶玻璃配方。
样品2a
向金属油漆罐中添加1.4份Resiflow LF(可获自EstronChemical的丙烯酸类消泡剂)、105份Elvacite 2903(酸#为5.2和羟值为9.5的固体丙烯酸类聚合物,可获自Ineos Acrylics)、52.5份KE-100(可获自Arakawa Chemical Co.的氢化松香酯)和52.5份Kristalex 3100(可获自Eastman Chemical Co.的α-甲基苯乙烯增粘剂)。加热这些组分到305°F,并搅拌直到均匀。施加真空,以除去任何水,和将设定温度下降到240°F。当温度达到设定点,约1/2h时,添加140份MAX 951并施加真空1/2小时以上。此刻,添加0.7份γ-氨丙基三乙氧基硅烷(获自Momentive Performance Materials的Silquest A1110),3.5份二月桂酸二丁锡和2.6份环氧丙氧丙基三甲氧基硅烷,并继续混合额外15分钟。将最终的粘合剂倾倒入另一容器内并在氮气下密封。
样品2b
制备具有与样品2a相同的配方的粘合剂,所不同的是环氧基硅烷的含量加倍成5.2份环氧丙氧丙基三甲氧基硅烷。
样品2a和样品2b都在熔体状态下是透明的,这表明相容性优异,但冷却为浑浊的粘合剂膜。对各自的固化膜使用Rheometrics RDA-III进行动态机械分析,且二者均显示出两个玻璃化转变温度。一个Tg在约-24℃处,和另一个在约50℃处,如图1所示。第二个,高的Tg相提供给未固化粘合剂以初始强度。高温(>110℃)下的平坦的平台模量G’是最终粘合剂的交联性质的证据。
进行下述操作步骤,以评估粘合剂性能。
粘度:
使用具有Thermosel加热装置和锭子27的Brookfield(布氏)粘度计,测定粘度。
从玻璃基材的剥离粘合性:
在烘箱内在250°F下加热粘合剂1小时,然后从加热枪中挤出到由1.5英寸×5.5英寸和厚度为0.125英寸的硅酮模具制框的清洁的玻璃基材上。然后将不锈钢丝网带包埋在熔融的粘合剂层内。接着添加另一粘合剂层。当冷却到室温时,用硅酮剥离纸覆盖粘合剂,并施加重量5分钟,以挤压粘合剂层成模具形状。粘合剂层的最终厚度为约1/4英寸。然后在测试之前,在72°F/50%RH下调理制成的粘结体2周,以确保湿气固化。剥离是在2英寸/分钟下180度剥离。
在室温和180°F下玻璃-PVC基材的搭接剪切试验:
如上施加粘合剂到清洁的PVC基材上。使用不锈钢刮涂涂布器(BYK-Gardner)以获得0.020英寸的控制厚度。在粘合剂层之上撒厚度0.010in的玻璃珠隔离物,以控制最终粘合层厚度。使用手压,粘结1英寸×4英寸的清洁的玻璃带,其中重叠区域为1英寸×1英寸。然后,在测试之前,在72°F/50%RH下调理制成的粘结体2周,以确保湿气固化。在Instron内,在室温下,或者在烘箱内在180°F下加热样品0.5h之后,并从烘箱中取出之后立即测试,在0.5英寸/分钟下牵拉样品。
初始强度:
如上所述制备并测试搭接剪切粘结体,但在粘结后5分钟或15分钟之后很大程度上未固化地测试。这一试验表征粘结的结构在完全固化之前经受得住在制造中处理的能力。热熔体具有在初始状态下高强度的优点,这将运转存量(working inventory)最小化。
肖民硬度A:
使用ASTM A型硬度计(型号306L),在固化(23℃/50%RH)之后测试厚度为0.5英寸的粘合剂层。
将样品2a和2b的配方与可以商品名PURFECT GLAZE G商购于National Starch and Chemical Company的基于异氰酸酯封端的聚氨酯的常规湿气固化性热熔体比较用作窗户镶玻璃配混料。表2中示出了粘合剂性能的结果。
表2
  样品2a   样品2b   Purfect Glaze G
  离开玻璃的180°剥离(lbs)   30   40   20
  样品2a   样品2b   Purfect Glaze G
  搭接剪切(玻璃/PVC)(lbs)
  72°F   106   156   97
  180°F   7   41   10
  肖氏硬度A   61   52   50
  初始强度(lbs)
  冷却5分钟之后   32   38   5
  冷却15分钟之后   39   48
本发明提供不含气泡的粘结体,其在玻璃上具有改进得多的剥离性和初始强度。另外,在可比的硬度下,剪切强度可以更高。
实施例3
示出了使用增粘剂将硅烷官能的液体聚合物与非反应性固体丙烯酸类聚合物增容。
使用实施例2所述的操作步骤,以使用非硅烷反应性的聚合物制备粘合剂。配方内的成分为0.8份Resiflow LF,60份表1内的丙烯酸类1,30份KE-100,30份Kristalex 3100,80份MAX 951,0.4份Silquest A-1110,2份二月桂酸二丁锡,和3份环氧丙氧丙基三甲氧基硅烷。粘合剂是透明的且在240°F下相容。将一部分该粘合剂置于266°F下的玻璃罐内数小时。它保持透明和纹理光滑,且没有相分离的迹象。然而,一旦冷却,粘合剂变得浑浊。
与玻璃的搭接剪切粘合作用为129lbs,如根据实施例2中的操作步骤测量。
可在不偏离本发明的主旨与范围的情况下,对本发明进行许多改进和变化,如对本领域技术人员来说显而易见的那样。本文所述的具体实施方案仅仅通过举例方式提供,和本发明仅仅受限于所附的权利要求书的条款,连同这些权利要求有权包括的等价物的整个范围。

Claims (16)

1.湿气可固化的热熔粘合剂组合物,它包含硅烷官能的液体聚合物与硅烷反应性聚合物。
2.湿气可固化的热熔粘合剂组合物,它包含硅烷官能的液体聚合物、非硅烷反应性聚合物和约10wt%-约50wt%的增容增粘剂。
3.权利要求1的粘合剂,其中该粘合剂进一步包含粘合促进剂。
4.权利要求3的粘合剂,其中该粘合剂进一步包含催化剂。
5.权利要求4的粘合剂,其中该粘合剂包含20-80wt%硅烷官能的聚合物,5-70wt%硅烷反应性聚合物,0.01-10wt%粘合促进剂,0.05-5wt%催化剂,和0-70wt%增粘剂。
6.权利要求5的粘合剂,其中所述硅烷反应性聚合物是固体。
7.权利要求6的粘合剂,其中所述硅烷反应性聚合物是丙烯酸类。
8.权利要求7的粘合剂,其中该粘合剂包含35-55wt%含聚氧化丙烯主链的硅烷官能的聚合物,20-40wt%含具有酸官能度的固体丙烯酸类的硅烷反应性聚合物,20-40wt%增粘剂,0.2-3wt%粘合促进剂,和0.05-5wt%催化剂。
9.权利要求2的粘合剂,其中所述非硅烷反应性聚合物是丙烯酸类聚合物。
10.权利要求9的粘合剂,其中该粘合剂包含约20wt%-约40wt%的增容增粘剂。
11.权利要求1或2的粘合剂,其中该粘合剂在140℃下的粘度小于100,000cP。
12.制备权利要求1的热熔粘合剂的方法,包括在升高的温度下反应性共混。
13.权利要求12的方法,其中所述温度为至少100℃。
14.一种制品,它包含至少第一和第二基材,其中第一基材通过权利要求1或2的粘合剂粘结到第二基材上,所述粘合剂已经湿气固化。
15.权利要求14的制品,其中第一和第二基材不同。
16.权利要求14的制品,其中所述第一或第二基材之一是玻璃。
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