CN107001676A - 热塑性树脂组合物成型体 - Google Patents

热塑性树脂组合物成型体 Download PDF

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Publication number
CN107001676A
CN107001676A CN201580063740.2A CN201580063740A CN107001676A CN 107001676 A CN107001676 A CN 107001676A CN 201580063740 A CN201580063740 A CN 201580063740A CN 107001676 A CN107001676 A CN 107001676A
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China
Prior art keywords
thermoplastic resin
formed body
weight
resin
foam sheet
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Granted
Application number
CN201580063740.2A
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CN107001676B (zh
Inventor
千叶俊辅
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Abstract

提供一种成型体及其制造方法、以及具有该成型体的层叠体,所述成型体由热塑性树脂组合物形成,按照JIS B0601‑1982测定的成型体的表面粗糙度的最大高度(Rmax)和按照JIS B0601‑1982测定的上述成型体的表面的算术平均粗糙度(Ra)满足式:9≤Rmax/(Ra+1)≤45,当将上述成型体的表面积设为100%时,该成型体的贯通孔的面积率为1%以上且20%以下,松密度为0.13g/cm3以上且0.50g/cm3以下。

Description

热塑性树脂组合物成型体
技术领域
本发明涉及由热塑性树脂组合物形成的成型体。
背景技术
对于室内装饰制品、例如桌布、灯罩、照明器具罩、隔断、拉窗纸、隔扇等,要求装饰性,在这些部件中使用了日本纸或合成树脂膜。
例如,在专利文献1中提出了将日本纸与合成树脂膜层叠而成的装饰合成树脂片材。在专利文献2中记载了将含有丙烯树脂和发泡剂的树脂组合物进行熔融挤出并拉伸而制造的高光泽的树脂膜,在专利文献3中记载了将含有丙烯树脂、低密度聚乙烯和发泡剂的树脂组合物进行熔融挤出并拉伸而制造的具有珍珠样光泽的树脂膜。在专利文献4中记载了将含有丙烯树脂、低密度聚乙烯和发泡剂的树脂组合物进行熔融挤出而得到的表面的平滑性优异的发泡片材。
现有技术文献
专利文献
专利文献1:日本特开2003-25514号公报
专利文献2:日本特表2002-524299号公报
专利文献3:日本特开2007-231192号公报
专利文献4:日本特开平9-235403号公报
发明内容
发明所要解决的问题
然而,由含有热塑性树脂和发泡剂的树脂组合物调制的上述的膜或片材并不具有日式的质地(Japanese-style texture),此外,在部件中使用了日本纸的上述的装饰合成树脂片材尽管具有日式的质地但并非能够适用于西式的设计、并对看的人给予现代化的印象、作为整体而具有日式现代化的质地。
基于所述状况,本发明所要解决的课题在于提供由热塑性树脂组合物形成、具有日式现代化的质地(Japanese-modern texture)的成型体。
用于解决问题的手段
根据本发明,提供以下所示的成型体、具有成型体的层叠体及成型体的制造方法。
[1]一种成型体,其由热塑性树脂组合物形成,
按照JIS B0601-1982测定的成型体的表面粗糙度的最大高度(Rmax)和按照JISB0601-1982测定的上述成型体的表面的算术平均粗糙度(centerline averageroughness,也可称为中心线平均粗糙度)(Ra)满足下式(1):
9≤Rmax/(Ra+1)≤45 式(1)
当将上述成型体的表面积设为100%时,该成型体的贯通孔的面积率为1%以上且20%以下,
松密度(bulk density)为0.13g/cm3以上且0.50g/cm3以下。
[2]根据[1]所述的成型体,其中,热塑性树脂组合物是含有2种不相容的热塑性树脂的组合物,当将热塑性树脂组合物中的热塑性树脂的总量设为100重量%时,上述2种不相容的热塑性树脂的合计量为90重量%以上。
[3]根据[2]所述的成型体,其中,2种不相容的热塑性树脂为转变温度不同的2种不相容的热塑性树脂。
[4]根据[3]所述的成型体,其中,转变温度不同的2种不相容的热塑性树脂中的转变温度较高的热塑性树脂即第一热塑性树脂(A)与转变温度较低的热塑性树脂即第二热塑性树脂(B)的转变温度的差为10℃以上且50℃以下,
当将上述第一热塑性树脂(A)和上述第二热塑性树脂(B)的合计量设为100重量%时,上述第一热塑性树脂(A)的含量为30重量%以上且90重量%以下,上述第二热塑性树脂(B)的含量为10重量%以上且70重量%以下。
[5]根据[1]~[4]中任一项所述的成型体,其为具有10μm以上且1000μm以下的厚度的膜。
[6]一种层叠体,其具有由[1]~[5]中任一项所述的成型体构成的层作为至少一个表层。
[7]一种[1]~[5]中任一项所述的成型体的制造方法,其含有以下工序:将含有发泡剂的热塑性树脂组合物进行熔融挤出而制作发泡片材的发泡片材制作工序;和
将上述发泡片材制作工序中得到的发泡片材进行双轴拉伸的拉伸工序。
发明效果
本发明能够提供由热塑性树脂组合物形成、且具有日式现代化的质地的成型体。
具体实施方式
本发明的成型体由热塑性树脂组合物形成,按照JIS B0601-1982测定的成型体的表面粗糙度的最大高度(Rmax)和按照JIS B0601-1982测定的成型体的表面的算术平均粗糙度(Ra)满足下式(1)。
9≤Rmax/(Ra+1)≤45 式(1)
本发明的成型体的贯通孔的面积率为1%以上且20%以下。该贯通孔是沿成型体的厚度方向贯通的孔。该贯通孔的面积率是当将成型体的表面积设为100%时贯通孔的开口部分在该成型体的表面中所占的面积的比例、即贯通孔部分的面积相对于成型体的表面积100%的比例,可以通过将成型体的表面图像进行图像分析而求出。贯通孔的面积率具体而言可以通过使用图像分析装置将所得到的图像利用图像分析软件进行分析而求出。从使成型体的质地良好的观点出发,贯通孔的面积率优选为3%以上且15%以下。
本发明的成型体的松密度为0.13g/cm3以上且0.50g/cm3以下。该松密度是成型体的重量相对于外尺寸体积的比、即重量除以由成型体的外尺寸计算的体积而得到的值。成型体的松密度通过成型体的贯通孔的面积率、成型体表面的凹凸、成型体内部的独立气泡等的增加而降低。从使成型体的质地良好的观点出发,松密度优选为0.15g/cm3以上且0.40g/cm3以下。
本发明的成型体优选为膜或片材,更优选为膜。在本发明的成型体为膜时,膜的厚度优选为10μm以上且1000μm以下,更优选为30μm以上且500μm以下。
作为本发明的成型体的适宜的制造方法,可列举出含有以下工序的方法:将含有发泡剂的热塑性树脂组合物进行熔融挤出而制作发泡片材的发泡片材制作工序;和将上述发泡片材制作工序中得到的发泡片材进行双轴拉伸的拉伸工序。该热塑性树脂组合物优选含有2种以上的不相容的热塑性树脂。通过将发泡片材进行双轴拉伸,发泡片材的气泡破裂,破裂的气泡的一部分相连而形成沿厚度方向贯通的孔(贯通孔)。在发泡片材的表面附近气泡破裂时,在发泡片材的表面形成凹部。伴随着上述贯通孔或凹部的形成,在贯通孔或凹部的周缘树脂凸起等,形成树脂密集的凸部。上述凸部相连而看到的部分恰好呈现日本纸中的纤维那样的外观,产生日式现代化的质地。具有这样形成的凹凸的成型体的表面粗糙度的最大高度(Rmax)主要受到像日本纸中的纤维那样所看到的密集的凸部的影响,具有日式现代化的质地的成型体的凹凸满足上述式(1)。当热塑性树脂组合物含有转变温度不同的2种以上的不相容的热塑性树脂时,通过上述方法制作的发泡片材中的不相容的热塑性树脂发生相分离,在发泡片材的厚度、外观、气泡等中容易产生不均,若将这样的发泡片材进行拉伸,则在发泡片材中相分离的各热塑性树脂中的转变温度较低的树脂的部分比转变温度较高的树脂的部分在拉伸时优先被拉长,转变温度较高的树脂的部分产生难以被拉长的拉伸时的伸长不均,更容易形成成型体表面的凹凸或贯通孔。
作为热塑性树脂,可列举出烯烃树脂、苯乙烯树脂、甲基丙烯酸树脂、丙烯酸树脂、酯树脂、酰胺树脂等,优选烯烃树脂或苯乙烯树脂。
所谓烯烃树脂是当将该烯烃树脂的全部量设为100重量%时含有50重量%以上的来源于碳原子数为2以上且10以下的烯烃的结构单元的树脂。作为碳原子数为2以上且10以下的烯烃,例如可列举出乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯、1-辛烯、1-癸烯等。
烯烃树脂也可以含有来源于除碳原子数为2以上且10以下的烯烃以外的单体的结构单元。作为除碳原子数为2以上且10以下的烯烃以外的单体,例如可列举出苯乙烯等芳香族乙烯基单体;丙烯酸、甲基丙烯酸等不饱和羧酸;丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯等不饱和羧酸酯;醋酸乙烯酯等乙烯基酯化合物;1,3-丁二烯、2-甲基-1,3-丁二烯(异戊二烯)等共轭二烯;二环戊二烯、5-亚乙基-2-降冰片烯等非共轭二烯。
作为烯烃树脂,优选乙烯树脂、丙烯树脂、或丁烯树脂。
所谓乙烯树脂是含有50重量%以上的来源于乙烯的结构单元的树脂,例如可列举出乙烯均聚物、乙烯-1-丁烯共聚物、乙烯-1-己烯共聚物、乙烯-1-辛烯共聚物、乙烯-1-丁烯-1-己烯共聚物等。也可以使用两种以上的乙烯树脂。
所谓丙烯树脂是含有50重量%以上的来源于丙烯的结构单元的树脂,例如可列举出丙烯均聚物、丙烯-乙烯共聚物、丙烯-1-丁烯共聚物、丙烯-1-己烯共聚物、丙烯-1-辛烯共聚物、丙烯-乙烯-1-丁烯共聚物、丙烯-乙烯-1-己烯共聚物、丙烯-乙烯-1-辛烯共聚物等。也可以使用两种以上的丙烯树脂。
所谓丁烯树脂是含有50重量%以上的来源于1-丁烯的结构单元的树脂,例如可列举出1-丁烯均聚物、1-丁烯-乙烯共聚物、1-丁烯-丙烯共聚物、1-丁烯-1-己烯共聚物、1-丁烯-1-辛烯共聚物、1-丁烯-乙烯-丙烯共聚物、1-丁烯-乙烯-1-己烯共聚物、1-丁烯-乙烯-1-辛烯共聚物、1-丁烯-丙烯-1-己烯共聚物、1-丁烯-丙烯-1-辛烯共聚物等。也可以使用两种以上的丁烯树脂。
所谓苯乙烯树脂是含有50重量%以上的来源于苯乙烯或苯乙烯衍生物的结构单元的树脂。作为苯乙烯衍生物,例如可列举出对甲基苯乙烯、对叔丁基苯乙烯、α-甲基苯乙烯、对甲氧基苯乙烯。苯乙烯树脂也可以含有来源于除苯乙烯或苯乙烯衍生物以外的单体的结构单元,例如可列举出碳原子数为2以上且10以下的烯烃;丙烯酸、甲基丙烯酸等不饱和羧酸;丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯等不饱和羧酸酯;醋酸乙烯酯等乙烯基酯化合物;1,3-丁二烯、2-甲基-1,3-丁二烯(异戊二烯)等共轭二烯;二环戊二烯、5-亚乙基-2-降冰片烯等非共轭二烯。
所谓甲基丙烯酸树脂是含有50重量%以上的来源于甲基丙烯酸酯的结构单元的树脂,例如可列举出聚(甲基丙烯酸甲酯)、聚(甲基丙烯酸乙酯)、聚(甲基丙烯酸丁酯)、聚(甲基丙烯酸2-乙基己酯)等。
所谓丙烯酸树脂是含有50重量%以上的来源于丙烯酸酯的结构单元的树脂,例如可列举出聚(丙烯酸甲酯)、聚(丙烯酸乙酯)、聚(丙烯酸丁酯)、聚(丙烯酸2-乙基己酯)等。
所谓酯树脂是含有50重量%以上的来源于多元羧酸与多元醇的酯的结构单元的树脂,例如可列举出聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸丁二醇酯等。
所谓酰胺树脂是含有50重量%以上的以酰胺键重复的结构单元的树脂,例如可列举出聚(ε-己内酰胺)、聚十二烷酰胺、聚(己二酰己二胺)、聚(六亚甲基十二烷酰胺)、聚(对亚苯基对苯二甲酰胺)、聚(间亚苯基对苯二甲酰胺)等。
作为上述的热塑性树脂的制造方法,可以采用使用了公知的聚合用催化剂的公知的聚合方法。
在热塑性树脂组合物含有2种不相容的热塑性树脂的情况下,当将热塑性树脂组合物中的热塑性树脂的总量设为100重量%时,上述2种不相容的热塑性树脂的合计量优选为90重量%以上。在热塑性树脂组合物含有2种不相容的热塑性树脂的情况下,作为不相容的热塑性树脂2种的组合,例如可列举出烯烃树脂和烯烃树脂、烯烃树脂和苯乙烯树脂、烯烃树脂和甲基丙烯酸树脂、烯烃树脂和丙烯酸树脂、烯烃树脂和酯树脂、或烯烃树脂和酰胺树脂等组合,优选为烯烃树脂和烯烃树脂、或烯烃树脂和苯乙烯树脂,更优选为丙烯树脂和乙烯树脂、或丙烯树脂和苯乙烯树脂。在热塑性树脂组合物含有2种不相容的热塑性树脂、进而含有与上述2种不相容的热塑性树脂不同的热塑性树脂的情况下,该进一步的热塑性树脂可以是与上述2种不相容的热塑性树脂中的一者相容的树脂,也可以与上述2种不相容的热塑性树脂的两者不相容。
在本发明的成型体的制造中使用的热塑性树脂组合物中,优选含有转变温度不同的2种不相容的热塑性树脂。当将上述2种不相容的热塑性树脂中的转变温度较高的热塑性树脂设为第一热塑性树脂(A),将转变温度较低的热塑性树脂设为第二热塑性树脂(B)时,将热塑性树脂组合物中的上述第一热塑性树脂(A)和上述第二热塑性树脂(B)的合计量设为100重量%,上述热塑性树脂组合物中的上述第一热塑性树脂(A)的含量为30重量%以上且90重量%以下,上述第二热塑性树脂(B)的含量为10重量%以上且70重量%以下,将上述热塑性树脂组合物中的热塑性树脂的总量设为100重量%,该热塑性树脂组合物中的上述第一热塑性树脂(A)和上述第二热塑性树脂(B)的合计量优选为90重量%以上。其中,所谓转变温度,在结晶性热塑性树脂的情况下为树脂的熔融峰值温度,在非晶性热塑性树脂的情况下为树脂的玻璃化转变温度,均可以通过差示扫描量热测定而求出。上述第一热塑性树脂(A)与上述第二热塑性树脂(B)的转变温度的差优选为10℃以上且50℃以下。
将热塑性树脂组合物中的上述第一热塑性树脂(A)和上述第二热塑性树脂(B)的合计量设为100重量%,更优选该热塑性树脂组合物中的上述第一热塑性树脂(A)的含量为40重量%以上且80重量%以下、上述第二热塑性树脂(B)的含量为20重量%以上且60重量%以下,进一步优选上述第一热塑性树脂(A)的含量为50重量%以上且70重量%以下、上述第二热塑性树脂(B)的含量为30重量%以上且50重量%以下。为了增大式(1)的Rmax/(Ra+1)的值,优选增多上述第二热塑性树脂(B)的含量。如上所述,在拉伸时,转变温度较低的树脂(B)的部分比转变温度较高的树脂(A)的部分优先被拉长。认为通过增多上述第二热塑性树脂(B)的含量,容易伸长的部分增加,该部分进一步被伸长而变薄,上述第一热塑性树脂(A)的部分以几乎不伸长的状态残留,Rmax变大,Rmax/(Ra+1)的值变大。
按照JIS K7210-1999在温度230℃及载荷2.16kgf的条件下测定的上述第一热塑性树脂(A)的熔体质量流动速率(MFR(A))优选为1g/10分钟以上且30g/10分钟以下。
按照JIS K7210-1999在温度230℃及载荷2.16kgf的条件下测定的上述第一热塑性树脂(A)的熔体质量流动速率(MFR(A))和按照JIS K7210-1999在温度230℃及载荷2.16kgf的条件下测定的上述第二热塑性树脂(B)的熔体质量流动速率(MFR(B))优选满足下式(2)。
-0.5≤log(MFR(A))-log(MFR(B))≤0.5式(2)
作为第一热塑性树脂(A),优选丙烯树脂。丙烯树脂的熔融峰值温度优选为125℃以上且140℃以下。
作为第二热塑性树脂(B),优选乙烯树脂或苯乙烯树脂。乙烯树脂和苯乙烯树脂的密度优选为0.860g/cm3以上且0.905g/cm3以下。其中,密度按照JIS K7112-1990中规定的水中置换法(23℃)来测定。
作为发泡剂,可列举出化学发泡剂、物理发泡剂等公知的发泡剂。也可以将化学发泡剂与物理发泡剂并用。
作为化学发泡剂,可以为无机化合物,也可以为有机化合物,也可以将2种以上并用。
作为无机化合物,可列举出碳酸铵等碳酸盐;碳酸氢钠等碳酸氢盐等。
作为有机化合物,可列举出(a)有机酸或其盐:柠檬酸、琥珀酸、己二酸、酒石酸、苯甲酸等羧酸及其盐、(b)N-亚硝基化合物:N,N’-二亚硝基对苯二甲酰胺、N,N’-二亚硝基五亚甲基四胺、(c)偶氮化合物:偶氮二甲酰胺、偶氮双异丁腈、偶氮环己腈、偶氮二氨基苯、偶氮二羧酸钡、(d)磺酰肼化合物:苯磺酰肼、甲苯磺酰肼、p,p’-氧代双(苯磺酰肼)、二苯基砜-3,3’-二磺酰肼、(e)叠氮化合物:叠氮化钙、4,4’-二苯基二磺酰基叠氮、对甲苯磺酰基叠氮等。
作为物理发泡剂,可列举出氮、二氧化碳等不活泼气体或挥发性有机化合物等。作为物理发泡剂,优选超临界状态的二氧化碳、氮或它们的混合物。物理发泡剂也可以将两种以上并用。
发泡剂优选为化学发泡剂,更优选为有机酸或其盐、或者有机酸或其盐与碳酸氢盐的混合物。
本发明的成型体的制造中使用的热塑性树脂组合物中的发泡剂的含量在每100重量份热塑性树脂的总量中,优选为0.1重量份以上且3重量份以下。
为了提高成型体的贯通孔的面积率,优选增多发泡剂的含量。通过增多发泡剂的含量,将树脂组合物进行熔融挤出而制作的发泡片材中的气泡变多。认为通过将气泡多的发泡片材进行拉伸,发泡片材的气泡容易破裂、相连而变成贯通孔,贯通孔的面积率变高。此外,为了增大式(1)的Rmax/(Ra+1)的值,优选增多发泡剂的含量。气泡多的发泡片材表面附近的气泡也多,通过进行拉伸,在发泡片材的表面附近气泡容易破裂,表面变成更粗糙的状态。这种情况下,认为Rmax和Ra均变大,但Rmax进一步变大。
当添加作为发泡剂的化学发泡剂时,可以在热塑性树脂中直接添加化学发泡剂,也可以将以热塑性树脂作为基质(base)树脂的化学发泡剂的母料添加到热塑性树脂中。当将母料的全部量设为100重量%时,优选母料中的化学发泡剂的含量为20重量%以上且80重量%以下。
本发明的成型体的制造中使用的热塑性树脂组合物也可以进一步含有有机纤维、无机填充材料、有机聚合物珠或其他的添加剂。
作为有机纤维,例如可列举出聚酯纤维、聚酰胺纤维、聚氨酯纤维、聚酰亚胺纤维、聚烯烃纤维、聚丙烯腈纤维、洋麻等植物纤维,优选聚酯纤维。
当含有有机纤维时,有机纤维的含量在每100重量份热塑性树脂的总量中,优选为1重量份以上且30重量份以下。
作为无机填充材料,可列举出为粉末状、薄片状、或颗粒状的无机填充材料、为纤维状的无机填充材料等。
作为为粉末状、薄片状、或颗粒状的无机填充材料,例如可列举出滑石、云母、碳酸钙、硫酸钡、碳酸镁、粘土、氧化铝、二氧化硅、硫酸钙、硅砂、炭黑、氧化钛、氢氧化镁、沸石、钼、硅藻土、绢云母、火山砂(日语原文为:シラス)、氢氧化钙、亚硫酸钙、硫酸钠、膨润土、石墨等。
作为为纤维状的无机填充材料,例如可列举出纤维状氧硫化镁、钛酸钾纤维、氢氧化镁纤维、硼酸铝纤维、硅酸钙纤维、碳酸钙纤维、碳纤维、玻璃纤维、金属纤维等。
无机填充材料可以单独使用,也可以将2种以上并用。
无机填充材料也可以是以偶联剂或表面活性剂将表面处理过的材料。作为偶联剂,例如可列举出硅烷偶联剂或钛偶联剂。作为表面活性剂,例如可列举出高级脂肪酸、高级脂肪酸酯、高级脂肪酸酰胺、高级脂肪酸盐等。
为粉末状、薄片状、或颗粒状的无机填充材料的平均粒径优选为10μm以下,更优选为5μm以下。
上述的平均粒径是使用离心沉降式粒度分布测定装置,悬浮在水或醇等分散介质中进行测定,由过筛法的积分分布曲线求出的50%当量粒径(D50)。
为纤维状的无机填充材料的平均纤维长度通常为3μm以上且20μm以下。平均纤维直径优选为0.2μm以上且1.5μm以下。此外,长宽比优选为10以上且30以下。另外,为纤维状的无机填充材料的平均纤维长度及平均纤维直径是通过电子显微镜测定的值,长宽比是平均纤维长度相对于平均纤维直径的比(平均纤维长度除以平均纤维直径而得到的值)。
当含有无机填充材料时,无机填充材料的含量在每100重量份热塑性树脂的总量中,优选为0.1重量份以上且30重量份以下。
作为其他的添加剂,例如可列举出中和剂、抗氧化剂、紫外线吸收剂、耐光剂、耐候剂、润滑剂、抗静电剂、抗粘连剂、加工助剂、颜料、发泡核剂、增塑剂、阻燃剂、交联剂、交联助剂、高亮度化剂、抗菌剂、光扩散剂等。这些添加剂可以单独使用,也可以将2种以上并用。此外,在发泡片材制作工序中,为了防止树脂的劣化物等附着在后述的T型模或圆形模上,也可以含有高级脂肪酸金属盐,为了使成型体具有日式现代化的质地,将在发泡片材制作工序中使用的发泡剂的含量设为100重量份,优选将高级脂肪酸金属盐的含量设定为50重量份以下,更优选设定为25重量份以下。
在将含有发泡剂的热塑性树脂组合物进行熔融挤出而制作发泡片材的发泡片材制作工序中,具体而言,优选通过单螺杆挤出机或双螺杆挤出机将含有发泡剂的热塑性树脂组合物进行熔融混炼,由T型模或圆形模将热塑性树脂组合物熔融挤出并使其发泡,利用冷却辊冷却固化为片材状。
挤出机内的混炼温度优选比发泡剂的分解开始温度低。混炼温度更优选为比发泡剂的分解开始温度低2℃以上的温度,进一步优选为比发泡剂的分解开始温度低5℃以上的温度。挤出机内的热塑性树脂的滞留时间优选为1分钟以上且10分钟以下。
从T型模或圆形模进行熔融挤出时的热塑性树脂组合物的温度优选比发泡剂的分解开始温度高。熔融挤出时的热塑性树脂组合物的温度更优选为比发泡剂的分解开始温度高5℃以上的温度,进一步优选为比发泡剂的分解开始温度高10℃以上的温度。
作为挤出机的旋转速度,可列举出20rpm~70rpm。为了增大成型体的贯通孔的面积率,优选降低挤出机的旋转速度(喷出量)。若降低挤出机的旋转速度(喷出量),则所得到的发泡片材的厚度相对变薄。此外,若降低挤出机的旋转速度(喷出量),则挤出机内的树脂压力变低,来自发泡剂的气泡容易变大,所得到的发泡片材的发泡倍率存在变高的倾向。认为若将这样的发泡片材进行拉伸,则发泡片材的气泡容易破裂、相连而变成贯通孔,贯通孔的面积率变高。
作为利用冷却辊冷却固化为片材状时的线速度,可列举出0.3m/分钟~1.2m/分钟。为了增大式(1)的Rmax/(Ra+1),优选提高利用冷却辊冷却固化为片材状时的线速度。通过提高上述线速度,熔融挤出后的树脂组合物被冷却的冷却速度变慢。因此,认为不相容的两种树脂的相分离变得容易进行,在发泡片材中,转变温度低的树脂(B)聚集的部分(区域)的面积变大,在拉伸时容易被伸长的部分的面积增加,该部分进一步被伸长而变薄,树脂(A)的部分以几乎没伸长的状态残留,所以Rmax变大,Rmax/(Ra+1)变大。
在将上述发泡片材制作工序中得到的发泡片材进行双轴拉伸的拉伸工序中,作为将发泡片材进行双轴拉伸的方法,可列举出逐步双轴拉伸方式、同时双轴拉伸方式、管式双轴拉伸方式等拉伸方式。
在上述拉伸工序中,将热塑性树脂组合物中包含的热塑性树脂中的具有最高的转变温度的热塑性树脂的转变温度设为TX(单位:℃),拉伸温度优选为(TX-10)℃以上且(TX+10)℃以下。
在上述拉伸工序中,纵向拉伸倍率优选为3倍以上且8倍以下,横向拉伸倍率优选为3倍以上且8倍以下。纵向拉伸倍率与横向拉伸倍率的比率优选为0.77以上且1.3以下。为了增大成型体的贯通孔的面积率,优选提高拉伸倍率。认为通过提高拉伸倍率,由于在拉伸时发泡片材更多地被伸长,所以发泡片材的气泡容易破裂相连而变成贯通孔,贯通孔的面积率变高。
本发明的成型体也可以作为与其他的树脂或材料层叠而成的层叠体使用,那样的情况下,层叠体具有由本发明的成型体构成的层作为至少一个表层。作为层叠体,例如可列举出具有由本发明的成型体构成的表层和基材层的层叠体等。在具有由本发明的成型体构成的表层和基材层的层叠体中,通过由本发明的成型体构成的表层的贯通孔,可见到与上述表层相邻的基材层的表面。
作为具有本发明的成型体作为至少一个表层的层叠体的制造方法,例如可列举出以下方法:将含有发泡剂的热塑性树脂组合物进行熔融挤出而制作发泡片材,将所得到的发泡片材与其他的树脂层叠,通过以真空/加压成形或冲压成形等进行拉伸,从而一边将片材拉伸一边赋予立体形状的方法;将本发明的成型体嵌入模具内通过吹塑成形等与其他的树脂粘接的方法。也可以通过制作具有由互不相同的树脂组合物形成的两种以上的层的发泡片材,并将上述发泡片材进行双轴拉伸,使发泡片材的至少一个表层为由本发明的成型体构成的层,使其他的层为与由本发明的成型体构成的层不同的层。
本发明的成型体和层叠体例如可以用于拉窗用膜、袋、包装纸、照明用罩、隔扇等门用装饰膜、或包、文具等树脂制品等用途中。
作为上述照明用罩,例如可列举出荧光灯或白炽灯泡的罩等灯罩等。
实施例
以下,通过实施例对本发明进行说明。
以下示出各种物性值的测定方法及评价方法。
(1)贯通孔的面积率
将纵20cm×横20cm的膜试验片的表面用图像分析装置进行图像分析,将试验片的面积(400cm2)设为100%,求出贯通孔的面积率(单位:%)。
图像分析装置为SEIKO EPSON株式会社制的扫描仪GT-X970,将所得到的图像利用个人电脑的图像分析软件(旭化成株式会社制“A像くん”版本2.20)进行图像分析。
(2)算术平均粗糙度(Ra)及最大高度(Rmax)
按照JIS B0601-1982,测定成型体的Rmax及Ra。具体而言,使用三维表面粗糙度计(株式会社小坂研究所制SE-30KS),沿膜的MD方向、对2000μm的长度以0.5mm/秒的速度、沿膜的TD方向以10μm的间距测定100次,分析所得到的粗糙度曲线,求出Ra(单位为μm)及Rmax(单位为μm)。
使用触针前端半径为2μm、顶角为60°的金刚石触针,将测定张力设定为0.7mN,将截止值设定为0.08mm。
(3)熔融峰值温度(Tm)、玻璃化转变温度(Tg)
使用差示扫描型量热计(TA Instruments公司制MDSC),将试样10mg在氮气氛下220℃下进行5分钟热处理,之后,以冷却速度5℃/分钟冷却至-80℃,在-80℃下保温1分钟。接着,以加热速度5℃/分钟从-80℃加热至180℃而测定DSC曲线,将DSC曲线中峰高度最高的峰的峰顶点的温度作为熔融峰值温度,将表示伴随玻璃化转变行为的比热容变化的基线位移的拐点下的温度作为玻璃化转变温度。
(4)质地官能评价
让5名专门小组成员进行膜的质地官能评价,通过评价为日式的质地、且具备闪烁的光泽感和蕾丝般的透明感、整体为日式现代化的质地的人数,如下进行判定。
判定基准
等级A:评价为具有上述质地的专门小组成员为3名以上。
等级B:评价为具有上述质地的专门小组成员为1~2名。
等级C:评价为具有上述质地的专门小组成员为0名。
(5)目视评价
使用目视及倍率为10倍的放大镜观察膜。
观察的结果:
“到处存在贯通孔,在贯通孔的周边存在树脂密集而凸起那样的部分,该部分显示日本纸中的纤维互相缠绕那样的样子,看见为纤维状的部分也存在纤维以束状聚集或致密地互相缠绕那样的部分和不是这样的部分,是整体有凹凸、厚度不均的膜”的情况下,将目视评价结果设定为1,
“没有观察到日本纸中的纤维互相缠绕那样的模样或纤维的浓淡”的情况下,将目视评价结果设定为2。
(6)厚度
发泡片材的厚度使用尾崎制作所制线性量规(linear gauge)D-100S(测定压力3.5mN、测头直径5mm)进行测定,设为将在各片材中的任意的纵50mm横50mm内大概等间隔地对纵3点×横3点的9点的测定结果平均而得到的数值。
膜的厚度使用尾崎制作所制线性量规D-100S(测定压力3.5mN、测头直径5mm)进行测定,设为将在各膜中的任意的纵50mm横50mm内大概等间隔地对纵3点×横3点的9点的测定结果平均而得到的数值。另外,在测定前项的目视评价中为1的膜的厚度时,在测定范围内包含看见为纤维状的部分。
(7)松密度
关于发泡片材的松密度,测定纵50mm横50mm的片材重量,作为具有前项中测定的厚度的长方体的密度进行计算。
关于拉伸膜的松密度,测定纵50mm横50mm的膜重量,作为具有前项中测定的厚度的长方体的密度进行计算。
(8)发泡倍率
发泡片材的发泡倍率作为发泡片材中含有的树脂的密度除以前项中测定的发泡片材的松密度而得到的值求出。另外,“发泡片材中含有的树脂的密度”是由发泡片材中含有的各树脂的密度和各树脂的含量计算的重量平均值。其中,发泡剂母料中含有的树脂由于相对于发泡片材中含有的全部树脂量仅含有少量,所以在算出“发泡片材中含有的树脂的密度”时不作考虑。
[实施例1]
将下述丙烯树脂A(熔融峰值温度为132℃)50重量份、下述苯乙烯树脂(玻璃化转变温度为100℃)48重量份及下述发泡剂母料2重量份的粒料共混物通过Tanabe PlasticsMachinery株式会社制片材成型机(自由调节型单螺杆挤出机VS-40及片材加工机VFC40-252)的挤出机进行熔融混炼,将熔融混炼后的树脂组合物从T型模挤出并使其发泡,成形为发泡片材。在发泡片材成形时,将挤出机的螺杆旋转速度设定为50rpm,将挤出机温度设定为215℃,将线速度设定为1.0m/分钟。所得到的发泡片材的厚度为1.1mm,松密度为0.59g/cm3,发泡倍率为1.5倍。
丙烯树脂A:住友化学株式会社制Noblen S131[熔体质量流动速率(230℃,2.16kg):2g/10分钟、密度:0.890g/cm3]
苯乙烯树脂:Toyo Styrene株式会社制Toyo styrol HI H650[熔体质量流动速率(190℃,2.16kg):3.4g/10分钟、密度:0.870g/cm3]
发泡剂母料:三协化成(株)制Cellmic MB3274[发泡剂:碳酸氢钠及柠檬酸(发泡剂母料中的发泡剂的含量:40重量%)、树脂:低密度聚乙烯(发泡剂母料中的树脂的含量:60重量%)]
接着,将所得到的发泡片材通过双轴拉伸试验装置((株)东洋精机制作所制)以拉伸温度为130℃、纵向拉伸倍率为4倍及横向拉伸倍率为4倍(纵向拉伸倍率/横向拉伸倍率=1)的条件进行拉伸,得到开有孔的膜。所得到的膜的厚度为99μm,贯通孔的面积率为8.7%,Ra为1.29μm,Rmax为89.77μm,松密度为0.21g/cm3。所得到的膜的目视评价结果为1。膜的质地官能试验的结果为等级A。
[实施例2]
除了在发泡片材成形中,使用70重量份的丙烯树脂A、28重量份的苯乙烯树脂以外,与实施例1同样地实施,得到开有孔的膜。所得到的发泡片材的厚度为1.0mm,松密度为0.64g/cm3,发泡倍率为1.4倍。所得到的膜的厚度为102μm,贯通孔的面积率为12.6%,Ra为0.50μm,Rmax为14.75μm,松密度为0.19g/cm3。所得到的膜的目视评价结果为1。膜的质地的官能试验的结果为等级A。
[实施例3]
将下述丙烯树脂A(熔融峰值温度为132℃)70重量份、下述乙烯树脂A(熔融峰值温度为115℃)28重量份及下述发泡剂母料2重量份的粒料共混物通过Tanabe PlasticsMachinery株式会社制片材成型机(自由调节型单螺杆挤出机VS-40及片材加工机VFC40-252)的挤出机进行熔融混炼,将熔融混炼后的树脂组合物从T型模挤出并使其发泡,成形为发泡片材。在发泡片材成形时,将挤出机的螺杆旋转速度设定为50rpm,将挤出机温度设定为215℃,将线速度设定为0.5m/分钟。所得到的发泡片材的厚度为0.8mm,松密度为0.48g/cm3,发泡倍率为1.9倍。
丙烯树脂A:住友化学株式会社制Noblen S131[熔体质量流动速率(230℃,2.16kg):2g/10分钟、密度:0.890g/cm3]
乙烯树脂A:住友化学株式会社制Excellen VL-100[熔体质量流动速率(190℃,2.16kg):0.8g/10分钟、密度:0.900g/cm3]
发泡剂母料:三协化成(株)制Cellmic MB3274[发泡剂:碳酸氢钠及柠檬酸(发泡剂母料中的发泡剂的含量:40重量%)、树脂:低密度聚乙烯(发泡剂母料中的树脂的含量:60重量%)]
接着,将所得到的发泡片材通过双轴拉伸试验装置((株)东洋精机制作所制)以拉伸温度为130℃、纵向拉伸倍率为4倍及横向拉伸倍率为4倍(纵向拉伸倍率/横向拉伸倍率=1)的条件进行拉伸,得到开有孔的膜。所得到的膜的厚度为243μm,贯通孔的面积率为5.1%,Ra为1.46μm,Rmax为48.58μm,松密度为0.22g/cm3。所得到的膜的目视评价结果为1。膜的质地的官能试验的结果为等级A。
[实施例4]
除了在发泡片材成形中,将挤出机的螺杆旋转速度设定为30rpm、将线速度设定为1.0m/分钟以外,与实施例3同样地实施,得到开有孔的膜。所得到的发泡片材的厚度为0.9mm,松密度为0.38g/cm3,发泡倍率为2.4倍。所得到的膜的厚度为105μm,贯通孔的面积率为6.1%,Ra为2.17μm,Rmax为125.59μm,松密度为0.16g/cm3。所得到的膜的目视评价结果为1。膜的质地的官能试验的结果为等级A。
[比较例1]
除了在发泡片材成形中,将挤出机的螺杆旋转速度设定为80rpm以外,与实施例3同样地实施,得到膜。所得到的发泡片材的厚度为1.1mm,松密度为0.68g/cm3,发泡倍率为1.3倍。所得到的膜的厚度为155μm,贯通孔的面积率为0%,Ra为0.65μm,Rmax为16.27μm,松密度为0.37g/cm3。在所得到的膜中不存在贯通孔,目视评价结果为2。膜的质地的官能试验的结果为等级C。
[比较例2]
将下述丙烯树脂A(熔融峰值温度为132℃)70重量份、下述乙烯树脂A(熔融峰值温度为115℃)28.5重量份及下述发泡剂母料1.5重量份的粒料共混物通过Tanabe PlasticsMachinery株式会社制片材成型机(自由调节型单螺杆挤出机VS-40及片材加工机VFC40-252)的挤出机进行熔融混炼,将熔融混炼后的树脂组合物从T型模挤出并使其发泡,成形为发泡片材。在发泡片材成形时,将挤出机的螺杆旋转速度设定为65rpm,将挤出机温度设定为215℃,将线速度设定为0.8m/分钟。所得到的发泡片材的厚度为1.4mm,松密度为0.70g/cm3,发泡倍率为1.3倍。
丙烯树脂A:住友化学株式会社制Noblen S131[熔体质量流动速率(230℃,2.16kg):2g/10分钟、密度:0.890g/cm3]
乙烯树脂A:住友化学株式会社制Excellen VL-100[熔体质量流动速率(190℃,2.16kg):0.8g/10分钟、密度:0.900g/cm3]
发泡剂母料:三协化成(株)制Cellmic MB3274[发泡剂:碳酸氢钠及柠檬酸(发泡剂母料中的发泡剂的含量:40重量%)、树脂:低密度聚乙烯(发泡剂母料中的树脂的含量:60重量%)]
接着,将所得到的发泡片材通过双轴拉伸试验装置((株)东洋精机制作所制)以拉伸温度为130℃、纵向拉伸倍率为2倍及横向拉伸倍率为2倍(纵向拉伸倍率/横向拉伸倍率=1)的条件进行拉伸,得到开有孔的膜。所得到的膜的厚度为648μm,贯通孔的面积率为0.1%,Ra为1.45μm,Rmax为46.33μm,松密度为0.24g/cm3。所得到的膜的目视评价结果为2。膜的质地的官能试验的结果为等级C。
[实施例5]
除了在拉伸中,将拉伸倍率设定为纵向拉伸倍率3倍及横向拉伸倍率3倍(纵向拉伸倍率/横向拉伸倍率=1)以外,与比较例2同样地实施,得到开有孔的膜。所得到的膜的厚度为235μm,贯通孔的面积率为3.4%,Ra为1.19μm,Rmax为42.50μm,松密度为0.31g/cm3。所得到的膜的目视评价结果为1。膜的质地的官能试验的结果为等级A。
[实施例6]
除了在拉伸中,将拉伸倍率设定为纵向拉伸倍率5倍及横向拉伸倍率5倍(纵向拉伸倍率/横向拉伸倍率=1)以外,与比较例2同样地实施,得到开有孔的膜。所得到的膜的厚度为79μm,贯通孔的面积率为4.4%,Ra为0.96μm,Rmax为19.42μm,松密度为0.33g/cm3。所得到的膜的目视评价结果为1。膜的质地的官能试验的结果为等级A。
[实施例7]
除了在拉伸中,将拉伸倍率设定为纵向拉伸倍率6倍及横向拉伸倍率6倍(纵向拉伸倍率/横向拉伸倍率=1)以外,与比较例2同样地实施,得到开有孔的膜。所得到的膜的厚度为52μm,贯通孔的面积率为12.7%,Ra为0.56μm,Rmax为13.97μm,松密度为0.24g/cm3。所得到的膜的目视评价结果为1。膜的质地的官能试验的结果为等级A。
[表1]
[表2]

Claims (7)

1.一种成型体,其由热塑性树脂组合物形成,
按照JIS B0601-1982测定的成型体的表面粗糙度的最大高度Rmax和按照JIS B0601-1982测定的所述成型体的表面的算术平均粗糙度Ra满足下式(1):
9≤Rmax/(Ra+1)≤45 式(1)
当将所述成型体的表面积设为100%时,该成型体的贯通孔的面积率为1%以上且20%以下,
松密度为0.13g/cm3以上且0.50g/cm3以下。
2.根据权利要求1所述的成型体,其中,热塑性树脂组合物是含有2种不相容的热塑性树脂的组合物,当将热塑性树脂组合物中的热塑性树脂的总量设为100重量%时,所述2种不相容的热塑性树脂的合计量为90重量%以上。
3.根据权利要求2所述的成型体,其中,2种不相容的热塑性树脂为转变温度不同的2种不相容的热塑性树脂。
4.根据权利要求3所述的成型体,其中,转变温度不同的2种不相容的热塑性树脂中的转变温度较高的热塑性树脂即第一热塑性树脂(A)与转变温度较低的热塑性树脂即第二热塑性树脂(B)的转变温度的差为10℃以上且50℃以下,
当将所述第一热塑性树脂(A)和所述第二热塑性树脂(B)的合计量设为100重量%时,所述第一热塑性树脂(A)的含量为30重量%以上且90重量%以下,所述第二热塑性树脂(B)的含量为10重量%以上且70重量%以下。
5.根据权利要求1~4中任一项所述的成型体,其为具有10μm以上且1000μm以下的厚度的膜。
6.一种层叠体,其具有由权利要求1~5中任一项所述的成型体构成的层作为至少一个表层。
7.一种权利要求1~5中任一项所述的成型体的制造方法,其含有以下工序:将含有发泡剂的热塑性树脂组合物进行熔融挤出而制作发泡片材的发泡片材制作工序;和
将所述发泡片材制作工序中得到的发泡片材进行双轴拉伸的拉伸工序。
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