CN101595177A - 粘合剂及使用该粘合剂的层合体 - Google Patents
粘合剂及使用该粘合剂的层合体 Download PDFInfo
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- CN101595177A CN101595177A CNA2008800036487A CN200880003648A CN101595177A CN 101595177 A CN101595177 A CN 101595177A CN A2008800036487 A CNA2008800036487 A CN A2008800036487A CN 200880003648 A CN200880003648 A CN 200880003648A CN 101595177 A CN101595177 A CN 101595177A
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- ethylene
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Abstract
本发明的目的在于提供一种粘合剂以及使用该粘合剂的层合体,所述粘合剂为与极性材料的粘合性优异,同时高速流延膜成型或拉伸成型、挤出涂布成型后的粘合性特别优异,耐白化性也优异的聚丙烯类粘合剂。本发明涉及一种粘合性树脂组合物,是含有聚丙烯成分(A)、乙烯·丙烯·α-烯烃共聚物成分(B)、乙烯·α-烯烃共聚物成分(C)及不饱和羧酸及/或其衍生物(D)的、经接枝加成得到的树脂组合物,其特征在于,成分(A)、(B)及(C)的总和100质量份中,成分(A)为5~80质量份,成分(B)为5~70质量份,成分(C)为1~40质量份,正癸烷可溶成分的乙烯/丙烯/α-烯烃的比为5~95/5~95/1~50摩尔%,并且接枝率为0.01~5wt%。
Description
技术领域
本发明涉及一种新型粘合剂以及使用该粘合剂的层合体。更详细而言,本发明涉及一种粘合剂以及使用该粘合剂的层合体,所述粘合剂为与极性材料的粘合性优异,高速流延膜成型或拉伸成型、挤出涂布成型后的粘合性特别优异,耐白化性也优异的聚丙烯类粘合剂。
背景技术
聚丙烯一直被广泛用作刚性、耐热性、透明性等优异的热塑性成型材料。该聚丙烯为非极性材料,因此缺乏与例如乙烯·乙烯醇共聚物等极性材料的粘合性,为了改良粘合性,用不饱和羧酸或其衍生物将聚丙烯改性的技术广为人知。另外,由于聚丙烯柔软性差,所以用作粘合剂时通常在聚丙烯中配合软质橡胶成分。如上所述在聚丙烯中配合软质橡胶成分时,可以得到改善了粘合性的聚丙烯类粘合剂(例如专利文献1及专利文献2),但另一方面对于用高速流延膜成型或拉伸成型、挤出涂布成型之类的成型法得到的层合体,专利文献1、2中得到的粘合剂的粘合力不充分,期待进一步提高粘合力。另外,由于专利文献1、2中记载的软质橡胶成分在深拉深加工之类二次加工时引起白化,所以也要求改良耐白化性。
专利文献1:特开平9-111069号公报
专利文献2:特开平4-300933号公报。
发明内容
本发明的目的在于提供一种粘合剂以及使用该粘合剂的层合体,所述粘合剂为与极性材料的粘合性优异,同时高速流延膜成型或拉伸成型、挤出涂布成型后的粘合性特别优异,耐白化性也优异的聚丙烯类粘合剂。
本发明人等为了解决上述课题,经过潜心研究,结果完成了本发明。即,本发明为一种粘合性树脂组合物,是含有聚丙烯成分(A)、乙烯·丙烯·α-烯烃共聚物成分(B)、乙烯·α-烯烃共聚物成分(C)及不饱和羧酸及/或其衍生物(D)的、经接枝加成得到的树脂组合物,其特征在于,在成分(A)、(B)及(C)的总和100质量份中,成分(A)为5~80质量份,成分(B)为5~70质量份,成分(C)为1~40质量份,正癸烷可溶成分的乙烯/丙烯/α-烯烃的比为5~95/5~95/1~50摩尔%,并且接枝率为0.01~5wt%。另外,本发明为至少含有一层粘合剂层的层合体,所述粘合剂层含有该粘合性树脂组合物。
利用本发明的粘合性树脂组合物,可以得到与极性材料牢固地粘合的层合体,同时也可以得到即使在高速流延膜成型或拉伸成型、挤出涂布成型中粘合性也优异的层合体。另外,可以得到深拉深等二次加工后也无白化的层合体。
具体实施方式
下面更详细地说明本发明。
本发明的聚丙烯类粘合剂为含有聚丙烯成分(A)、乙烯·丙烯·α-烯烃共聚物成分(B)、乙烯·α-烯烃共聚物成分(C)及不饱和羧酸及/或其衍生物(D)的接枝加成得到的树脂组合物,其特征在于,在成分(A)、(B)及(C)的总和100质量份中,成分(A)为5~80质量份,成分(B)为5~70质量份,成分(C)为1~40质量份,正癸烷可溶成分的乙烯/丙烯/α-烯烃的比为5~95/5~95/1~50摩尔%,并且接枝率为0.01~5wt%。
下面说明各成分。
(A)聚丙烯
本发明中使用的聚丙烯成分(A)为丙烯的均聚物及/或丙烯·α-烯烃共聚物。
作为α-烯烃没有限定,优选举出碳原子数为2的乙烯及/或碳原子数为4~20的α-烯烃,上述α-烯烃可以单独使用1种,也可以使用2种以上。作为本发明中优选的α-烯烃,是碳原子数为2的乙烯或碳原子数为4~10的α-烯烃,其中可以特别优选使用碳原子数为2的乙烯或碳原子数为4~8的α-烯烃。此处,丙烯·α-烯烃共聚物中,由丙烯衍生的结构单元的含量至少为50摩尔%以上、小于100%。
聚丙烯成分(A)的特性粘数[η]在0.1~10dl/g的范围,在上述范围时可以得到成型性和机械强度优异的粘合剂。
作为聚丙烯(A)的制备方法,没有特别限定,可以采用使用齐格勒-纳塔催化剂、金属茂类催化剂等公知的催化剂的公知方法进行制备。另外,可以优选使用结晶性聚合物,使用共聚物时可以为无规共聚物,也可以为嵌段共聚物。并且,只要满足成型性、具有能够耐受在形成成型体时的使用的强度即可,对立规性、分子量也没有特别限定。还可以直接利用市售的树脂。
本发明中优选使用的聚丙烯(A)为均聚聚丙烯(homopolypropylene)或丙烯·α烯烃无规共聚物。另外,也可以混合使用几种不同的全同聚丙烯。进而,可以是接枝有少量马来酸酐等的聚丙烯,另外,也可以是接枝少量马来酸酐等后,进一步用肼、碳二亚胺等修饰接枝单体得到的聚丙烯。
(B)乙烯·丙烯·α-烯烃共聚物
本发明中的乙烯·丙烯·α-烯烃共聚物(B)用下述(i)~(ii)规定。(i)含有45~90摩尔%丙烯成分,10~25摩尔%乙烯成分,1~30摩尔%来自碳原子数为4~20的α-烯烃的成分单元,(ii)在135℃萘烷中的特性粘数[η]在0.1~10dl/g的范围。作为α-烯烃可以较优选地使用碳原子数为4~10的α-烯烃,只要在该范围内即可,可以单独使用1种,也可以使用2种以上。关于各单体成分的比率,优选丙烯:50~85摩尔%,乙烯:10~22摩尔%,α-烯烃:5~28摩尔%,更优选丙烯:55~80摩尔%,乙烯:10~20摩尔%,α-烯烃:10~28摩尔%。关于(ii),特性粘数[η]优选在0.5~8的范围,更优选在0.8~6的范围。在上述范围时,可以得到柔软性与机械强度的平衡优异、粘合力高的粘合剂。
作为乙烯·丙烯·α-烯烃共聚物(B)的制备方法,没有特别限定,可以采用使用齐格勒-纳塔催化剂、金属茂类催化剂等公知的催化剂的公知方法进行制备。并且,只要满足成型性、具有能够耐受形成成型体时的使用的强度即可,对立规性、分子量也没有特别限定。还可以直接利用市售的树脂。本发明中,只要满足上述条件,也可以是接枝有少量马来酸酐等的物质。另外,只要满足上述条件,也可以是接枝少量马来酸酐等后,进一步用肼、碳二亚胺等修饰接枝单体得到的物质。
(C)乙烯·α-烯烃共聚物
本发明的乙烯·α-烯烃共聚物成分(C)用下述(i)~(ii)规定。(i)含有50~99摩尔%乙烯成分,1~50摩尔%来自碳原子数为3~20的α-烯烃的成分单元,(ii)在135℃萘烷中的特性粘数[η]在0.1~10dl/g的范围。作为α-烯烃,可以较优选地使用碳原子数为3~10的α-烯烃,只要在该范围内即可,可以单独使用1种,也可以使用2种以上。关于各单体成分的比率,优选乙烯:55~98摩尔%,α-烯烃:2~45摩尔%,更优选乙烯:60~95摩尔%,α-烯烃:5~40摩尔%。关于(ii),特性粘数[η]优选在0.5~8的范围,更优选在0.8~6的范围。在上述范围时,可以得到柔软性与机械强度的平衡优异、粘合力高的粘合剂。
作为乙烯·α-烯烃共聚物(C)的制备方法,没有特别限定,可以采用使用齐格勒-纳塔催化剂、金属茂类催化剂等公知的催化剂的公知方法进行制备。并且,只要满足成型性、具有能够耐受形成成型体时的使用的强度即可,对立规性、分子量也没有特别限定。还可以直接利用市售的树脂。本发明中,只要满足上述条件,也可以是接枝有少量马来酸酐等的物质。另外,只要满足上述条件,也可以是接枝少量马来酸酐等后,进一步用肼、碳二亚胺等修饰接枝单体得到的物质。
本发明的粘合剂可以为组合物的一部分被接枝改性的形态。作为接枝单体,可以优选使用不饱和羧酸及/或其衍生物。作为不饱和羧酸及/或其衍生物,可以举出具有1个以上羧基的不饱和化合物、具有羧基的化合物与烷基醇的酯、具有1个以上酸酐基的不饱和化合物等,作为不饱和基团,可以举出乙烯基、1,2-亚乙烯基、不饱和环状烃基等。另外,本发明中使用不饱和羧酸及/或其衍生物时,可以单独使用1种,也可以组合使用2种以上。其中,优选不饱和二羧酸或其酸酐,特别优选使用马来酸、4-降冰片烯-1,2-二羧酸或它们的酸酐。
不饱和羧酸及/或其衍生物相对于100重量份组合物的含量通常为0.01~5重量份,优选为0.01~3重量份。通过使不饱和羧酸及/或其衍生物的含量在上述范围,本发明的聚烯烃组合物对聚酯或乙烯·乙烯醇共聚物等显示出高粘合强度。不饱和羧酸及/或其衍生物的含量例如可以通过适当选择接枝条件容易地进行控制。
<接枝方法>
本发明中使选自不饱和羧酸及/或其衍生物中的接枝单体进行接枝时,对其方法没有特别限定,可以采用溶液法、熔融混炼法等现有公知的接枝聚合法。例如有将聚合物熔融,向其中加入接枝单体,使其进行接枝反应的方法;或者将聚合物溶解于溶剂中制成溶液,向其中加入接枝单体,使其进行接枝反应的方法等。
<粘合剂>
作为本发明的粘合剂的制备方法,没有特别限定,可以采用公知的方法。例如可以举出将聚丙烯(A)、乙烯·丙烯·α烯烃共聚物(B)、乙烯·α烯烃共聚物(C)或者进而根据需要配合的其他成分一起或依次熔融混炼的方法。进行接枝改性时,有下述方法:在(A)、(B)、(C)成分同时存在的状态下进行接枝改性,或者将(A)或(B)或(C)成分的一部分接枝改性,之后将所得的接枝改性物与未改性树脂一起熔融混炼,得到改性聚烯烃组合物的方法等。其中,使聚丙烯(A)的一部分或全部接枝改性后,将未改性成分熔融混合的方法有用。
作为熔融混炼的方法,例如可以举出将树脂组合物干混合后,用单螺杆或双螺杆的螺杆挤出机、班伯里混合机、辊、各种捏和机等进行熔融混炼的方法等,工业上优选使用挤出机。关于熔融混炼的温度,只要(A)、(B)、(C)熔融即可,没有特别限定,通常在160~300℃、优选在180℃~250℃的温度范围内实施。
本发明的粘合剂树脂组合物优选正癸烷可溶成分的乙烯/丙烯/α-烯烃的比为5~95/5~95/1~50摩尔%(其中,总和不超过100摩尔%。)。较优选为15~75/25~65/1~20、更优选为20~60/30~60/5~15摩尔%(其中,各自总和不超过100摩尔%。)。通过采用上述组成,可以得到与极性材料牢固粘合的层合体,同时也可以得到即使进行了高速流延膜成型或拉伸成型、挤出涂布成型粘合性也优异的层合体。另外,可以得到深拉深等二次加工后也无白化的层合体。
在不损害本发明目的的范围内,本发明的粘合剂树脂组合物中可以配合能够混合的其他树脂、弹性体等(例如高压法LDPE、HDPE)。其他树脂等的配合可以与上述(A)、(B)、(C)同时进行,也可以由(A)、(B)、(C)得到粘合剂后进行混合。
在不损害本发明的目的的范围内,本发明的粘合剂树脂组合物中也可以加入公知的生产稳定剂、耐热稳定剂、耐热老化剂、填料等。本发明中,特别是为了赋予粘合性时,优选配合所谓增粘剂。作为赋予粘合性的物质,例如可以举出松香衍生物、萜烯树脂、石油树脂及它们的氢化物,其中,优选氢化萜烯树脂,氢化石油树脂。增粘剂优选以70~98重量%粘合剂、2~30重量%增粘剂的比例进行配合。
<层合体>
本发明的粘合剂优选用作层合体的粘合层。作为构成层合体的其他热塑性树脂层的树脂,可以使用各种热塑性树脂,例如聚烯烃、聚酯、聚酰胺或乙烯·乙烯醇共聚物,其中优选使用乙烯·乙烯醇共聚物。
作为乙烯·乙烯醇共聚物,含有20~50摩尔%、优选含有25~48摩尔%来自乙烯的聚合单元的共聚物较理想。上述共聚物可以利用常用方法将相当的乙烯·乙酸乙烯酯共聚物皂化而进行制备。
本发明的层合体优选为在本发明的聚丙烯类粘合用树脂组合物层的至少一面上,层合乙烯·乙烯醇共聚物层得到的层合体。
本发明的层合体例如可以通过分别熔融各层的组合物或树脂,在熔融状态下层合进行制备。另外,还可以通过在膜或金属管的表面上涂布熔融状态的粘合剂来制备层合体。
实施例
下面,举出实施例及比较例更具体地说明本发明,但本发明只要不超出其主旨即可,不受这些实施例的任何限制。
(各种测定方法)
本实施例等中,根据下述方法实施测定。
[熔体流动速率(MFR)]
根据ASTM D1238,在230℃、2.16kg负荷下实施测定。
[密度]
基于JIS K7112测定密度。
[特性粘数[η]]
基于ASTM D1601测定[η]。
[正癸烷可溶成分的单体组成分析]
使试样加热溶解于正癸烷后,放冷,冷却至室温。在该状态下溶解于正癸烷的成分成为正癸烷可溶成分。分析正癸烷可溶成分的单体组成时,使用在该溶液中混合丙酮使聚合物成分析出后,测定所得聚合物的IR的方法。
(使用的聚烯烃)
实施例及比较例中使用的聚烯烃如下所示。需要说明的是,只要没有特别说明,可以采用任一种常用方法进行聚合来制备。
改性PP-1:改性均聚聚丙烯
(马来酸酐接枝量=1.0wt%,[η]=0.8)
改性PP-2:改性均聚聚丙烯
(马来酸酐接枝量=3.0wt%,[η]=0.4)
PP-1:无规聚丙烯
(丙烯=96mol%,乙烯=3mol%,丁烯=1mol%,[η]=2.0)
PEBR-1:乙烯·丙烯·α-烯烃共聚物
(乙烯=13mol%,丙烯=68mol%,丁烯=19mol%,[η]=1.9)
EPR-1:乙烯·丙烯共聚物
(乙烯=80mol%,丙烯=20mol%,[η]=1.9)
EPR-2:乙烯·丙烯共聚物
(乙烯=80mol%,丙烯=20mol%,[η]=2.2)
LDPE:高压法低密度聚乙烯
(MFR=8g/10分钟)
[实施例1]
(流延膜的粘合力)
<粘合剂的制备>
使用单螺杆挤出机,在230℃下,将(A)20重量%[η]为0.8的改性均聚聚丙烯(改性PP-1)、(B)55重量%[η]为1.9的乙烯·丙烯·α-烯烃共聚物(PEBR-1)和(C)25重量%[η]为2.2的乙烯·丙烯共聚物(EPR-2)熔融混炼,得到粘合剂-1。所得粘合剂-1的熔体流动速率为5.2g/10分钟。
<3层层合体的制备>
在下述条件下将由以下所示组成构成的各层共挤出,成型3层膜。
[内层]
作为乙烯·乙烯醇共聚物(以下称为EVOH),将(株)可乐丽(kuraray)制EVAL(注册商标)F101A(MFR=1.0g/10分钟)在220℃下使用直径40mm、L/D=28的螺杆进行挤出。
[外层]
在230℃下,使用直径50mm、有效长度L/D=28的螺杆,将市售聚丙烯(普瑞曼聚合物公司制F327D,MFR=7)挤出。
[中间层]
在230℃下,使用直径40mm、有效长度L/D=28的螺杆,将粘合剂-1挤出。
<层合体成型条件>
被挤出的用作外层、内层及中间层的树脂在进料区部分(feedblock)内以内层、中间层、外层的顺序层合。模温度为230℃,共挤出成厚度约70μm的膜状的各树脂的层合体,一边用冷却辊冷却,一边以20m/分钟的速度拉出。各层的厚度为外层(聚丙烯)/中间层(粘合剂)/内层(EVOH)=40/10/20μm。另外,以40m/分钟拉出时,各层的厚度为外层(聚丙烯)/中间层(粘合剂)/内层(EVOH)=20/5/10μm。成型的层合体的层间粘合力示于表1。
<层合体的粘合力评价>
将上述制备的层合体切割成15mm宽,使用拉伸试验机,通过T-peel法,在室温23℃下测定EVOH层与粘合剂层的界面的粘合力(单位:N/15mm)。十字头速度设为300mm/min。
表1
配合配方 | 实施例1 | 实施例2 | 比较例1 | 比较例2 |
改性PP-1(接枝量=1.0wt%,[η]=0.8) | 20 | 20 | 20 | 20 |
PEBR-1([η]=1.9)乙烯=13mol%,丙烯=68mol%,丁烯=19mol% | 55 | 35 | - | 40 |
EPR-2([η]=2.2)乙烯=80mol%,丙烯=20mol% | 25 | 25 | 25 | - |
PP-1([η]=2.0)乙烯=3mol%,丙烯=96mol%,丁烯=1mol% | - | 20 | 55 | 40 |
总份数 | 100 | 100 | 100 | 100 |
组合物的MFR[g/10min] | 5.2 | 5.7 | 5.4 | 9.2 |
C2/C3/α烯烃比 | 34/53/13 | 41/48/11 | 80/20/0 | 13/68/19 |
剥离强度[N/15mm](成型速度=20m/min) | 8.1 | 8.7 | 9.3 | 1.9 |
剥离强度[N/15mm](成型速度=40m/min) | 4.7 | 4.9 | 1.5 | 0.5 |
[实施例2,比较例1~2]
根据表1所示的配合配方,采用与实施例1相同的方法制备粘合剂。所得粘合剂的物性及成型的层合体的测定·评价结果示于表1。
[实施例3]
(拉伸膜的粘合力)
<粘合剂的制备>
使用单螺杆挤出机,在230℃下将(A)75.5重量%[η]为2.0的无规聚丙烯(PP-1)、(B)15重量%[η]为1.9的乙烯·丙烯·α-烯烃共聚物(PEBR-1)、(C)5重量%[η]为2.2的乙烯·丙烯共聚物(EPR-2)和(D)4.5重量%[η]为0.4的改性均聚聚丙烯(改性PP-2)熔融混炼,得到粘合剂-1。所得粘合剂-1的熔体流动速率为7.9g/10分钟。
<5层层合体的制备>
在下述条件下将由以下所示组成构成的各层共挤出,成型5层拉伸膜。
1)5层片材的成型
[外层及内层]
使用直径40mm、有效长度L/D=28的螺杆,在230℃下,将市售聚丙烯(普瑞曼聚合物公司制E-233GV,MFR=1)挤出。
[粘合层]
用直径40mm、有效长度L/D=28的螺杆,在230℃下挤出粘合剂-1。
[中间层]
作为乙烯·乙烯醇共聚物(以下称为EVOH),将(株)可乐丽制EVAL(注册商标)F101B(MFR=1.0g/10分钟),使用直径30mm、L/D=24的螺杆在220℃下挤出。
[片材成型条件]
被挤出的用作外层、内层、粘合层及中间层的树脂在进料区部分内以内层、粘合层、中间层、粘合层、外层进行层合。模温度为220℃,共挤出成厚度约850μm的片状的各树脂的层合体,一边用冷却辊冷却,一边以1m/分钟的速度拉出。各层的厚度为外层(聚丙烯)/粘合层(粘合剂-1)/中间层(EVOH)/粘合层(粘合剂-1)/内层(聚丙烯)=350/50/50/50/350μm。
2)5层拉伸膜成型
[拉伸膜成型条件]
在140℃下预热后,以1.5m/分钟的拉出速度、面积比为6倍同时双轴拉伸,在100℃下退火,室温下冷却,由此成型拉伸膜。各层的厚度为外层(聚丙烯)/粘合层(粘合剂-1)/中间层(EVOH)/粘合层(粘合剂-1)/内层(聚丙烯)=60/8/8/6/60μm。成型的层合体的层间粘合力示于表1。
<层合体的粘合力评价>
将上述制备的层合体切割成15mm宽,使用拉伸试验机,通过T-peel法,在室温23℃下测定EVOH层与粘合剂层的界面的粘合力(单位:N/15mm)。十字头速度设为300mm/min。
表2
配合配方 | 实施例3 | 比较例3 | 比较例4 |
改性PP-2(接枝量=3.0wt%,[η]=0.4) | 4.5 | 4.5 | 4.5 |
PEBR-1([η]=1.9)乙烯=13mol%,丙烯=68mol%,丁烯=19mol% | 15 | 10 | - |
EPR-2([η]=2.2)乙烯=80mol%,丙烯=20mol% | 5 | - | 25 |
PP-1([η]=2.0)乙烯=3mol%,丙烯=96mol%,丁烯=1mol% | 75.5 | 85.5 | 70.5 |
总份数 | 100 | 100 | 100 |
组合物的MFR[g/10min] | 7.9 | 8.8 | 6.1 |
C2/C3/α烯烃比 | 30/56/14 | 13/68/19 | 80/20/0 |
拉伸后的剥离强度[N/15mm] | 3.9 | 2.5 | 2.8 |
[比较例3~4]
根据表2所示的配合配方,采用与实施例3相同的方法制备粘合剂。所得粘合剂的物性及成型的层合体的测定·评价结果示于表2。
[实施例4]
(挤出涂布膜的粘合力及耐白化性)
<粘合剂的制备>
在230℃下,用单螺杆挤出机,将(A)20重量%[η]为0.8的改性均聚聚丙烯(PP-1)、(B)55重量%[η]为1.9的乙烯·丙烯·α-烯烃共聚物(PEBR-1)和(C)25重量%[η]为1.9的乙烯·α-烯烃共聚物(EPR-1)熔融混炼,得到粘合剂-1。所得粘合剂-1的熔体流动速率为5.2g/10分钟。
<3层层合体的制备>
在下述条件下将由以下所示组成构成的各层共挤出涂布,成型3层膜。
[外层及中间层]
在290℃下,使用直径50mm、有效长度L/D=28的螺杆,将市售聚丙烯(普瑞曼聚合物公司制F329RA,MFR=24)及粘合剂-1挤出。
[层合体成型条件]
被挤出的用作外层及内层的树脂在进料区部分内以内层、外层的顺序层合。模温度为290℃,共挤出成厚度约40μm的膜状的各树脂的层合体在熔融状态下与铝箔(厚度20μm)表面接触后,用附有夹紧辊的冷却辊冷却,以50m/分钟的速度拉出。各层的厚度为外层(聚丙烯)/内层(粘合剂)=20/20μm。成型的层合体的层间粘合力示于表3。
<层合体的粘合力评价>
将上述制备的层合体切割成15mm宽,使用拉伸试验机,通过T-peel法,在室温23℃下测定铝箔与粘合剂层的界面的粘合力(单位:N/15mm)。十字头速度设为300mm/min。
<深拉深成型后的耐白化性评价>
将上述制备的层合体用啮合深度5mm的模进行深拉深成型,目视确认壁面有无白化。
表3
配合配方 | 实施例4 | 实施例5 | 实施例6 | 比较例5 | 比较例6 |
改性PP-1(接枝量=1.0wt%,[η]=0.8) | 20 | 20 | 20 | 20 | 20 |
PEBR-1([η]=1.9)乙烯=13mol%,丙烯=68mol%,丁烯=19mol% | 55 | 35 | 30 | - | 35 |
EPR-1([η]=1.9)乙烯=80mol%,丙烯=20mol% | 25 | 25 | 20 | 25 | - |
PP-1([η]=2.0)乙烯=3mol%,丙烯=96mol%,丁烯=1mol% | - | 20 | 20 | 55 | 45 |
LDPE(MFR=8) | - | - | 10 | - | - |
总份数 | 100 | 100 | 100 | 100 | 100 |
组合物的MFR[g/10min] | 5.3 | 5.7 | 5.9 | 5.4 | 5.9 |
C2/C3/α烯烃比 | 34/53/13 | 41/48/11 | 40/49/11 | 80/20/0 | 13/68/19 |
剥离强度[N/15mm] | 3.4 | 2.8 | 2.5 | 0.77 | 0.89 |
5mm拉深加工后有无白化 | 无 | 无 | 无 | 有 | 无 |
[实施例5~6,比较例5~6]
根据表3所示的配合配方,采用与实施例4相同的方法制备粘合剂。所得粘合剂的物性及成型的层合体的测定·评价结果示于表3。
Claims (12)
1、一种粘合性树脂组合物,是含有聚丙烯成分(A)、乙烯·丙烯·α-烯烃共聚物成分(B)、乙烯·α-烯烃共聚物成分(C)及不饱和羧酸及/或其衍生物(D)的、经接枝加成得到的树脂组合物,其特征在于,成分(A)、(B)及(C)的总和100质量份中,成分(A)为5~80质量份,成分(B)为5~70质量份,成分(C)为1~40质量份,正癸烷可溶成分的乙烯/丙烯/α-烯烃的比为5~95/5~95/1~50摩尔%,并且接枝率为0.01~5wt%。
2、如权利要求1所述的粘合性树脂组合物,其中,成分(B)中的丙烯成分为45~90摩尔%,乙烯成分为10~25摩尔%,来自碳原子数为4~20的α-烯烃的成分单元为1~30摩尔%。
3、如权利要求2所述的粘合性树脂组合物,其中,成分(B)在135。℃萘烷中的特性粘数[η]为0.1~10dl/g。
4、如权利要求1所述的粘合性树脂组合物,其中,成分(C)中的乙烯成分为50~99摩尔%,来自碳原子数为3~20的α-烯烃的成分单元为1~50摩尔%。
5、如权利要求4所述的粘合性树脂组合物,其中,成分(C)在135℃萘烷中的特性粘数[η]为0.1~10dl/g。
6、如权利要求1所述的粘合性树脂组合物,其中,聚丙烯成分(A)在135℃萘烷中的特性粘数[η]为0.1~10dl/g。
7、一种粘合剂,含有权利要求1所述的粘合性树脂组合物。
8、如权利要求7所述的粘合剂,其中还含有增粘剂。
9、一种层合体,具有至少一层含有权利要求7或8所述的粘合剂的层。
10、如权利要求9所述的层合体,是通过成型速度为40m/min以上的流延膜成型法成型得到的。
11、如权利要求9所述的层合体,是以2倍以上的面积比拉伸得到的。
12、如权利要求9所述的层合体,是通过挤出涂布法成型得到的。
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CN102971374A (zh) * | 2010-07-05 | 2013-03-13 | 住友化学株式会社 | 组合物、层叠结构及层叠结构的制造方法 |
CN103210034A (zh) * | 2010-12-09 | 2013-07-17 | 三井化学株式会社 | 改性聚丙烯组合物及使用了该组合物的层叠体 |
CN103210034B (zh) * | 2010-12-09 | 2015-09-30 | 三井化学株式会社 | 改性聚丙烯组合物及使用了该组合物的层叠体 |
CN111770961A (zh) * | 2018-03-15 | 2020-10-13 | 三井化学株式会社 | 树脂组合物以及单层和多层膜 |
CN109796912A (zh) * | 2018-12-27 | 2019-05-24 | 广州鹿山新材料股份有限公司 | 一种改性聚丙烯热熔胶及其制备方法 |
CN109796912B (zh) * | 2018-12-27 | 2022-03-11 | 广州鹿山新材料股份有限公司 | 一种改性聚丙烯热熔胶及其制备方法 |
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US20100063198A1 (en) | 2010-03-11 |
JP5261196B2 (ja) | 2013-08-14 |
TW200838961A (en) | 2008-10-01 |
KR101128181B1 (ko) | 2012-03-22 |
EP2110408A1 (en) | 2009-10-21 |
KR20090126254A (ko) | 2009-12-08 |
JPWO2008093805A1 (ja) | 2010-05-20 |
US8445582B2 (en) | 2013-05-21 |
CN101595177B (zh) | 2012-08-08 |
EP2110408A4 (en) | 2011-03-16 |
TWI427128B (zh) | 2014-02-21 |
WO2008093805A1 (ja) | 2008-08-07 |
EP2110408B1 (en) | 2014-05-07 |
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