CN102015951A - 具有延长的敞开时间的热熔粘合剂 - Google Patents
具有延长的敞开时间的热熔粘合剂 Download PDFInfo
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Abstract
本发明涉及热熔粘合剂组合物,其包含至少一种25℃下为固体的热塑性、硅烷接枝的聚α-烯烃,和至少一种熔点或软化点为-10~40℃的软树脂。这些热熔粘合剂组合物特别适合作为层合粘合剂,且甚至在薄层下也具有延长的敞开时间,但是尽管如此仍然快速地建立很高的初期强度且获得热稳定的粘合连接。
Description
技术领域
本发明涉及热熔粘合剂、特别是层合(Kaschier-)粘合剂领域。
现有技术
热熔粘合剂已长久公知且用作层合粘合剂。如果将熔融的粘合剂以薄层涂覆,则存在的很大问题是,这些粘合剂具有短的敞开时间,即粘合剂在薄层中快速冷却且在此过程中凝固,使得粘合剂不再润湿接合部件的表面,且由此不再能形成粘合连接。对于基于无定形热塑性材料的热熔粘合剂的情形而言特别如此。这类热熔粘合剂的另一缺陷是甚至在施用之后该粘合剂也是热塑性的的问题。这点导致的结果是,粘合连接中的粘合剂在加热该粘合连接时再次熔融,由此导致连接在负荷下被破坏。
聚氨酯热熔粘合剂是反应性热熔粘合剂且是优选的,因为它们在施用之后与水分反应并交联,且由此使得能够实现非常热稳定的粘合。但是,这些粘合剂仅在施用之后即时是极软的,且仅在一定时间段内建立起它们的强度,即在它们交联时。因此,虽然反应性聚氨酯热熔粘合剂在薄层中具有长的敞开时间,但是其具有低初始强度的很大问题。
基于硅烷接枝的聚α-烯烃的热熔粘合剂对于本领域技术人员而言是已知的,例如公开于US 5,994,747和DE 40 00 695 A1中。这些粘合剂具有非常令人感兴趣的性能,因为首先这些热熔粘合剂同样是反应性热熔粘合剂,由此可以实现高强度和高热稳定性。其次,初始强度也是非常高的。但是,这些粘合剂在薄层中也具有非常短的敞开时间,迄今为止在没有预先再活化(再熔融)时这对于它们用作层合粘合剂的用途而言是有害的。
发明概述
由此本发明的目的是提供热熔粘合剂,其甚至在薄层中也具有延长的敞开时间,但是尽管如此仍然快速地建立很高的初期强度且导致热稳定的粘合连接。
令人吃惊地现已发现,依据权利要求1的热熔粘合剂组合物能够解决这个问题。该热熔粘合剂组合物具有宽的粘结范围且导致具有高负荷能力的极其热稳定的粘合。另外,在采用这种热熔粘合剂组合物制得的粘合连接的情形下能够发现大大降低的蠕变行为。从职业卫生和作业安全性角度来看该热熔粘合剂组合物是非常有利的。
本发明的其它方面是依据权利要求12的该热熔粘合剂组合物用于粘合聚烯烃膜、泡沫体或织物的用途,依据权利要求14的复合体以及依据权利要求17的用于制备复合体的方法。
本发明的优选实施方式形成从属权利要求的主题。
发明的具体实施方式
第一方面,本发明涉及一种热熔粘合剂组合物,其包含
a)至少一种在25℃下为固体的热塑性、硅烷接枝的聚α-烯烃(P);和
b)至少一种软树脂(WH),其熔点或软化点为-10~40℃。
该热熔粘合剂组合物包含在25℃下为固体的热塑性、硅烷接枝的聚α-烯烃(P)。
本文中的“α-烯烃”依据常规定义理解为通式CxH2x(x对应着碳原子数)的链烯烃,其在第一个碳原子(α-碳)处具有C-C双键。这种α-烯烃的实例是乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯和1-辛烯。由此,例如,在本文的意义上1,3-丁二烯或2-丁烯或是苯乙烯均不是α-烯烃。
本文中“聚α-烯烃”依据常规定义理解为源于α-烯烃的均聚物和源于不同α-烯烃的共聚物。
优选地,硅烷接枝的聚α-烯烃(P)的软化点为70~150℃,特别地为80~120℃,优选地为90~110℃。
在此,软化点通过环球法来测量,例如依据DIN EN 1238。
这种硅烷接枝的聚α-烯烃(P)对于本领域技术人员而言是众所周知的。它们可以例如通过将不饱和硅烷如乙烯基三甲氧基硅烷接枝到聚α-烯烃上来得到。这种硅烷接枝的聚α-烯烃的详细描述公开于例如US 5,994,747和DE 40 00 695 A1中,因此将其内容引入本申请中。
特别适宜的硅烷接枝的聚α-烯烃(P)是硅烷接枝的聚乙烯或聚丙烯。
另外优选作为硅烷接枝的聚α-烯烃(P)的是硅烷接枝的聚α-烯烃,其是借助于茂金属催化剂制备的聚α-烯烃且其上接枝有硅烷基团。特别是硅烷接枝的聚丙烯均聚物或聚乙烯均聚物。
硅烷接枝的聚α-烯烃(P)的接枝度有利地是大于1重量%、特别地大于3重量%的硅烷,基于聚α-烯烃的重量计。优选地,这种接枝度为2~15重量%,优选为4~15重量%,最优选为8~12重量%。如果使用经由茂金属催化剂制得的聚α-烯烃用于该硅烷接枝的聚α-烯烃,则该接枝度优选为8~12重量%。
如果该热熔粘合剂组合物具有至少两种不同的硅烷接枝的聚α-烯烃(P),则这是特别有利的。
所有硅烷接枝的聚α-烯烃(P)的比例典型地大于50重量%,优选为60~90重量%。
已发现,如果该热熔粘合剂组合物另外包含在室温下为固体的热塑性聚α-烯烃(P′)、特别是无规立构聚α-烯烃(APAO),则是特别有利的。
这些无规立构的聚α-烯烃可以通过α-烯烃,特别是乙烯、丙烯、1-丁烯的聚合例如使用Ziegler催化剂来制备。能够制备α-烯烃的均聚物或共聚物。它们相对于其它聚烯烃具有无定形结构。固体热塑性无规立构聚α-烯烃(P′)优选地具有90℃以上、特别地为90~130℃的软化点。分子量Mn特别地为7000~25000g/mol。如果使用茂金属催化剂来制备无规立构聚α-烯烃(P′),则可能是有利的。
特别优选地,固体的硅烷接枝的聚α-烯烃(P)与固体的热塑性聚α-烯烃(P′)的重量比为1∶1~20∶1。已发现特别适宜的是,固体的热塑性聚α-烯烃(P′)的比例为5~40重量%,优选为15~35重量%,基于该热熔粘合剂组合物计。
该热熔粘合剂组合物另外包含至少一种熔点或软化点为-10~40℃的软树脂(WH)。由于软树脂(WH)在室温(23℃)下以非常接近于熔点或软化点的状态存在这一事实,所以其是室温下已是液体或是非常软的。软树脂可以是天然树脂或合成树脂。
特别地,这种软树脂(WH)是选自链烷烃树脂、烃树脂、聚烯烃、聚酯、聚醚、聚丙烯酸酯或氨基树脂种类的中到较高分子量的化合物。
该软树脂(WH)的熔点或软化点优选为0~25℃,特别地为10~25℃。
在一个优选实施方式中,该软树脂(WH)是烃树脂,特别地是脂肪族C5-C9烃树脂。
其它适宜的软树脂是,例如,聚萜烯树脂,例如作为Arizona Chemical,USA的SylvaresTR A25商业销售的那些,松香脂和妥而油酯(Tallharzester),例如作为Arizona Chemical,USA的SylvatacRE 12、SylvatacRE 10、SylvatacRE 15、SylvatacRE 20、SylvatacRE 25或SylvatacRE 40商业销售的那些。
其它适宜的软树脂是,例如,EscorezTM 5040(Exxon MobilChemical)。
其它适合作为软树脂的烃树脂是,例如,Picco A10(Eastman Kodak)和Regalite R1010(Eastman Kodak)。
所有软树脂(WH)的比例典型地为20~40重量%,特别地为25~35重量%,基于该热熔粘合剂组合物计。
另外已表明,如果所有软树脂(WH)与所有硅烷接枝的聚α-烯烃(P)的重量比小于0.5,则是有利的。优选地,这种重量比为0.2~0.4,且最优选地为0.3~0.4。
如果需要的话,该热熔粘合剂组合物可以另外包含其它热塑性聚合物。这些特别地是热塑性聚酯(TPE)、热塑性聚氨酯(TPU),以及至少一种选自乙烯、丙烯、丁烯、异丁烯、异戊二烯、乙酸乙烯酯、更高羧酸的乙烯基酯和(甲基)丙烯酸的酯的单体的均聚物或共聚物。乙烯-乙酸乙烯酯共聚物(EVA)特别适合作为这种额外的热塑性聚合物。当然,也可以使这些热塑性聚合物接枝。
该热熔粘合剂组合物另外优选地包含至少一种催化硅烷基团的反应的催化剂,特别地用量为0.01~1.0重量%,优选为0.01~0.5重量%,基于该热熔粘合剂组合物计。这种催化剂特别地是有机锡化合物,优选二月桂酸二丁基锡(DBTL)。
另外,该热熔粘合剂组合物可以包含其它成分。适宜的其它成分特别地是选自增塑剂、粘结促进剂、UV吸收剂、UV和热稳定剂、光学增白剂、杀真菌剂、颜料、染料、填料和干燥剂的成分。
但是已表明,如果所有在25℃下为固体的热塑性、硅烷接枝的聚α-烯烃(P)和所有软树脂(WH)和所有任选地存在的固体热塑性聚α-烯烃(P′)的总重大于该热熔粘合剂组合物的80重量%,优选地大于90重量%,则是特别有利的。
基本上由25℃下为固体的热塑性、硅烷接枝的聚α-烯烃(P),软树脂(WH),任选地固体的热塑性聚α-烯烃(P′)和催化硅烷基团反应的催化剂构成的热熔粘合剂组合物,已证实是特别有利的。
在水的作用下,特别是空气湿气形式的水的作用下,该硅烷接枝的聚α-烯烃(P)的硅烷基团水解以形成硅烷醇基团(-SiOH),其本身彼此反应并由此通过形成硅氧烷基团(-Si-O-Si-)而导致该热熔粘合剂组合物的交联。这种热熔粘合剂组合物被称为反应性热熔粘合剂。
因此有利的是要注意,使用尽可能经很好干燥的原材料来制备该热熔粘合剂组合物,且在制备、储存和施用期间保护该粘合剂尽可能不与水或空气湿气接触。
原则上,以热熔粘合剂领域中技术人员公知的常规方式和方法来进行该制备。
该热熔粘合剂组合物通过加热,通过熔融热塑性内含物而液化。该热熔粘合剂组合物的粘度应适合于施用温度。典型地,施用温度为100~200℃。在这种温度下,该粘合剂是可很好加工的。在此温度范围内,粘度优选为1500~50000mPas。如果该粘度实质上更高,则施用将是非常困难的。如果实质上更低,则粘合剂是如此稀液状的,使得在其由于冷却而凝固之前在施用期间从待粘合的材料表面上流掉。
由于冷却而发生的粘合剂凝固和硬化导致快速地建立粘合连接的强度和高的初始粘结强度。使用粘合剂时要注意,在粘合剂仍未过于强烈地冷却的时间内进行粘合,即粘合过程持续的时间必须在粘合剂仍是液体或至少仍是粘性且可变形的时候。除了这种物理类凝固方法之外,粘合剂也将通过水、特别是空气湿气的作用在冷却之后进行进一步交联,且由此在典型地几小时或几天的短时间内进一步获得机械强度。相对于非反应性热熔粘合剂组合物,反应性热熔粘合剂组合物不可以可逆地加热并由此再次液化。因此,这种粘合剂的使用特别是对于其中粘合的复合体在其使用或寿命期间与高温接触而不损坏粘合的那些应用而言是有利的。这种热熔粘合剂的使用同样是有利的,因为由于交联,这种粘合剂显示显著更低的蠕变。
已经表明,甚至在薄层中,依据本发明的所述热熔粘合剂组合物也具有延长的敞开时间,即典型地几分钟、特别地3~10分钟的敞开时间,在此期间能够与接合部件。该粘合剂能够在该敞开时间内很好地润湿接合部件的表面。另外,初期强度快速地建立,这就允许所形成的粘合连接在短时间内能一定程度地传导力。本文中,薄层理解为粘合剂层厚度小于1mm、典型地0.05~0.5mm、特别地约0.1mm。由于由水引起的交联反应,最终可以实现非常高的最终强度,典型地为1~2MPa。
由于不存在异氰酸酯,依据本发明的所述热熔粘合剂组合物从职业卫生和作业安全性角度来看是特别有利的。
另外它们具有非常宽的粘合范围。特别地,在许多情形下甚至可以不使用底漆来粘合非极性塑料,如聚乙烯或聚丙烯。
特别地,由于延长的敞开时间,现有技术中许多情形下在与接合部件的表面接合之前所需的粘合剂“再活化”(再熔融)不再是必须的。这样导致大大简化的粘合过程,这当然另外给使用依据本发明的粘合剂带来了成本上的吸引力。
另外已表明,所述热熔粘合剂组合物是非常存储稳定的,具有良好加工性能,特别地是在100~200℃的施用温度范围内,且在这些温度下甚至在相当长时间内都是粘度稳定的。固化进行时无气味,快速,且甚至在以厚层施用的情形下也无气泡。该粘合剂的特征在于良好粘结性和对环境影响的良好稳定性。
由此已表明,上述热熔粘合剂组合物可以最佳地用于聚烯烃膜或泡沫体或织物的粘合。
特别优选地,它们用作层合粘合剂用于粘合聚烯烃膜或泡沫体或织物。
另外,该热熔粘合剂组合物也非常适合于粘合夹心板(Sandwich Panels)。
本发明的另一方面涉及复合体,该复合体具有第一基材(S1)且其是聚烯烃膜或泡沫体或织物,如上所述的热熔粘合剂组合物(K),或者通过水的作用而交联的如上所述的热熔粘合剂组合物(K′),以及第二基材(S2)。
在此,该热熔粘合剂组合物或交联的热熔粘合剂组合物设置在第一基材(S1)与第二基材(S2)之间。
图1示意性地显示了这样的复合体(1),其包含第一基材(S1)和第二基材(S2)以及热熔粘合剂组合物(K),或者通过水的作用而交联的热熔粘合剂组合物(K′),所述热熔粘合剂组合物设置在第一与第二基材之间,且由此将这两个基材彼此粘合。
作为“聚烯烃膜”,特别理解为厚度为0.05mm~5mm的柔性片状聚烯烃,其可以卷起来。因此,除了厚度小于1mm的严格意义上的“膜”之外,还使用密封幅面体(-bahnen),如典型地例如用于密封管道、屋顶或游泳池而厚度典型地为1~3mm的那些,特定情形下甚至厚度最高达到5mm。这种聚烯烃膜通常通过刷涂、浇铸、压延或挤出来制备,且典型地可以卷材商购获得或者现场制备。它们可以具有单层或多层结构。对于本领域技术人员而言清楚的是,甚至聚烯烃膜也可以仍含有其它添加剂和加工助剂,如填料、UV稳定剂和热稳定剂、增塑剂、润滑剂、杀生物剂、阻燃剂、抗氧剂、颜料(例如二氧化钛或炭黑)、和染料。也就是说,并不100%由聚烯烃构成的那些膜也可以指定为聚烯烃膜。
第二基材(S2),在许多情形下也称为载体,可以是不同类型和性质的。例如,该基材可以包含塑料,特别地聚烯烃或ABS,金属,经涂覆的金属,塑料,木材,木质材料或纤维材料。该基材优选是实心的(fester)成形体。
特别地,所述第二基材(S2)是纤维材料,特别地是天然纤维材料。
另外,第二基材(S2)优选是聚丙烯。
如果需要的话,第二基材(S2)的表面可以进行预处理。特别地,这种预处理可以是清洗或涂覆底漆。但是优选地,施加底漆并非必须的。
所述复合体优选地是工业制造的制品,特别是用于内部装饰的制品,优选运输工具中的内置部件或家具工业的制品。
用于制备车辆、特别是汽车的内部包覆部件的用途是特别重要的。这些内部包覆部件的实例是门侧部件、控制面板、衣帽架、顶棚(Fertighimmel)、移动式天窗、中央控制台、手套箱、遮光板、柱、门把手和扶手、地板、承重地板和行李箱组件,以及送货车和卡车的休息舱壁和后舱壁。
本发明的另一方面还是制备如上所述复合材料的方法。这种方法包括如下步骤:
(i)熔融如上所述的热熔粘合剂组合物,
(ii)施用该熔融的热熔粘合剂组合物到聚烯烃膜(S1)之上,
(iii)加热该聚烯烃膜,
(iv)使第二基材(S2)与熔融的热熔粘合剂组合物进行接触。
为此,特别地,采用真空深拉方法或压力层合用于密封方法中。
在真空深拉方法的情形下,该聚烯烃膜(S1)(由空气不能渗透的材料构成的装饰)典型地气密地夹持在框架中。在该膜下面存在其上已放置载体的下模具。将下模具和载体钻孔钻透或是气体可渗透的。在下面将该设备进一步进行气密性封闭。当空气从这个装置中吸出时,装饰材料自身在其表面上所施加的大气压作用下正好贴靠到载体部件上。在施加真空或负压(Unterdruck)之前加热该装饰材料。由于产生的真空或负压,该装饰材料是空气不能渗透的。
通过加热聚烯烃膜(S1),该膜变软且可以适合于载体的几何形状,不会形成皱折。
这里所使用的聚烯烃膜在许多情形下是装饰膜且具有表面结构。这种塑料膜上的表面结构可以,例如,在粘结之前、之中或之后进行冲压。
在此特别有利的是,可以将该粘合剂直接施用到聚烯烃膜上,且并不施用到载体上(例如对于聚氨酯分散体粘合剂而言正是这种情况)。
因此,该接触步骤特别地在压力下进行,特别地0.1~1巴、优选地至少0.8巴的压力(对应于施加直至0.9巴、优选地直至0.2巴的真空)。
该压力优选地通过在第二基材(S2)与聚烯烃膜(S1)之间的空间中施加负压来产生。上述压力由此特别地通过施加直至0.9巴、优选至少0.2巴的负压来实现。
该接触步骤优选地在50℃或更高的粘合剂温度下,特别地50~200℃的温度、优选地100~150℃的温度下进行。
压力层合方法中,将熔融的热熔粘合剂组合物施用到载体和/或泡沫体或织物(S1)(装饰)的表面上。可能情况下,载体与装饰的粘合在加热的作用下进行,同时接合和加压。
实施例
表1所用原材料的特征及其名称
通过将按照表2中所述的重量份的内含物在150℃的温度下和在惰性气氛中于搅拌釜内彼此混合而制得粘合剂组合物。
粘度
在将封闭管中的各个热熔粘合剂在加热炉中于140℃下熔融20分钟之后,称重9.7g粘合剂到一次性套管中,并在表2中所述的各个温度下在粘度计中恒温20分钟。在130℃或190℃下,以每分钟10转在Brookfield DV-2Thermosel粘度计上使用27号锭子进行粘度测量。选择测量5分钟之后获得的数值作为粘度。表2中,将130℃下的测量值称为“Visk130”,且190℃下的测量值称为“Visk190”。
初期强度的建立
将该热熔粘合剂熔融,并在140℃的粘合剂温度下施用到PP试样(100mm×25mm×5mm)上且接合到第二PP试样(粘合剂厚度:1mm,重叠面积:25mm×25mm)上。借助于Zwick拉力试验机Z020以10mm/min的测量速率在23℃和50%相对空气湿度下,通过在不同时间(tx)之后测量这些拉伸剪切强度试样(从施加熔融粘合剂起测量)来测量初期强度。表2中列出了时间tx之后测量的最大张力(“σmax”)。出于实际原因,通过这种方法在3分钟(tx)以下不能进行测量。
图2显示了初期强度构建曲线,即在施加了实施例1和2以及对比实施例Ref.1的粘合剂(tx)之后相对于时间的最大张力(σmax)的变化图。从现有曲线中外推出以虚线表示的曲线部分以及3分钟以下的点。
敞开时间
将热熔粘合剂在140℃下熔融,并借助于刮刀将大约20g以500μm的层厚和60mm的宽度,施用到位于150℃温度的加热板之上的硅烷化纸(B700白色,Laufenberg &Sohn,德国)的硅烷化侧上,形成约30cm的带。粘合剂施用之后立即将由此涂布的纸置于调节在23℃下的山毛榉木板上。在30秒的规则时间间隔(“ty”)之后,此时将硅烷化纸带(10cm×1cm)以纸侧置于粘合剂上,用手指快速按压并再缓慢地剥去。敞开时间的终点确定为从粘合剂施加的时刻测量的、粘合剂不再保持粘附于被覆纸(Deck-Papier)上的时间。
软化点
依据DIN EN 1238,通过环球法测量软化点。
表2热熔粘合剂组合物
在此,由表2和图2的结果看出,实施例1和2相对于相应的对比实施例Ref.1具有显著更长的敞开时间。实施例显示出强度的快速建立。另外,所有粘合剂在它们交联之后具有相当的最终强度。
Claims (18)
1.热熔粘合剂组合物,其包含:
a)至少一种在25℃下为固体的热塑性、硅烷接枝的聚α-烯烃(P);和
b)至少一种软树脂(WH),其熔点或软化点为-10~40℃。
2.权利要求1的热熔粘合剂组合物,其特征在于,该硅烷接枝的聚α-烯烃(P)的软化温度为70~150℃,特别地为80~120℃,优选地为90~110℃。
3.权利要求1或2的热熔粘合剂组合物,其特征在于,该硅烷接枝的聚α-烯烃(P)是硅烷接枝的聚乙烯或聚丙烯。
4.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,该硅烷接枝的聚α-烯烃(P)是借助于茂金属催化剂制备的且其上接枝有硅烷基团的聚α-烯烃。
5.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,该组合物另外包含在室温下为固体的热塑性聚α-烯烃(P′)、特别是无规立构聚α-烯烃(APAO)。
6.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,该组合物包含至少两种不同的硅烷接枝的聚α-烯烃(P)。
7.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,该软树脂(WH)的熔点或软化点为0~25℃,特别地为10~25℃。
8.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,该软树脂(WH)为烃树脂,特别地是脂肪族C5-C9-烃树脂。
9.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,该软树脂(WH)的用量为20-40重量%,特别地为25-35重量%,基于该热熔粘合剂组合物计。
10.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,所有软树脂(WH)与所有硅烷接枝的聚α-烯烃(P)的重量比小于0.5,优选地为0.2~0.4,最优选地为0.3~0.4。
11.前述权利要求任一项所述的热熔粘合剂组合物,其特征在于,所有25℃下为固体的热塑性、硅烷接枝的聚α-烯烃(P)和所有软树脂(WH)和所有任选地存在的固体热塑性聚α-烯烃(P′)的重量总和大于该热熔粘合剂组合物的80重量%,优选地大于90重量%。
12.权利要求1~11中任一项的热熔粘合剂组合物用于粘合聚烯烃膜或泡沫体或织物的用途。
13.权利要求1~11中任一项的热熔粘合剂组合物作为层合粘合剂用于粘合聚烯烃膜或泡沫体或织物的用途。
14.复合体(1),其具有
-第一基材(S1),其是聚烯烃膜或泡沫体或织物;
-依据权利要求1~11中任一项的热熔粘合剂组合物,或者通过水的作用而交联的依据权利要求1~11中任一项的热熔粘合剂组合物,以及
-第二基材(S2);
其中,该热熔粘合剂组合物或交联的热熔粘合剂组合物设置在第一基材(S1)与基材(S2)之间。
15.权利要求14的复合体,其特征在于,该第二基材(S2)是纤维材料,特别是天然纤维材料。
16.权利要求14的复合体,其特征在于,该第二基材(S2)是聚丙烯。
17.用于制备权利要求14~16中任一项的复合体的方法,包括如下步骤:
(i)熔融依据权利要求1~11中任一项的热熔粘合剂组合物,
(ii)施用该熔融的热熔粘合剂组合物到聚烯烃膜(S1)上,
(iii)加热该聚烯烃膜,
(iv)使第二基材(S2)与熔融的热熔粘合剂组合物进行接触。
18.权利要求17的方法,其特征在于,该接触步骤在特别是0.1~1巴、优选地至少0.8巴的压力下进行。
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EP20080155272 EP2113545A1 (de) | 2008-04-28 | 2008-04-28 | Heissschmelzklebstoffe mit verlängerter Offenzeit |
PCT/EP2009/055110 WO2009133093A1 (de) | 2008-04-28 | 2009-04-28 | Heissschmelzklebstoffe mit verlängerter offenzeit |
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CN108472605A (zh) * | 2015-12-11 | 2018-08-31 | 汉高股份有限及两合公司 | 用于配混和施加粘合剂的方法 |
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ZA201006546B (en) | 2011-12-28 |
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