CN101184818A - 用于粘结金属组件和塑料的基于丁腈橡胶共混物的胶粘片 - Google Patents
用于粘结金属组件和塑料的基于丁腈橡胶共混物的胶粘片 Download PDFInfo
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Abstract
一种胶粘片,包括至少一种可热活化粘合剂,所述粘合剂基于至少一种丁腈橡胶S1和至少一种丁腈橡胶S2,以及至少一种反应性树脂的共混物,所述至少一种丁腈橡胶S1具有不大于25重量%的丙烯腈分率,且所述至少一种丁腈橡胶S2具有不小于30重量%的丙烯腈分率。
Description
本发明涉及用于便携式消费电子制品(portable consumer electronicsarticle)中粘结金属部件和塑料的、由至少两种组成不同的丁腈橡胶和至少一种反应性树脂构成的共混物,其随后的粘接即使在低于-15℃的低温下也具有高结合强度和抗震性。
使用双面压敏胶带粘结金属部件和塑料通常有效。为此需要的粘合力足以将金属组件固定和粘牢在塑料上。所用的金属优选为钢(包括不锈钢)和铝。所用的塑料为,例如,PVC、ABS、PC或基于这些聚合物的共混物。然而,对于便携式消费电子制品,该要求在不断提高。一方面,这些制品变得更小,从而粘结面积也变得更小。另一方面,由于便携式制品在非常宽的温度范围内使用而且可能受到机械载荷(碰撞、坠落等),该粘结需要满足额外的要求。这些要求对于金属和塑料的粘结尤其存在问题。在坠落的情况下,塑料可能吸收一些能量,而金属根本不变形。此时胶带必须吸收大部分能量。对此使用可热活性片材会特别有效,可热活性片材能够在活化后显示出特别高的粘合力。
可热活化粘合剂可分为两类:
a)热塑性可热活化片材
b)反应性可热活化片材。
热塑性可热活化片材早已为人所知,且基于例如聚酯或共聚酰胺。其商品实例可得自3M公司(产品615,615S)或tesa(产品8440)。然而,就在便携式消费电子制品中的应用而言,这些热塑性可热活化片材还有一些缺点。特别是涉及在一定温度和压力应用下的“渗出(oozing)”,因为在该应用中主要加工冲切物(diecut),从而它们的形状发生改变。
还可以使用反应性可热活化片材。如果弹性体组件具有高弹性,这些片材具有明显较好的尺寸稳定性。然而,反应性树脂会发生交联反应,这显著增加了结合的强度。因此,对于该粘结,可以使用,例如基于丁腈橡胶和酚醛树脂的可热活化片材,如,购自例如tesa的产品8401。然而,这些反应性可热活化片材的缺点是,结合强度取决于固化条件。由于消费电子装置是大批量制造的,各组件的制造周期非常短,从而在此施加了特别苛刻的要求。
丁腈橡胶的高流动粘度赋予可热活化片材高的尺寸稳定性,并且,由于交联反应,在金属和塑料上还具有高粘合力。然而,高尺寸稳定性和低流动性能也有以下缺点:由于强度高,可热活化片材在低温下极快硬化且变得易碎,因此在非常低的温度下,该粘结变得对冲击敏感和易断裂。
迄今,在制造于高温和低温下均具有非常高的结合强度,从而适用于宽温度范围的可热活化片材方面尚未取得成功。
考虑到现有技术,本发明的目的是提供用于便携式消费电子制品中将金属部件固定到塑料上的可热活化胶粘片,其适用于宽的温度范围。
该片材应该有利地经受在-20℃下的冷冲击测试,并且其特征在于,在-20℃至+50℃的温度范围内具有高的结合强度。
根据本发明,该目的可以通过胶粘片而实现,该胶粘片包括至少一种可热活化粘合剂,所述粘合剂基于至少一种丁腈橡胶S1和至少一种丁腈橡胶S2,以及反应性树脂的共混物,所述至少一种丁腈橡胶S1具有不大于25重量%的丙烯腈分率,且所述至少一种丁腈橡胶S2具有不小于30重量%的丙烯腈分率,所述反应性树脂能够自身交联,与其他反应性树脂交联,和/或与丁腈橡胶S1和S2交联。
本发明的两种合成丁腈橡胶S1和S2及至少一种反应性树脂的共混物优选是具有以下性质中的两种或两种以上的共混物,非常优选是具有所有以下性质的共混物:
a)共混物为微相分离形式,其特征在于,在DSC(差示扫描量热法或动态扫描量热法)中具有至少两个不同的玻璃化转变温度,
b)至少一个玻璃化转变温度大于10℃和至少一个玻璃化转变温度小于-20℃,
c)通过测试方法A测量得到的下落高度(drop height),在室温(RT)下大于1m,在-20℃的温度下大于25cm,
d)通过测试方法B测量得到的结合强度,在室温(RT)下大于3N/mm2,在-20℃的温度下大于6N/mm2。
特别是借助于极低温度(低于-20℃)下和高温(>10℃)下的微相分离及两个玻璃化转变温度的发展(低温和高温下粘合性能的组合),本发明的共混物的混合获得在胶粘片的粘结性能方面的改进。
由于热力学不相容聚合物嵌段的化学结合,该嵌段共聚物的特征在于微相分离,换句话说,热力学相容聚合物嵌段发生联系,而热力学不相容聚合物嵌段分隔为空间隔离的区域,而没有宏观相分离。根据组成,产生具有不同结构的相(“区域形成(domain forming)”)。对于本发明,由此测量或观察到的微相分离是不需要产生“理想”结构的。
测定微相分离的存在的典型方法包括,例如,
·透射电子显微镜法(TEM),使用与着色剂作用不同的物质;
·原子力显微镜法(AFM),借助表面拓扑法,对照硬度或粘合的差异
·散射法(中子散射,小角x-射线散射),在具有不同物质/辐射作用截面的相的物质中进行;
·量热法,例如差示量热法(DSC)或差示热分析法(DTA),还有用于具有不同软化点的相的物质的流变测量法;
·NMR旋转扩散法(spin diffusion),用于具有不同动力学相的物质。
具有低玻璃化转变温度的区域在低温下低温冲击强度和粘合性上升;高温区域在高温下保持结合强度,及冲切物在压力和温度下的尺寸稳定性。
本文记录的玻璃化转变温度对应于准稳态(quasi-steady state)实验,例如DSC(差示或动态扫描量热法)中得到的那些。
丁腈橡胶S1和S2的总重量分率相对于反应性可热活化片材的全部组成优选为25重量%至70重量%,更优选为30重量%至60重量%。
金属部件和塑料的结合取决于表面粗糙度、曲率或尺寸,使用层厚为25至300μm的可热活化片材;在一特别优选的实施方案中,层厚为50至250μm。
本发明的可热活化粘合剂基于至少两种丁腈橡胶(即,丙烯腈丁二烯橡胶)S1和S2的共混物。
可用的丙烯腈丁二烯橡胶为EniChem的EuropreneTM,或者Bayer的KrynacTM和PerbunanTM,或者Zeon的BreonTM and NipolTM。可用的氢化丙烯腈丁二烯橡胶为Bayer的TherbanTM和Zeon的ZetpolTM。丙烯腈丁二烯橡胶是热聚合的或冷聚合的。
丁腈橡胶S1非常优选的丙烯腈分率小于25重量%。然而,为了防止完全相分离,丙烯腈分率基于S1的全部量应有利地大于15重量%。另一标准是丁腈橡胶S1的玻璃化转变温度。为了获得微相分离,DSC中的静态玻璃化转变温度应该优选小于-30℃,更优选小于-35℃。丁腈橡胶S1的另一标准为Mooney粘度。由于需要确保低温下的高柔性,Mooney粘度应该低于100(Mooney ML 1+4,100℃)。这类丁腈橡胶的商品实例包括Zeon Chemicals的NipolTM N917。
特别是丁腈橡胶S2的丙烯腈分率大于30重量%。然而,为了防止完全相分离,丙烯腈分率基于S2的总量应优选小于60重量%。为了获得微相分离,DSC中静态玻璃化转变温度应优选大于或等于-20℃,更优选大于-15℃。由于需要确保低温下的高柔性,S2的Mooney粘度同样应该低于100(Mooney ML 1+4,100℃)。这类丁腈橡胶的商品实例包括Zeon Chemicals的NipolTM 1002。
非常优选使用重量比介于20%丁腈橡胶S1∶80%丁腈橡胶S2和80%丁腈橡胶S1∶20%丁腈橡胶S2之间的丁腈橡胶。更优选丁腈橡胶S1和丁腈橡胶S2的重量比介于40∶60和60∶40之间。已发现选择均衡重量比,即基本上为50∶50,特别有利。
在共混物中反应性树脂的分率优选为75重量%至30重量%。
在反应性树脂概念下使用的一种非常优选的组分包括环氧树脂。在此环氧树脂的重均分子量优选从Mw=100g/mol至最大值Mw=10000g/mol,对于聚合环氧树脂而言。
例如,环氧树脂包括,双酚A和环氧氯丙烷的反应产物,环氧氯丙烷、缩水甘油酯、环氧氯丙烷和对-氨基苯酚的反应产物。
优选的商品实例包括Ciba Geigy的AralditeTM 6010、CY-281TM、ECNTM1273、ECNTM1280、MY 720、RD-2,Dow Chemical的DERTM 331、DERTM732、DERTM 736、DENTM 432、DENTM 438、DENTM 485,Shell Chemical的EponTM 812、825、826、828、830、834、836、871、872、1001、1004、1031等;以及同样来自Shell Chemical的HPTTM1071和HPTTM 1079。
可以同样有利地使用脂族环氧树脂;市售的并且非常适合的实例包括乙烯基环己烷二氧化物,例如Union Carbide Corp.的ERL-4206、ERL-4221、ERL 4201、ERL-4289或ERL-0400。
还可以有利地使用可溶可熔酚醛(Novolak)树脂;由此,可以使用的实例包括Celanese的Epi-RezTM 5132,Sumitomo Chemical的ESCN-001,CibaGeigy的CY-281,Dow Chemical的DENTM 431、DENTM 438、Quatrex 5010,Nippon Kayaku的RE 305S,Dai Nippon Ink Chemistry的EpiclonTM N673,或者Shell Chemical的EpikoteTM 152。
另外,对于反应性树脂,也可以使用三聚氰胺树脂,例如Cytec的CymeITM 327和323。
另外,对于反应性树脂,也可以使用萜烯-酚醛树脂,例如ArizonaChemical的NIREZTM2019。
另外,对于反应性树脂,也可以使用酚醛树脂,例如Toto Kasei的YP 50,Union Carbide Corp.的PKHC,Showa Union Gosei Corp的BKR 2620。此外,对于反应性树脂,还可以使用和其他酚醛树脂组合的甲阶酚醛树脂(phenolicresole resin)。
另外,对于反应性树脂,也可以使用聚异氰酸酯,例如NipponPolyurethane Ind.的CoronateTM L,Bayer的DesmodurTM N3300或MondurTM489。
还可以使用上述两种或更多种反应性树脂的组合。
在本发明胶粘片的一种有利实施方案中,还可以将增强粘合力的树脂(增粘树脂)加入到共混物中,非常有利地,该树脂的分率基于共混物达30重量%。添加的增粘树脂毫无例外地包括所有已知的和在文献中描述的增粘剂树脂。典型的包括蒎烯树脂、茚树脂和松香,它们的岐化、氢化、聚合和酯化衍生物及盐,脂族和芳族烃树脂、萜烯树脂和萜烯-酚醛树脂,以及C5、C9和其他烃树脂。可以使用这些树脂和其他树脂的任意组合,以便根据要求调节所得粘合剂的性能。一般而言,可以使用任何与橡胶S1和/或S2相容(可溶)的树脂;特别可以提及所有的脂族、芳族和烷芳烃树脂,基于单一单体的烃树脂、氢化烃树脂、官能烃树脂和天然树脂。有关现有技术状态的描述特别参考Donatas Satas(van Nostrand,1989)的“Handbook ofPressure Sensitive Adhesive Technology”。
为了加速两个组分之间的反应,还可以任选将交联剂和促进剂加入到混合物中。
合适的促进剂包括,例如,咪唑,市售的有Shikoku Chem.Corp.的2M7、2E4MN、2PZ-CN、2PZ-CNS、P0505和L07N,或者Air Products的Curezol2MZ。还适合添加HMTA(六亚甲基四胺)作为交联剂。
此外,还可以使用胺,特别是叔胺用于加速。
还可以有利地使用的添加剂为增塑剂。在此,本发明的一个优选实施方案中,可以使用基于聚二醇醚、聚氧化乙烯、磷酸酯、脂族羧酸酯和苯甲酸酯的增塑剂。此外,还可以使用芳族羧酸酯、高分子量二醇、磺酰胺和己二酸酯(adipic ester)。
作为选择,还可以添加填料(例如,纤维、碳黑、氧化锌、二氧化钛、白垩、实心或空心玻璃珠、其他材料的微球体、硅石、硅酸盐)、成核剂、膨胀剂、粘合力增强添加剂和热塑性塑料、配合剂和/或防老化剂,该防老化剂是以例如主抗氧化剂和辅助抗氧化剂的形式或以光稳定剂的形式。
在进一步优选的实施方案中,向共混物中加入其他添加剂,例如聚乙烯醇缩甲醛、聚丙烯酸酯橡胶、氯丁二烯橡胶、乙烯-丙烯-二烯橡胶、甲基-乙烯基-硅氧烷橡胶、氟硅橡胶、四氟乙烯丙烯共聚物橡胶、丁基橡胶和苯乙烯-丁二烯橡胶。
可用的聚乙烯醇缩丁醛为Solutia的ButvarTM、Wacker的PioloformTM和Kuraray的MowitalTM。可用的聚丙烯酸酯橡胶为Zeon的Nipol ARTM。可用的氯丁二烯橡胶为Bayer的BayprenTM。可用的乙烯-丙烯-二烯橡胶为DSM的KeltanTM、Exxon Mobil的VistalonTM、和Bayer的Buna EPTM。可用的甲基-乙烯基-硅氧烷橡胶为Dow Corning的SilasticTM和GE Silicones的SiloprenTM。可用的氟硅橡胶为GE silicones的SilasticTM。可用的丁基橡胶为Exxon Mobil的Esso ButyITM。可用的苯乙烯-丁二烯为Bayer的Buna STM、EniChem的EuropreneTM、Bayer的Polysar STM。可用的聚乙烯醇缩甲醛为Ladd Research的FormvarTM。
在进一步优选的实施方案中,向共混物中加入其他添加剂,例如选自以下聚合物的热塑性材料:聚氨酯,聚苯乙烯,丙烯腈-丁二烯-苯乙烯三元共聚物,聚酯,不加增塑剂的聚氯乙烯,加增塑剂的聚氯乙烯,聚甲醛,聚对苯二甲酸丁二醇酯,聚碳酸酯,氟化聚合物如聚四氟乙烯,聚酰胺,乙烯-乙酸乙烯酯,聚乙酸乙烯酯,聚酰亚胺,聚醚,共聚酰胺,共聚聚酯,聚烯烃如聚乙烯、聚丙烯、聚丁烯和聚异丁烯,以及聚(甲基)丙烯酸酯。
可热活化片材的粘合力可通过进一步有目的的添加来提高。因而,可以使用,例如聚亚胺共聚物或聚乙酸乙烯酯共聚物作为提升粘合力的添加物。
制备方法
可以由溶液或在熔体中制备本发明的共混物。为了在溶液中制备该共混物,优选使用其中至少一种组分具有良好的溶解性的溶剂。使用已知的搅拌装置如混合器制备该混合物。为此,还可能需要引入热。随后具体地由溶液或由熔体将共混物涂覆在临时衬里上。由溶液涂覆之后,在干燥风道(drying tunnel)中将溶剂除去。
对于由熔体涂覆,事先将溶剂从共混物中除去。在一优选的实施方案中,在减压下在浓缩挤出机中将溶剂除去,这可以使用例如单螺杆或双螺杆挤出机进行,优选在不同或相同的真空段中将溶剂蒸馏出来,并具有进料预热器。然后通过熔体模头或挤出模头进行涂覆,如果需要或合乎要求,将粘合膜进行拉伸,以获得最佳涂层厚度。
在本发明的另一实施方案中,在熔体中制备共混物。优选可以使用混合器、双螺杆挤出机或行星式辊筒挤出机进行树脂的共混。
然后,由熔体再次进行涂覆,并优选再次在临时衬里上进行。通过熔体模头或挤出模头进行涂覆,如果需要或合乎要求,将粘合膜进行拉伸,以获得最佳涂层厚度。
用于共混物的衬里材料是技术工人熟悉的典型材料,例如膜(聚酯,PET,PE,PP,BOPP,PVC,聚酰亚胺)、无纺布、泡沫材料、织物,和机织膜,还有隔离纸(玻璃纸,HDPE,LDPE)。衬里材料应该已经用隔离涂层处理过。在本发明的一种非常优选的实施方案中,隔离涂层由硅氧烷隔离漆或氟化隔离漆组成。在一种优选的实施方案中,在隔离纸上直接涂覆可热活化粘合剂,然后进一步用作转移带(transfer tape)。为了制备较大膜层厚度,将两层或更多层粘合层层合在一起也会有利。特别优选在引入的热和压力下进行。
实施例
测试方法:
下落测试A)(见图1和3)
结合面积为2cm2。使用本发明的可热活化胶粘片(3)将1.5mm厚及2cm宽的铝(Al)片(1)和2cm宽及3mm厚的聚碳酸酯(PC)片(2)连结起来。
第一步,借助95℃的热板将200μm厚的可热活化片和铝层合。接着除去隔离片。在热压机中粘结测试样品(参见图3;1=铝片,2=聚碳酸酯片,3=可热活化粘合剂膜,4=压力机压头(press ram),5=压力),由Al一侧加热。在180℃加热压力机压头、5bar压力、加压时间5s下进行热活化。
接着进行下落测试(图中箭头:下落方向)。将50g重量的(4)固定在PC片上。然后,将整个组件从不同高度下落到钢板(5)上。测定在与可热活化片的结合力仍能够吸收冲击且Al/PC测试样品不会分开时的高度。另外,还在不同温度进行该测试。
结合强度B)(参见图2和3)
通过动态剪切实验测定结合强度(参见图2)。结合面积为2cm2。使用本发明的可热活化胶粘片(3)将1.5mm厚及2cm宽的铝(Al)片(1)和2cm宽及3mm厚的聚碳酸酯(PC)片(2)连结起来。
第一步,借助95℃的热板将200μm厚的可热活化片和铝层合。接着除去隔离片。在热压机中粘结测试样品(参见图3;1=铝片,2=聚碳酸酯片,3=可热活化粘合剂膜,4=压力机压头,5=压力),由Al一侧加热。在180℃加热压力机压头、5bar压力、加压时间5s下进行热活化。
随后,使用Zwick机械用缓慢增加的力F以10mm/min的速度将测试样品撕开。测量单位以N/mm2表示且为将测试样品(铝和聚碳酸酯)彼此分开时测得的最大力。在不同温度下进行测量:
-20℃,0%湿度
23℃,50%湿度
50℃,50%湿度.
在压制和热活化之后立即进行测量,等待约30分钟用来适应相应的温度范围。
手机实验c)
使用厚度为200μm的可热活化片材来粘结铝装饰片(trim piece)和PC手机外壳(casing)。粘结面积大约为4cm2。采用热压机在180℃、5bar压力,以5秒固化时间进行粘结。24小时后,在粘合之后将手机外壳冷却至-20℃。然后,将样品在该温度彼此相反扭曲(twist)。
分子量测定
依照以下参数通过凝胶渗透色谱法测量平均分子量Mw(重量平均值):
洗脱液:THF/0.1体积%三氟乙酸
前置柱:PSS-SDV,10μ,ID 8.0mm×50mm
柱:PSS-SDV,10μ,直柱(linear one),ID 8.0mm×300mm
泵TSP P 100
流速:0.5ml/min
样品浓度:1.5g/l
注入系统:TSPAS 3000,100μl注入体积
温度:25℃
检测器:Shodex RI 71
再次用甲苯作为内标物进行测量。
在柱的分离范围内使用聚苯乙烯标准物进行校正;利用已知的MarkHouwink系数a和K,将聚苯乙烯标准全部转换为PMMA标准。
摩尔质量平均值和它们的分布的计算是基于通用的(PMMA)标准,通过剥离法(WinGPC Version 6.20)用计算机辅助进行的。
所有的附图都是“PMMA摩尔质量当量(equivalents)”。
参考例1)
在混合器中在甲乙酮中将50重量%来自Zeon的Breon N36 C80(丁腈橡胶),40重量%的与8重量%HMTA(Rohm&Haas)共混的可溶可熔酚醛树脂,以及10重量%来自Bakelite的甲阶酚醛树脂9610 LW制备成30%浓度溶液(strength solution)。捏合时间为20h。然后将可热活化粘合剂由溶液涂覆在玻璃纸隔离纸上并在100℃下干燥10分钟。干燥之后的涂层厚度为100μm。然后,将两层这样的片层用辊式层合机在100℃层合在一起。其后涂层厚度为200μm。
参考例2)
在混合器中在甲乙酮中将50重量%来自Zeon的Nipol N1094-80(丁腈橡胶),40重量%的与8重量%HMTA(Rohm&Haas)共混的可溶可熔酚醛树脂Durez 33040,以及10重量%来自Bakelite的甲阶酚醛树脂9610 LW制备成30%浓度溶液。捏合时间为20h。然后将可热活化粘合剂由溶液涂覆在玻璃纸隔离纸上并在100℃下干燥10分钟。干燥之后的涂层厚度为100μm。然后,将两层这样的片层用辊式层合机在100℃层合在一起。其后涂层厚度为200μm。
实施例3)
在混合器中在甲乙酮中将25重量%来自Zeon的Nipol N1094-80(丁腈橡胶),25重量%来自Zeon的Breon N36 C80(丁腈橡胶),40重量%的与8重量%HMTA(Rohm&Haas)共混的可溶可熔酚醛树脂Durez 33040,以及10重量%来自Bakelite的甲阶酚醛树脂9610 LW制备成30%浓度溶液。捏合时间为20h。然后将可热活化粘合剂由溶液涂覆在玻璃纸隔离纸上并在100℃下干燥10分钟。干燥之后的涂层厚度为100μm。然后,将两层这样的片层用辊式层合机在100℃层合在一起。其后涂层厚度为200μm。
实施例4)
在混合器中在甲乙酮中将27.5重量%来自Zeon的Nipol N1094-80(丁腈橡胶),27.5重量%来自Zeon的Breon N36 C80(丁腈橡胶),45重量%的与8重量%HMTA(Rohm&Haas)共混的可溶可熔酚醛树脂Durez 33040,以及10重量%来自Bakelite的甲阶酚醛树脂9610 LW制备成30%浓度溶液。捏合时间为20h。然后将可热活化粘合剂由溶液涂覆在玻璃纸隔离纸上并在100℃下干燥10分钟。干燥之后的涂层厚度为100μm。然后,将两层这样的片层用辊式层合机在100℃层合在一起。其后涂层厚度为200μm。
结果:
用与参考例1和2相同的方法测试本发明的可热活化粘合剂片3和4。参考例1表示基于具有高丙烯腈分率(36重量%)的丁腈橡胶的可热活化片材。参考例2是基于具有23重量%的低丙烯腈分率的丁腈橡胶。所有实施例都使用相同的固化条件,以粘合铝和PC-例如,在制造手机时经常出现的应用。在粘合之后,对样品进行下落实验,结果列在表1中。各下落高度以cm记录。
表1:
实施例 | 测试方法A,室温 | 测试方法A,-20℃ |
参考例1 | >150cm | 8cm |
参考例2 | >150cm | 15cm |
实施例3 | >150cm | 50cm |
实施例4 | >150cm | 60cm |
从表1显然可知,本发明的实施例3和4在-20℃具有明显更好的冷冲击灵敏性,这进而反映在更高的下落高度上。相反,室温下,差异非常微小,所有实施例都具有高的耐冲击性。
另外,在不同温度下测量各实施例的结合强度。再次,所有的实施例都保持结合/固化条件恒定。结果列在表2中。
表2
实施例 | 测试方法B,室温 | 测试方法B,+50℃ | 测试方法B,-20℃ |
参考例1 | 4.3N/mm2 | 1.5N/mm2 | 4.8N/mm2 |
参考例2 | 3.9N/mm2 | 1.0N/mm2 | 5.5N/mm2 |
实施例3 | 3.6N/mm2 | 1.0N/mm2 | 8.1N/mm2 |
实施例4 | 3.8N/mm2 | 0.9N/mm2 | 9.2N/mm2 |
从表2显然可知,本发明的实施例3和4尤其在低温下结合强度最大。与出色的低温冲击强度相结合的事实表明,本发明实施例表现出明显更好的低温性能。
在室温和+50℃下,参考例1具有最高值,由于该例仅基于具有较高丙烯腈分率的丁腈橡胶,因此,在动态剪切实验中表现出最低的流动性能。然而,在本发明的实施例3和4及参考例2之间的差异相对较小。
在最后的测试中,相应于实际应用,粘合手机外壳和铝装饰片。然后,在-20℃下将手机外壳进行扭曲。在参考例1和2的情况中,该粘合非常容易打开。相反,本发明的实施例3和4在低温下扭曲毫无问题,从而表现出明显更好的低温粘合性能。与之大不相同的,在室温,所有四个实施例都表现出毫无问题的性能和高粘合水平。
Claims (9)
1.一种胶粘片,包括至少一种可热活化粘合剂,所述粘合剂基于至少一种丁腈橡胶S1和至少一种丁腈橡胶S2,以及至少一种反应性树脂的共混物,所述至少一种丁腈橡胶S1具有不大于25重量%的丙烯腈分率,且所述至少一种丁腈橡胶S2具有不小于30重量%的丙烯腈分率。
2.如权利要求1的胶粘片,其特征在于所述至少一种丁腈橡胶S1的丙烯腈分率为15重量%~25重量%。
3.如前述权利要求至少一项的胶粘片,其特征在于所述至少一种丁腈橡胶S2的丙烯腈分率为30重量%~60重量%。
4.如前述权利要求至少一项的胶粘片,其特征在于选择丁腈橡胶S1和S2,使得通过DSC测量时,该共混物显示至少两个不同的玻璃化转变温度,特别是该玻璃化转变温度之一为至少10℃,且该玻璃化转变温度之一不高于-20℃。
5.如前述权利要求至少一项的胶粘片,其特征在于丁腈橡胶S1和丁腈橡胶S2的重量比为20∶80至80∶20,优选40∶60至60∶40,非常优选为约50∶50。
6.如前述权利要求至少一项的胶粘片,其特征在于所述至少一种反应性树脂相对于该共混物存在的分率为30重量%~75重量%。
7.如前述权利要求至少一项的胶粘片,其特征在于所述至少一种反应性树脂为酚醛树脂、萜烯酚醛树脂和/或环氧树脂。
8.如前述权利要求至少一项的胶粘片,其特征在于将增粘树脂加入到该共混物中,特别以相对于该共混物高达30重量%的分率加入到该共混物中。
9.胶粘片用于粘结电子制品中的金属部件的用途。
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DE102005025056A DE102005025056A1 (de) | 2005-05-30 | 2005-05-30 | Nitrilkautschuk-Blends zur Fixierung von Metallteilen auf Kunststoffen |
DE102005025056.4 | 2005-05-30 | ||
PCT/EP2006/004973 WO2006128629A1 (de) | 2005-05-30 | 2006-05-24 | Klebstofffolie auf basis von nitrilkautschuk-blends zur fixierung von metallteilen auf kunststoffen |
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CN102215654A (zh) * | 2010-04-09 | 2011-10-12 | 许西岳 | 电子产品金属外壳与塑料件组合结构 |
CN103421435A (zh) * | 2012-05-21 | 2013-12-04 | 德莎欧洲公司 | 可吸收光的热活化胶粘剂及含有这种胶粘剂的胶带 |
CN103594549A (zh) * | 2012-08-13 | 2014-02-19 | 德莎欧洲公司 | 制造太阳能模块的方法 |
CN102083607B (zh) * | 2008-07-03 | 2015-03-25 | 德莎欧洲公司 | 增加模铸组件中塑料和金属之间的粘结稳定性的可热活化粘合剂 |
CN106118566A (zh) * | 2015-05-05 | 2016-11-16 | 德莎欧洲公司 | 具有含连续聚合物相的胶粘剂的胶带 |
CN107849412A (zh) * | 2015-08-11 | 2018-03-27 | 德莎欧洲股份公司 | 基于丙烯腈丁二烯橡胶的压敏胶粘剂 |
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DE102005035905A1 (de) * | 2005-07-28 | 2007-02-01 | Tesa Ag | Nitrilkautschuk Blends zur Fixierung von Metallteilen auf Kunststoffen |
DE102006058935A1 (de) * | 2006-12-12 | 2008-02-28 | Tesa Ag | Verbundmittelkopf-Sicherungselement |
US7934531B2 (en) * | 2008-04-18 | 2011-05-03 | Brady Worldwide, Inc. | Method and apparatus for applying heat activated transfer adhesives |
DE102008053447A1 (de) * | 2008-09-11 | 2010-04-15 | Tesa Se | Klebemasse mit hohem Repulsionswiderstand |
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JP6864471B2 (ja) * | 2016-12-26 | 2021-04-28 | マクセルホールディングス株式会社 | 熱接着テープおよび熱接着テープの製造方法 |
DE102017221039B4 (de) * | 2017-11-24 | 2020-09-03 | Tesa Se | Verfahren zur Herstellung einer Haftklebemasse auf Basis von Acrylnitril-Butadien-Kautschuk |
DE102022100562A1 (de) | 2022-01-11 | 2023-07-13 | Tesa Se | Poly(meth)acrylat-basierte Haftklebemassen enthaltend mindestens einen Acrylnitril-Butadien-Kautschuk |
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2005
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CN102083607B (zh) * | 2008-07-03 | 2015-03-25 | 德莎欧洲公司 | 增加模铸组件中塑料和金属之间的粘结稳定性的可热活化粘合剂 |
CN102215654A (zh) * | 2010-04-09 | 2011-10-12 | 许西岳 | 电子产品金属外壳与塑料件组合结构 |
CN103421435A (zh) * | 2012-05-21 | 2013-12-04 | 德莎欧洲公司 | 可吸收光的热活化胶粘剂及含有这种胶粘剂的胶带 |
CN103594549A (zh) * | 2012-08-13 | 2014-02-19 | 德莎欧洲公司 | 制造太阳能模块的方法 |
CN106118566A (zh) * | 2015-05-05 | 2016-11-16 | 德莎欧洲公司 | 具有含连续聚合物相的胶粘剂的胶带 |
CN107849412A (zh) * | 2015-08-11 | 2018-03-27 | 德莎欧洲股份公司 | 基于丙烯腈丁二烯橡胶的压敏胶粘剂 |
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WO2006128629A1 (de) | 2006-12-07 |
EP1893709A1 (de) | 2008-03-05 |
JP2008542483A (ja) | 2008-11-27 |
MX2007014573A (es) | 2008-02-05 |
DE102005025056A1 (de) | 2006-12-07 |
KR20080015125A (ko) | 2008-02-18 |
CN101184818B (zh) | 2012-12-26 |
TW200700528A (en) | 2007-01-01 |
US20060269743A1 (en) | 2006-11-30 |
EP1893709B1 (de) | 2012-10-10 |
US7569640B2 (en) | 2009-08-04 |
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