CN1315969C - 丙烯酸压敏粘合剂 - Google Patents
丙烯酸压敏粘合剂 Download PDFInfo
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Abstract
本发明涉及包括下列组分的溶液或混溶性共混物的溶剂型丙烯酸压敏粘合剂和热熔型(或无溶剂)丙烯酸压敏粘合剂:a.至少一种疏水性(甲基)丙烯酸系聚合物,b.具有1,000-20,000的数均分子量和选自聚酯多元醇、丙烯酸多元醇、聚碳酸酯多元醇和聚醚多元醇中的至少一种基本上水不溶性多元醇,c.作为交联剂的至少一种过渡金属配合物,d.任选的一种或多种增粘树脂,g.任选的一种或多种溶剂,h.任选的一种或多种的增塑剂,粘合促进剂,颜料,填料,抗氧化剂和UV稳定剂。该粘合剂使用基本不溶于水和可与在粘合剂组合物中使用的丙烯酸系聚合物混溶的多元醇。
Description
本发明涉及丙烯酸压敏粘合剂组合物。
丙烯酸压敏粘合剂的优点在现有技术中是众所周知的。丙烯酸压敏粘合剂的许多实例描述在Pressure Sensitive AdhesivesTechnology,第1版,1996,Istvan Benedek和Luc J.Heymans中。然而,普通丙烯酸压敏粘合剂(PSA)具有两个主要的缺点。
一个缺点是对低表面能基材的相对低劣的附着力,虽然它们具有对许多高表面能基材的非常良好的附着力。这是因为丙烯酸PSA一般具有较高的表面能和较高的极性。在过去的几年里,低表面能材料比如聚烯烃和泡沫塑料的使用大大增加,而且PSA产品的许多应用要求对低表面能基材的良好附着力。因此,对于不仅对高表面能基材具有良好附着力,而且对低表面能基材具有良好附着力的丙烯酸PSA存在巨大需求。
第二个缺点是相对低的粘性,尤其是具有高剪切阻力的丙烯酸PSA。丙烯酸PSA很难同时具有高粘性和高剪切阻力,因为增高的粘性通常降低了剪切阻力。然而,许多高档应用要求PSA既具有高剪切阻力又具有高粘性。
JP 6-322355公开了含有水溶性聚醚多元醇和水溶性基础聚合物比如携带磺酸盐基团的聚丙烯酸酯类的水溶性或水分散性压敏粘合剂。多元醇在JP 6-322355中的作用是简单用于增塑基础聚合物。此类丙烯酸压敏粘合剂固有地具有非常低劣的耐水性或防潮性,因此不适合于大多数PSA应用。另外,与其它普通丙烯酸压敏粘合剂类似,这些粘合剂具有低粘性和对低表面能基材不具有良好的附着力。
EP 684,295也公开了含有0.75-5份的具有100-1000的分子量的水溶性润湿剂的水分散性PSA组合物。类似地,这些PSA组合物由于水溶性润湿剂而具有非常低劣的耐水性或防潮性,并且还共有其它普通丙烯酸PSA的缺陷。
因此,本发明的目的是克服此类普通丙烯酸压敏粘合剂的上述缺点。
本发明用包括下列组分的溶液或混容性共混物的溶剂型丙烯酸压敏粘合剂和热熔型(或无溶剂)丙烯酸压敏粘合剂达到了该目的:
a.至少一种疏水性(甲基)丙烯酸系聚合物,
b.具有1,000-20,000的数均分子量和选自聚酯多元醇、丙烯酸多元醇、聚碳酸酯多元醇和聚醚多元醇中的至少一种基本上水不溶性多元醇,
c.作为交联剂的至少一种过渡金属配合物,
d.任选的一种或多种增粘树脂,
e.任选的一种或多种溶剂,
f.任选的一种或多种的增塑剂,粘合促进剂,颜料,填料,抗氧化剂和UV稳定剂。
该粘合剂使用基本不溶于水和可与在粘合剂组合物中使用的丙烯酸系聚合物混容的多元醇。
而且,在本发明粘合剂配制料中的多元醇的作用与现有技术的那些大不相同。与EP 684,295或JP 6-322355相反,多元醇在这里不只是增塑基础树脂,而是增进附着力和改进粘合剂的剪切阻力。在US4,140,115中,水溶性的多元醇被分散于粘合剂基质中(即与粘合剂基质不相容),从而降低了附着力。
水溶性多元醇在该发明中不是非常有用的,因为在多元醇和丙烯酸共聚物之间具有低劣的相容性,这使得粘合剂性能变得不理想和减低了防潮性或耐水性。
因此,本发明提供了针对PSA的新方法,它包括将基本上水不溶性多元醇与丙烯酸树脂共混,从而改进对低表面能基材的附着力以及改进其它性能。通过将此类多元醇引入到丙烯酸PSA中,该粘合剂显示了对高表面能基材(例如金属基材)和低表面能基材(例如聚醚聚氨酯泡沫塑料)的改进附着力。通过该方法,还可以配制不仅具有高粘性而且具有高剪切阻力的PSA。
本发明的基础树脂是疏水性的和基本上不溶于水,不象JP6-322355的那些。它们优选是(甲基)丙烯酸烷基酯,其中烷基优选具有1-22个碳原子。适合的(甲基)丙烯酸烷基酯单体包括丙烯酸乙酯,丙烯酸丁酯,丙烯酸2-乙基苄酯,丙烯酸月桂基酯,丙烯酸鲸蜡基酯,丙烯酸硬脂基酯,丙烯酸二十烷基酯和它们的混合物以及相应的甲基丙烯酸酯单体。
(甲基)丙烯酸酯可以以大约50到99wt%的量使用。
在本发明中的多元醇基本上不溶于水,是具有至少两个端部羟基的低聚物,比如聚酯多元醇,丙烯酸多元醇,聚碳酸酯多元醇,聚醚多元醇,和它们的混合物。这些多元醇的有用分子量范围是大约300到大约20,000和优选大约1,000到大约20,000。适合于本发明的商品多元醇的一些实例包括、但不限于羟基终端的聚(氧化烯)(Poly-G20-56,POLY-G 30-56,POLY-G-55-56,POLY-G 30-28,出自ArchChemicals),聚(四氢呋喃二醇)(POLY-THF MW650,POLY-THF 2000和POLY-THF 4500,出自BASF),丙烯酸多元醇(Acryflow P-120,出自Lyondell Chemical),聚四亚甲基醚二醇(Terathane III,出自Dupont),和由己二酸和2,2,4-三甲基-1,3-戊二醇获得的聚酯多元醇(LEXOREZ 1180-35,出自Inolex Chemical)。
多元醇优选以大约5到50wt%的量使用。
本发明的交联剂可以是选自过渡金属配合物比如乙酰丙酮根过渡金属配合物中的单或多价金属离子。它们可以优选以大约0.05到2.0wt%的量使用。
如果使用的话,本发明的增粘树脂可以选自下列组中:
i)松香酸,聚合松香酸,松香酯和它们的混合物;
ii)氢化松香酸,氢化松香酯和它们的混合物;
iii)聚萜烯和萜烯酚醛树脂;
iv)通过苯乙烯,α-甲基苯乙烯,乙烯基甲苯和它们的混合物的反应所生产的芳族树脂;
v)酚醛改性芳族树脂,苯甲酸酯树脂,香豆酮-茚树脂,合成酚树脂,和它们的混合物。
它们可以优选以至多大约0到大约50wt%的量使用。
倘若使用,适合的溶剂可以是脂族酯,比如乙酸乙酯,脂族烃类比如庚烷和己烷,卤化脂族烃类,芳族烃类比如甲苯和二甲苯,脂族醇类比如甲醇,乙醇或异丙醇,脂族酮比如丙酮,和脂族酯类比如乙酸乙酯和它们的混合物。它们可以以大约0到90wt%的量使用。
本发明的粘合剂组合物可以含有任选其量为大约0.1到10.0wt%/每一添加剂的各种添加剂,比如抗氧化剂,UV稳定剂,颜料,填料,增塑剂和粘合促进剂。
(甲基)丙烯酸系聚合物组分理想地是下列组分的反应产物:
i)大约50到99wt%的具有含有大约1到22个碳原子的烷基的至少一种(甲基)丙烯酸酯单体;
ii)0到大约50wt%的选自具有含大约1到22个碳原子的烷基的(甲基)丙烯酸酯单体、乙酸乙烯酯和苯乙烯中的至少一种单体;和
iii)大约0.5到大约20wt%的选自单官能羧酸单体,多官能羧酸单体,单官能羟基单体,多官能羟基单体,丙烯酸氰基烷基酯,丙烯酰胺类,丙烯腈类,例如(甲基)丙烯酸,(甲基)丙烯酰胺,(甲基)丙烯腈,丁二醇单丙烯酸酯和乙烯基吡咯烷酮中的至少一种极性单体。
该配制料的优点包括:
1)具有该多元醇的粘合剂显著增加了对聚醚聚氨酯泡沫塑料(低表面能基材)的附着力,尽管所有配制料具有对钢基材的良好附着力;
2)具有该多元醇的粘合剂显示了在70℃下的增高的剪切阻力,这是由于在多元醇和丙烯酸共聚物之间的H-键合网络;
3)因为该多元醇具有比在溶液中的丙烯酸系聚合物低得多的粘度,所以可以配制具有比通常可获得的粘合剂高50%的固体含量的丙烯酸压敏粘合剂。
用于压敏粘合剂配制料的丙烯酸系聚合物由溶液聚合、乳液聚合或固体聚合来制备。虽然能够使用由乳液聚合获得的丙烯酸系聚合物,但在本发明中优选使用由溶液聚合或固体聚合获得的丙烯酸系聚合物。
丙烯酸系聚合物能够以溶液或固体(或无溶剂)形式使用。当使用丙烯酸系聚合物溶液时,压敏粘合剂配制料的其它组分能够直接混合到聚合物溶液中,以获得均匀的粘合剂溶液。
粘合制品通过使用直接涂布或转移涂布来制备。在直接涂布方法中,通过将粘合剂溶液的涂层施涂于原始基材并除去涂层中的溶剂,以便提供覆盖基材表面的由粘合剂组合物的固体部分组成的粘合层来制备粘合制品。在转移涂布方法中,首先在硅酮剥离纸上涂布粘合剂。在蒸干溶剂之后,粘合涂层由此粘结于原始基材。
当使用丙烯酸固体时,通过使用热熔体加工将粘合剂的其它组分与聚合物混合。粘合制品通过将这种热熔粘合剂施涂于基材上,形成覆盖基材表面的均匀粘合层来制备。
用于测定剥离附着力和剪切的试验方法是在Test Method forPressure-Sensitive Tapes,第13版,2001年8月,Pressure-Sensitive Tape Council,Glenview,III.中描述的那些,该文献在这里引入供参考。
剥离附着力(PSTC-101)
剥离附着力是在特定角度和脱除速率下测定的从试板上去除涂覆的柔性片材所需的力。在实施例中,该力按磅/英寸(lb/in)涂层片材的宽度来表示。粘合剂的涂层被施涂于硅酮剥离纸上。在粘合涂层在烘箱中在大约125℃下干燥大约5分钟之后,将它粘结于Mylar薄膜。从涂覆的Mylar薄膜上切取1×8英寸的试样。在74和50%相对湿度下调节过夜之后,揭下剥离纸并将试样粘结于清洁的不锈钢试板的水平面。该粘结物然后用自动滚筒辊压。在将该粘结物调节达特定停留时间之后,该粘结物在剥离试验仪中在180°角度下以12英寸/分钟的恒定剥离速度剥离。结果作为按lb/in计的平均负荷报道。
剪切阻力(PSTC-107)
剪切阻力是粘合剂的内聚力或内部强度的衡量标准。它是从标准平坦表面上以与附加了一定压力的该表面平行的方向拉动粘合带所需的力的量为基础。它根据在恒定负荷下从不锈钢试板上拉动标准面积的粘合剂涂覆的片材所需的时间来测量。
这些试验用施加于不锈钢板的粘合剂涂层带进行,其中使得各带的1×1英寸部分与该板牢固地接触,该带的一个端部自由。附有涂层带的板固定在支架上,使得该板形成178°的角度,然后在伸长的胶带自由端悬挂恒重。
环结粘性测量(PSTC-16)
环结粘性通过沿纵向切取Mylar涂覆的层压件的5×1英寸样品使用环结粘性试验仪来测定。在74和50%相对湿度下调理一整夜之后,通过用胶带将端部粘贴在一起将该层压件合拢成环结。然后将环结固定在环粘性试验仪上,以及将不锈钢板夹紧在试验仪的底座上,当开始试验时,使该环结与不锈钢板接触,然后拉动。从钢板上拉动所使用的负荷作为环结粘性(lb/in2)记录。
下列丙烯酸系聚合物、增粘剂和多元醇用来举例说明本发明:
丙烯酸聚合物A是具有40wt%的聚合物固体含量和大约0.1wt%的交联剂(乙酰丙酮酸铝)含量的丙烯酸共聚物(54wt%丙烯酸2-乙基己基酯,31wt%丙烯酸甲酯,10wt%丙烯酸异辛酯,5wt%丙烯酸)。
丙烯酸聚合物B是具有45wt%的聚合物固体含量和大约0.2wt%的交联剂(乙酰丙酮酸铝)含量的丙烯酸共聚物(57wt%丙烯酸2-乙基己基酯,31wt%丙烯酸乙酯,7wt%丙烯酸,3wt%乙烯基吡咯烷酮)。
丙烯酸聚合物C是具有35wt%的聚合物固体含量的丙烯酸共聚物(73wt%丙烯酸2-乙基己基酯,20wt%丙烯酸甲酯,7wt%丙烯酸)。
增粘剂A是具有75℃的软化点的苯乙烯和α-甲基苯乙烯的苯酚改性共聚物(Sylvares 520,出自Arizona Chemicals)。
增粘剂B是具有85℃的软化点的由苯乙烯型共聚单体聚合的树脂(Regalrez 1085,出自Eastman Chemicals)。
多元醇A是具有大约2000的分子量的羟基终端的聚(氧化烯)多元醇(Poly G 20-56,出自Arch Chemicals)。
多元醇B是具有大约2000的分子量的聚四氢呋喃多元醇(POLYTHF 2000,出自BASF)。
多元醇C是具有大约3500的分子量的聚四亚甲基醚二醇(TERTHANE III,出自Dupont)。
本发明的粘合剂组合物可以任选进一步包括总量低于20wt%的本领域已知的添加剂,例如增塑剂,粘合促进剂,颜料,填料,抗氧化剂和UV稳定剂等。
以下实施例仅举例说明,决不用来限制本发明的范围。
实施例I
制备根据本发明的压敏粘合剂(样品I),并与普通丙烯酸压敏粘合剂(购自UCB Chemicals,Smyrna,GA30080的Solucryl 303)比较。
样品I的组成
丙烯酸聚合物A 53wt%
增粘剂A 36wt%
多元醇A 11wt%
在Mylar薄膜上的3.5密尔干燥涂覆的粘合剂的附着力试验结果如下所示:
样品I | Solucryl 303* | |
在不锈钢上的180°剥离(20min停留时间) | 7.2lb/in | 4.5lb/in |
在高密度聚乙烯上的180°剥离(20min停留时间) | 2.8lb/in | 0.6lb/in |
样品I显示了比Solucryl 303更好的对高表面能基材(不锈钢)和低表面能基材(聚乙烯)的附着力。
实施例II
含有聚醚多元醇的压敏粘合剂配制料与没有聚醚多元醇的类似配制料比较。
样品II-A | 样品II-B | |
丙烯酸聚合物A | 53wt% | 53wt% |
丙烯酸聚合物B | 11wt% | |
增粘剂A | 33.5wt% | 33.5wt% |
增粘剂B | 2.5wt% | 2.5wt% |
多元醇A | 11wt% |
以下比较了样品II-A和样品II-B的附着力性能。获得了在Mylar薄膜上的干燥粘合剂的3.5密尔厚涂层的试验结果。
样品II-A | 样品II-B | |
在不锈钢上的180°剥离(20min停留时间) | 7.2lb/in | 8.5lb/in |
剪切阻力(2psi,70℃) | >72小时 | ~8小时 |
在不锈钢上的环结粘性 | 7.0lb/in2 | 8.0lb/in2 |
对聚醚聚氨酯泡沫塑料的附着力 | 良好 | 低劣 |
本发明的样品II-A显示了明显更好的70℃剪切阻力。尤其,虽然不含多元醇的配制料(样品II-B)具有良好的对不锈钢的附着力,但对聚醚聚氨酯泡沫塑料的附着力是低劣的和粘合剂容易从泡沫塑料上除去。另一方面,样品II-A具有非常强的对泡沫塑料的附着力和在不破坏泡沫塑料表面结构的情况下不能从泡沫塑料上去除。
实施例III
下表示出了分别含有不同多元醇的三种压敏粘合剂配制料。
样品III-A | 样品III-B | 样品III-C | |
丙烯酸聚合物B | 50 | 50 | 50 |
增粘剂A | 30 | 30 | 30 |
多元醇A | 20 | ||
多元醇B | 20 | ||
多元醇C | 20 |
以上三种配制料的附着力性能用在Mylar薄膜上的干燥粘合剂的~2密尔厚涂层测定。
样品III-A | 样品III-B | 样品III-C | Solucryl328* | |
在不锈钢上的180°剥离(20min停留时间) | 2.1lb/in | 3.4lb/in | 4.0lb/in | 2.0lb/in |
在高密度聚乙烯上的180°剥离(20min停留时间) | 1.1lb/in | 1.5lb/in | 1.7lb/in | 0.5lb/in |
在聚丙烯上的180°剥离(20min停留时间) | 1.2lb/in | 1.5lb/in | 1.7lb/in | 0.6lb/in |
(*UCB Chemical,Smyrna,GA 30080)
含有多元醇的所有三种配制料具有更好的附着力,尤其对于低表面能基材,比如聚乙烯和聚丙烯。
Claims (9)
1、包括下列组分的溶液或混容性共混物的丙烯酸压敏粘合剂组合物:
a.至少一种疏水性(甲基)丙烯酸系聚合物,
b.具有1,000-20,000的数均分子量和选自聚酯多元醇、丙烯酸系多元醇、聚碳酸酯多元醇和聚醚多元醇中的至少一种基本上水不溶性多元醇,
c.作为交联剂的至少一种过渡金属或铝的配合物,
d.任选的一种或多种增粘树脂,
e.任选的一种或多种溶剂,
f.任选的一种或多种的增塑剂、粘合促进剂、颜料、填料、抗氧化剂和UV稳定剂。
2、根据权利要求1的丙烯酸压敏粘合剂组合物,其中:
a.以30到95wt%的量存在,
b.以5到50wt%的量存在,
c.以0.05到2.0wt%的量存在,
d.以至多50wt%的量存在,
e.以至多90wt%的量存在,和
f.以10wt%的量存在,
条件是组合物各组分之和为100%。
3、根据权利要求1的丙烯酸压敏粘合剂组合物,其中(甲基)丙烯酸系聚合物包括下列组分的反应产物:
i)50到99wt%的具有含有1到22个碳原子的烷基的至少一种(甲基)丙烯酸烷基酯单体;
ii)0到50wt%的选自具有含1到22个碳原子的烷基的(甲基)丙烯酸烷基酯单体、乙酸乙烯酯和苯乙烯中的至少一种其它单体;和
iii)0.5到20wt%的选自单官能羧酸单体、多官能羧酸单体、单官能羟基单体、多官能羟基单体、丙烯酸氰基烷基酯、丙烯酰胺类、丙烯腈类、丁二醇单丙烯酸酯和乙烯基吡咯烷酮中的至少一种极性单体,
条件是组合物各组分之和为100%。
4、根据权利要求1的丙烯酸压敏粘合剂组合物,其中交联剂(c)选自乙酰丙酮根过渡金属或铝的配合物。
5、根据权利要求1的丙烯酸压敏粘合剂组合物,其中增粘树脂d.选自:
i)松香酸,聚合松香酸,松香酯和它们的混合物;
ii)氢化松香酸,氢化松香酯和它们的混合物;
iii)聚萜烯和萜烯酚醛树脂;
iv)由苯乙烯,α-甲基苯乙烯,乙烯基甲苯和它们的混合物的反应产物组成的芳族树脂;
v)酚醛改性芳族树脂,苯甲酸酯树脂,香豆酮-茚树脂、合成酚树脂、和它们的混合物。
6、根据权利要求1的丙烯酸压敏粘合剂组合物,其中溶剂(e)选自脂族酯,脂族烃,卤化脂族烃,芳族烃,脂族醇,脂族酮和它们的混合物。
7、根据权利要求6的丙烯酸压敏粘合剂组合物,其中脂族烃是庚烷或己烷,芳族烃是甲苯或二甲苯,脂族醇是甲醇,乙醇或异丙醇,脂族酮是丙酮和脂族酯是乙酸乙酯。
8、根据权利要求1的丙烯酸压敏粘合剂组合物,另外含有0.1到2.0wt%的抗氧化剂或UV稳定剂。
9、通过用权利要求1的丙烯酸压敏粘合剂组合物涂布基材片所形成的粘合剂涂覆的片材。
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- 2003-07-09 MX MXPA05001109A patent/MXPA05001109A/es unknown
- 2003-07-09 CA CA002493998A patent/CA2493998A1/en not_active Abandoned
- 2003-07-09 KR KR1020057001779A patent/KR20050026087A/ko not_active Application Discontinuation
- 2003-07-09 DE DE60329682T patent/DE60329682D1/de not_active Expired - Lifetime
- 2003-07-09 EP EP03766137A patent/EP1527146B1/en not_active Expired - Lifetime
- 2003-07-09 ES ES03766137T patent/ES2333217T3/es not_active Expired - Lifetime
- 2003-07-29 TW TW092120643A patent/TW200403319A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5433892A (en) * | 1990-12-13 | 1995-07-18 | Lohmann Gmbh & Co. Kg | Electrically conductive transparent pressure-sensitive adhesive films; process for their production; and their use in the production of miomedical electrodes |
CN1129230A (zh) * | 1994-10-11 | 1996-08-21 | 美国Basf公司 | 改良的胶乳组合物 |
CN1282360A (zh) * | 1997-11-20 | 2001-01-31 | 阿什兰公司 | 压敏阻燃型粘合剂 |
CN1284106A (zh) * | 1998-01-27 | 2001-02-14 | 美国3M公司 | 不发白的乳液压敏粘合剂 |
Also Published As
Publication number | Publication date |
---|---|
ES2333217T3 (es) | 2010-02-18 |
CA2493998A1 (en) | 2004-02-12 |
EP1527146A1 (en) | 2005-05-04 |
AU2003250919A1 (en) | 2004-02-23 |
US7465493B2 (en) | 2008-12-16 |
JP2005534754A (ja) | 2005-11-17 |
US20060099413A1 (en) | 2006-05-11 |
EP1527146B1 (en) | 2009-10-14 |
DE60329682D1 (de) | 2009-11-26 |
MXPA05001109A (es) | 2005-09-08 |
KR20050026087A (ko) | 2005-03-14 |
WO2004013246A1 (en) | 2004-02-12 |
TW200403319A (en) | 2004-03-01 |
ATE445681T1 (de) | 2009-10-15 |
CN1675329A (zh) | 2005-09-28 |
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