CN102471646B - 表面保护膜 - Google Patents
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Abstract
本发明提供一种对高凹凸的被粘物的粘接特性、经时粘接稳定性、透明性、复卷性和耐热性优异的表面保护膜。该表面保护膜由表面层(A)和粘接层(X)的至少2层构成,其特征在于,表面层(A)由聚烯烃树脂构成,粘接层(X)由下述组合物形成,该组合物包含20~99.8重量%的重均分子量(Mw)在10,000~300,000的范围内的苯乙烯类弹性体、和0.2~80重量%的重均分子量(Mw)在200~9,000的范围内的苯乙烯类低聚物。
Description
技术领域
本发明涉及在光学制品、建材、汽车部件等中所使用的表面保护膜。详细而言,涉及粘接特性、特别是对表面凹凸大的被粘物的粘接性和粘接力的经时稳定性优异,另外,耐热性优异,对被粘物等的污染少,而且从卷筒状抽出时的抽出性容易的表面保护膜。
背景技术
表面保护膜主要粘附在建材用或光学用途用的树脂制品、金属制品、玻璃制品等被粘物上使用,发挥在这些制品的输送、保管和加工时防止刮伤或异物混入的作用。这些表面保护膜一般由没有粘接性的表面层和用于与上述被粘物粘接的粘接层构成。表面层通常由聚乙烯或聚丙烯等聚烯烃、或者对苯二甲酸乙二醇酯等聚酯、聚氯乙烯等乙烯基聚合物形成。
近年来,进行着在液晶屏、等离子显示器(PDP)或背投式屏等中使用的部件的所谓的光学制品的开发。对于用于保护这些光学制品的表面保护膜,不仅期望防止刮伤和异物混入,而且期望在粘贴了表面保护膜的状态下能够实现制品检查这样的透明性、和即使在高温状态下粘贴或经过热处理工序也表现适度的粘接力等的特性。
另外,关于光学制品,有很多例如棱镜板这样的表面凹凸大的部件,期望有对于这些高凹凸部件也能够表现适度的粘接力和即使随着时间的经过也能够表现稳定的粘接力的保护膜。
另一方面,在建材或汽车部件用途中使用表面保护膜时,有在粘贴了表面保护膜的状态下进行热成形的情况,因而要求很高的耐热性。
另外,对于粘接力比较高的表面保护膜而言,由于难以从卷筒状的制品中抽出,因此以粘接层上贴合了离型膜的状态制成卷筒状,在向被粘物粘贴时剥下该离型膜而使用。如果采用这样的工序,则产生大量的废弃物,所以需要一种即使没有离型膜也能够容易地从卷筒中抽出的表面保护膜。
在日本特开2006-116769号公报中公开了以聚乙烯成分为主体的表面保护膜。然而,在该公报的方法中,虽然对一部分用途部件可以适用,但粘接力低,另外透明性也不够,在被粘物的用途方面存在限制。
在日本特开2007-126512号公报中公开了包括含有作为异丁烯类嵌段共聚物的苯乙烯类弹性体和增粘树脂的粘接层的表面保护膜。然而,在该公报的方法中,在高凹凸的被粘物上贴合时,粘接力的经时稳定性不够,而期望进一步的改良。
现有技术文献
专利文献
专利文献1:日本特开2006-116769号公报
专利文献2:日本特开2007-126512号公报
发明内容
发明所要解决的课题
本发明在于提供一种作为在光学制品、建材制品或汽车部件的保管、输送、加工、检查时用于保护的表面保护膜所要求的特性,特别是对表面凹凸大的被粘物的粘接特性、透明性、耐热性和从卷筒的抽出性优异的表面保护膜。
用于解决课题的方法
本发明的发明人鉴于上述课题而进行了深入的研究,结果发现,通过具有由某种特定的树脂组合物构成的表面层的表面保护膜能够解决上述课题,从而完成了本发明。
即,本发明是一种表面保护膜,其由表面层(A)和粘接层(X)的至少2层构成,其特征在于,表面层(A)由聚烯烃树脂构成,粘接层(X)由下述组合物形成,该组合物包含20~99.8重量%的重均分子量(Mw)在10,000~300,000的范围内的苯乙烯类弹性体和0.2~80重量%的重均分子量(Mw)在200~9,000的范围内且软化点在60~160℃的范围内的苯乙烯类低聚物(苯乙烯类弹性体和苯乙烯类低聚物的合计为100重量%。)。
另外,本发明是一种表面保护膜,其特征在于,上述粘接层(X)由下述组合物形成,该组合物相对于包含上述苯乙烯类弹性体和苯乙烯类低聚物的组合物100重量份,含有0.5~1000重量份结晶性聚烯烃和/或聚烯烃类弹性体。
此外,本发明是一种表面保护膜,其为将上述表面层(A)和粘接层(X)的至少2层从T-模头挤出成形而得到的多层膜。
发明的效果
本发明的表面保护膜在粘接特性、特别是对高凹凸被粘物的粘接特性和经时稳定性、透明性、复卷力和耐热性优异,作为光学用途、建材用途、汽车部件用途的保护膜而在产业上的利用价值极高。
具体实施方式
下面,对本发明进行详细说明。
本发明的表面保护膜由表面层(A)和粘接层(X)的至少2层、或根据需要由表面层(A)、基材层(B)和粘接层(X)的至少3层构成。在这里,将粘接层(X)设为最内层时,表面层(A)位于最外层,将膜制成卷筒状时,表面层(A)与粘接层(X)接触。
表面层(A)由聚烯烃树脂构成。
作为聚烯烃树脂,能够列举聚丙烯和聚乙烯等公知的聚烯烃树脂。作为聚丙烯,能够列举均聚丙烯、无规聚丙烯、嵌段聚丙烯,作为聚乙烯,能够列举高压法低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯。在这些聚烯烃树脂中,从复卷性的观点出发,优选利用高压法低密度聚乙烯,从透明性、耐热性的观点出发,优选利用均聚丙烯或嵌段聚丙烯。
在形成上述表面层(A)的组合物中,在无损于作为本发明的表面保护膜的特性的范围,还可以添加抗静电剂、脱模剂、抗氧化剂、耐候剂、结晶成核剂等各种添加剂、其他的聚烯烃树脂、蜡、聚酯、聚酰胺、弹性体等树脂改性剂。
本发明的表面保护膜的粘接层(X)由下述组合物形成,该组合物包含20~99.8重量%的重均分子量(Mw)在10,000~300,000的范围内的苯乙烯类弹性体、和0.2~80重量%的重均分子量(Mw)在200~9,000的范围内且软化点在60~160℃的范围内的苯乙烯类低聚物(苯乙烯类弹性体和苯乙烯类低聚物的合计为100重量%。)。
作为苯乙烯类弹性体,能够使用具有聚苯乙烯相作为硬链段的公知的苯乙烯类弹性体。具体而言,能够列举苯乙烯-丁二烯共聚物(SBR)、苯乙烯-异戊二烯-苯乙烯共聚物(SIS)、苯乙烯-丁二烯-苯乙烯共聚物(SBS)、苯乙烯-乙烯基异戊二烯-苯乙烯聚合物等苯乙烯与二烯的共聚物以及它们的氢化物(例如乙-烯乙烯-丁二烯-苯乙烯共聚物(SEBS)等)或苯乙烯-异丁烯-苯乙烯三嵌段共聚物(SIBS)、苯乙烯-异丁烯二嵌段共聚物(SIB)。优选为苯乙烯-异丁烯-苯乙烯三嵌段共聚物(SIBS)、苯乙烯-异丁烯二嵌段共聚物(SIB)。
上述苯乙烯类弹性体由凝胶渗透色谱法(GPC)测得的重均分子量(以下简记为Mw)在10,000~300,000的范围内,优选在15,000~250,000的范围内,更优选在20,000~200,000的范围内。若Mw小于10,000或大于300,000,则保护膜的生产性差,故而不优选。
作为在粘接层(X)中使用的苯乙烯类低聚物,是由GPC测得的重均分子量(Mw)在200~9,000的范围内,且由JIS K2207测得的软化点在60~160℃的范围内的苯乙烯类低聚物。优选Mw在300~7,000且软化点在70~150℃的范围内,更优选Mw在500~5,000且软化点在80~140℃的范围内。
作为上述苯乙烯类低聚物,只要是满足上述分子量和软化点的苯乙烯类低聚物就没有特别限制,但具体而言,是由苯乙烯或α-甲基苯乙烯等至少一种的芳香族类单体构成(共)聚合物。详细而言,能够列举例如苯乙烯均聚物、α-甲基苯乙烯均聚物、苯乙烯-α-甲基苯乙烯共聚物、苯乙烯类单体-脂肪族类单体共聚物、α-甲基苯乙烯-脂肪族类单体共聚物、苯乙烯类单体-α-甲基苯乙烯-脂肪族类单体共聚物。
本发明的保护膜中的粘接层(X)由包含20~99.8重量%的上述苯乙烯类弹性体和0.2~80重量%的苯乙烯类低聚物(苯乙烯类弹性体和苯乙烯类低聚物的合计为100重量%。)的组合物形成。优选由包含30~99.5重量%的苯乙烯类弹性体和0.5~70重量%的苯乙烯类低聚物的组成物形成,更优选由包含50~98重量%的苯乙烯类弹性体和2~50重量%的苯乙烯类低聚物的组成物形成,更加优选由包含65~95重量%的苯乙烯类弹性体和3~15重量%的苯乙烯类低聚物的组合物形成(每种情况下苯乙烯类弹性体和苯乙烯类低聚物的合计都为100重量%。)。
本发明的保护膜中的粘接层(X)中,以粘接力、经时粘接力的控制和复卷力的控制为目的,也能够在上述组合物中添加结晶性聚烯烃和/或烯烃类弹性体。
作为结晶性聚烯烃,只要是熔点超过110℃的公知的聚烯烃就能够没有限制地使用,但具体而言,能够列举例如丙烯均聚物、丙烯-乙烯共聚物、丙烯-乙烯-1-丁烯共聚物、1-丁烯均聚物、1-丁烯-乙烯共聚物、1-丁烯-丙烯共聚物、4-甲基戊烯-1均聚物、4-甲基戊烯-1丙烯共聚物、4-甲基戊烯-1-1-丁烯共聚物、4-甲基戊烯-1-丙烯-1-丁烯共聚物、丙烯-1-丁烯共聚物、乙烯均聚物、乙烯-α-烯烃共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物等。
作为烯烃类弹性体,是熔点为110℃以下、优选熔点为100℃以下、更优选熔点为80℃以下或观测不到熔点的碳原子数2~20的α-烯烃聚合物或共聚物、或者乙烯和不饱和羧酸或不饱和羧酸酯的共聚物。具体而言,能够列举乙烯-丙烯共聚物、乙烯-1-丁烯共聚物、乙烯-1-己烯共聚物、乙烯-4-甲基戊烯-1共聚物、乙烯-1-辛烯共聚物、丙烯均聚物、丙烯-乙烯共聚物、丙烯-乙烯-1-丁烯共聚物、1-丁烯均聚物、1-丁烯-乙烯共聚物、1-丁烯-丙烯共聚物、4-甲基戊烯-1均聚物、4-甲基戊烯-1-丙烯共聚物、4-甲基戊烯-1-1-丁烯共聚物、4-甲基戊烯-1-丙烯-1-丁烯共聚物、丙烯-1-丁烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物等。从粘接力的经时稳定性的观点出发,优选为丙烯均聚物、丙烯-乙烯共聚物、丙烯-1-丁烯共聚物。更优选为丙烯-乙烯-1-丁烯共聚物。
作为将上述结晶性聚烯烃和/或烯烃类弹性体作为本发明的保护膜的粘接层(X)的一种成分使用时的含量,相对于上述包含苯乙烯类弹性体和苯乙烯类低聚物的组合物100重量份,为0.5~1000重量份,优选为1~700重量份,更优选为5~500重量份,更加优选为5~100重量份。通过添加结晶性聚烯烃和/或烯烃类弹性体,能够表现所期望的粘接力,还能够表现适于各种被粘物的粘接特性,故而优选。
通过添加了包含苯乙烯类弹性体和苯乙烯类低聚物的组合物以及根据需要的结晶性聚烯烃和/或烯烃类弹性体的组合物,能够形成本发明的表面保护膜中的粘接层(X)。另外,在本发明中,在无损于本发明的特性的范围,还可以含有酸改性聚烯烃、聚酯、聚酰胺等树脂改性剂、抗静电剂、结晶成核剂、抗氧化剂等各种添加剂。
在本发明中,在表面层(A)和粘接层(X)之间还可以设置至少1层的基材层(B)。以控制膜的机械强度和透明性为目的,另外,在表面层(A)与粘接层(X)的粘接力不足时,作为中间层可以使用聚烯烃树脂、粘接性树脂或者粘接剂。
作为基材层没有特别限制,但一般能够使用熔点为100℃以上的聚丙烯或聚乙烯等结晶性聚烯烃、或者聚酯、聚酰胺、聚烯烃类弹性体等。在将基材层作为粘接层使用时,可以使用改性聚烯烃、或者聚烯烃类弹性体、苯乙烯类弹性体、聚酯弹性体等。在这些之中,从生产性和透明性的观点出发,优选使用聚丙烯或聚烯烃弹性体作为中间层。
上述包含苯乙烯类弹性体和苯乙烯类低聚物的组合物以及根据需要的结晶性聚烯烃和/或烯烃类弹性体、以及根据需要的树脂改性剂或添加剂,能够通过与上述表面层(A)、根据需要的基材层(B)叠层,形成本发明的表面保护膜。
关于叠层表面层(A)和粘接层(X)、根据需要叠层基材层(B)的方法没有特别限制,但可以列举在预先由T-模头成形或吹塑成形所得到的表面层膜上,由挤出层压、挤出涂布等公知的叠层法进行叠层的方法;或将基材层和粘接层独立成膜后,将各个膜通过干式层压进行叠层的方法等,从生产性的观点出发,优选将表面层、基材层、粘接层的各成分供给多层的挤出机进行成形的共挤出成形。
作为本发明的表面保护膜中的表面层(A)的厚度,为0.1~100微米(μm),优选为0.3~50微米(μm),更优选为0.5~30微米(μm)、更加优选为1~20微米(μm)。作为粘接层(X)的厚度,为0.1~50微米(μm),优选为0.3~40微米(μm),更优选为0.5~30微米(μm)。
作为本发明的表面保护膜的厚度,为1~300微米(μm),优选为2~200微米(μm),更优选为3~100微米(μm)。
通过使用上述优选方式的表面层(A)、粘接层(X)和根据需要的基材层(B),可以得到粘接特性,特别是对于高凹凸的被粘物表现优异的粘接力,而且透明性优异的表面保护膜,特别是对于建材用途、光学用途能够很好地利用。
实施例
以下,通过实施例更加详细地说明本发明,但本发明并不限定于这些实施例。
[评价法]
粘接力(丙烯酸板):
将丙烯酸板切断为宽50毫米(mm)、长125毫米(mm),在该试验板上使用2kg的橡胶辊进行粘贴。然后,测定以300mm/分钟的速度剥离(180度剥离)时的剥离力,将每50毫米(mm)宽度的剥离力作为粘接力(N/50mm)。
粘接力(凹凸板):
在日新制钢株式会社制不锈钢HL精加工#180上粘贴保护膜,测定以300mm/分钟的速度剥离(180度剥离)时的剥离力,将每50毫米(mm)宽度的剥离力作为粘接力(N/50mm)。
复卷力:
使用卷筒状样品,测定以300mm/分钟的速度从卷筒拉剥时的剥离力(N/50mm),作为复卷力。
熔体流率(MFR):
以ASTM D1238为基准,在负荷2.16千克(kg)、温度230℃进行测定。
[实施例1]
用于表面层、基材层和粘接层,在兼具的单螺杆挤出机的模宽500毫米(mm)的三种三层T-模头成形机中供给以下树脂组合物,得到表面层厚度10微米(μm)、粘接层厚度10微米(μm)、基材层厚度30微米(μm)、总厚度50微米(μm)的表面保护膜。所得到的膜的评价结果表示在表1中。
表面层:
LD-1:高压法低密度聚乙烯
(密度0.920g/cm3,MFR(190℃)6g/10分钟)
100重量%
基材层:
PP-1:均聚丙烯
(熔点160℃,MFR(230℃)7g/10分钟)
90重量%
EL-1:乙烯-1-丁烯共聚物
(商品名:TAFMER,商标名:A-4085S,MFR=3.6g/10分钟,三井化学株式会社制) 10重量%
粘接层:
PEBR:丙烯-乙烯-1-丁烯共聚物
(乙烯含量13摩尔%,1-丁烯含量19摩尔%,观测不到熔点,MFR=7g/10分钟) 10重量%
SIBS:苯乙烯-异丁烯-苯乙烯三嵌段共聚物
(商品名:SIBSTAR,商标名:062T,MFR=8.0g/10分钟,Kaneka公司制) 70重量%
SL-1:苯乙烯类单体-脂肪族类单体共聚物
(商品名:FTR,商标名:FTR6125,Mw=1950,软化点125℃,三井化学株式会社制) 10重量%
PP-2:均聚丙烯
(商标名:F107BV,熔点=160℃,MFR=7g/10分钟,PrimePolymer公司制)10重量%
[实施例2、3和比较例1、2]
除了将各种层的树脂组成设为表1记载的树脂组成以外,与实施例1同样操作得到表面保护膜。所得到的膜的评价结果表示在表1中。
[表1]
*将SL-1+SIBS的合计作为100重量份,表示相对于此的重量份。
Claims (4)
1.一种表面保护膜,其特征在于:
其由表面层(A)和粘接层(X)的至少2层构成,表面层(A)由聚烯烃树脂构成,粘接层(X)由下述组合物形成,该组合物相对于包含50~98重量%的重均分子量(Mw)在10,000~300,000的范围内的苯乙烯类弹性体、和2~50重量%的重均分子量(Mw)在200~9,000的范围内的苯乙烯类低聚物的组合物100重量份,含有5~100重量份的结晶性聚烯烃和/或聚烯烃类弹性体,其中,所述苯乙烯类弹性体是苯乙烯-异丁烯-苯乙烯三嵌段共聚物(SIBS)和/或苯乙烯-异丁烯二嵌段共聚物(SIB)。
2.如权利要求1所述的表面保护膜,其特征在于:
苯乙烯类低聚物是苯乙烯类单体-脂肪族单体共聚物。
3.如权利要求1所述的表面保护膜,其特征在于:
聚烯烃类弹性体是丙烯-乙烯-1-丁烯共聚物。
4.如权利要求1~3中任一项所述的表面保护膜,其特征在于:
其为将表面层(A)和粘接层(X)的至少2层从T-模头挤出成形而得到的多层膜。
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