CN107614622A - 透明树脂组合物及其制造方法 - Google Patents
透明树脂组合物及其制造方法 Download PDFInfo
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Abstract
本发明的课题在于提供透明且耐热性优异,注射成型时没有外观不良的树脂组合物。该树脂组合物含有苯乙烯系树脂(A)和所述苯乙烯系树脂(A)以外的透明树脂(B),该苯乙烯系树脂(A)包括含有不饱和二羧酸酐系单体单元的共聚物,所述树脂组合物依据ASTM D1003测得的2mm厚的总透光率为88%以上,雾度为0.3%以下。苯乙烯系树脂(A)优选为含有苯乙烯系单体单元45~90质量%,以及不饱和二羧酸酐系单体单元、(甲基)丙烯酸系单体单元、(甲基)丙烯酸酯系单体单元等10~55质量%的共聚物,透明树脂(B)优选含有选自甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、以及苯乙烯-丙烯腈系共聚物中的至少1种。
Description
技术领域
本发明涉及透明树脂组合物及其制造方法。
背景技术
甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、苯乙烯-丙烯腈系共聚物等透明树脂被用于家电制品的部件、汽车部件、食品包装容器、建材、杂货等各种用途。另外,也发挥优异的透明性而用作光学膜、扩散板、导光板等液晶显示器用的光学构件。这些透明树脂的透明性等光学特性良好,但存在耐热性低等问题,仅应用于有限的用途。作为提高透明树脂的耐热性的技术,有专利文献1~2。
[现有技术文献]
[专利文献]
[专利文献1]WO2014/021264号公报
[专利文献2]WO2014/065129号公报
发明内容
发明要解决的问题
本发明的课题在于提供一种新型透明树脂组合物及其制造方法。
用于解决问题的方案
(1)一种树脂组合物,其含有苯乙烯系树脂(A)和上述苯乙烯系树脂(A)以外的透明树脂(B),该苯乙烯系树脂(A)包括含有不饱和二羧酸酐系单体单元的共聚物,该树脂组合物依据ASTM D1003测得的2mm厚的总透光率为88%以上,雾度为0.3%以下。
(2)如(1)所述的树脂组合物,其特征在于,苯乙烯系树脂(A)是含有苯乙烯系单体单元45~90质量%,以及选自不饱和二羧酸酐系单体单元、(甲基)丙烯酸系单体单元、(甲基)丙烯酸酯系单体单元和可与它们共聚的其它乙烯基系单体单元中的至少1种单体单元10~55质量%的共聚物。
(3)如(1)或(2)所述的树脂组合物,其特征在于,透明树脂(B)含有选自甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、和苯乙烯-丙烯腈系共聚物中的至少1种。
(4)如(1)~(3)中任一项所述的树脂组合物,其特征在于,苯乙烯系树脂(A)的含量为5~50质量%,透明树脂(B)的含量为95~50质量%。
(5)如(1)~(4)中任一项所述的树脂组合物,其特征在于,依据JIS K7206,以载荷50N、升温速度50℃/小时求出的苯乙烯系树脂(A)的维卡软化温度为110℃以上。
(6)一种成型体,是将(1)~(5)中任一项所述的树脂组合物注射成型而得到的。
(7)一种树脂组合物的制造方法,其具备如下工序:分别使用各自的定量给料机将包括含有不饱和二羧酸酐系单体单元的共聚物的苯乙烯系树脂(A)和上述苯乙烯系树脂(A)以外的透明树脂(B)供给至挤出机,进行熔融混炼。
(8)如(7)所述的树脂组合物的制造方法,其特征在于,苯乙烯系树脂(A)是含有苯乙烯系单体单元45~90质量%,以及选自不饱和二羧酸酐系单体单元、(甲基)丙烯酸系单体单元、(甲基)丙烯酸酯系单体单元和可与它们共聚的其它乙烯基系单体单元中的至少1种单体单元10~55质量%的共聚物。
(9)如(7)或(8)所述的树脂组合物的制造方法,其特征在于,透明树脂(B)含有选自甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、和苯乙烯-丙烯腈系共聚物中的至少1种。
(10)如(7)~(9)中任一项所述的树脂组合物的制造方法,其特征在于,苯乙烯系树脂(A)的含量为5~50质量%,透明树脂(B)的含量为95~50质量%。
(11)如(7)~(10)中任一项所述的树脂组合物的制造方法,其特征在于,依据JISK7206,以载荷50N、升温速度50℃/小时求出的苯乙烯系树脂(A)的维卡软化温度为110℃以上。
发明的效果
本发明的树脂组合物的透明性优异,因此对于要求耐热性和良好外观的家电制品的部件、汽车部件、建材、光学构件、食品容器等有用,特别是可得到注射成型时没有外观不良的成型体。
具体实施方式
<用语说明>
本申请说明书中,例如“A~B”是指A以上且B以下。
以下,对本发明的实施方式进行详细说明。
本发明的透明树脂组合物含有苯乙烯系树脂(A)和上述苯乙烯系树脂(A)以外的透明树脂(B),该苯乙烯系树脂(A)包括含有不饱和二羧酸酐系单体单元的共聚物,该树脂组合物依据ASTMD1003测得的2mm厚的总透光率为88%以上,雾度为0.3%以下。这种树脂组合物是通过分别使用各自的定量给料机将苯乙烯系树脂(A)和透明树脂(B)供给至挤出机并进行熔融混炼而得到的。
苯乙烯系树脂(A)是含有苯乙烯系单体单元和不饱和二羧酸酐系单体单元的共聚物,可以含有选自(甲基)丙烯酸系单体单元、(甲基)丙烯酸酯系单体单元和可与它们共聚的其它乙烯基系单体中的至少1种单体单元。作为苯乙烯系树脂(A),例如可举出苯乙烯-甲基丙烯酸甲酯-马来酸酐共聚物、苯乙烯-马来酸酐共聚物等。
苯乙烯系单体为苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、对甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、对叔丁基苯乙烯、α-甲基苯乙烯、α-甲基-对甲基苯乙烯等。其中优选苯乙烯。苯乙烯系单体可单独使用也可将2种以上并用。
不饱和二羧酸酐系单体为马来酸酐、衣康酸酐、柠康酸酐、乌头酸酐等。其中优选马来酸酐。不饱和二羧酸酐系单体可单独使用也可将2种以上并用。
(甲基)丙烯酸系单体单元为丙烯酸、甲基丙烯酸等,其中优选甲基丙烯酸。
(甲基)丙烯酸酯系单体单元例如为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸二环戊酯、甲基丙烯酸异冰片酯等各甲基丙烯酸酯单体;以及丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-甲基己酯、丙烯酸2-乙基己酯、丙烯酸癸酯等各丙烯酸酯单体。其中优选甲基丙烯酸甲酯单元。(甲基)丙烯酸酯单体可单独使用也可将2种以上并用。
作为可共聚的其它乙烯基系单体,可使用丙烯腈、甲基丙烯腈、乙基丙烯腈、富马腈等丙烯腈系单体、N-苯基马来酰亚胺等N-取代的马来酰亚胺系单体。
苯乙烯系树脂(A)的构成单元优选为苯乙烯系单体单元45~90质量%,以及选自不饱和二羧酸酐系单体单元、(甲基)丙烯酸系单体单元、(甲基)丙烯酸酯系单体单元和可与它们共聚的其它乙烯基系单体中的至少1种单体10~55质量%。更优选为苯乙烯系单体单元45~85质量%、不饱和二羧酸酐系单体单元10~30质量%、(甲基)丙烯酸酯系单体单元5~45质量%,这样耐热性与强度的平衡优异。各单体单元的组成分析是采用C-13NMR法在下述记载的测定条件下测得的值。
装置名:FT-NMRAVANCE300(BRUKER社制)
溶剂:氘代氯仿
浓度:14质量%
温度:27℃
累计次数:8000次
苯乙烯系树脂(A)的重均分子量(Mw)优选为5万~30万,更优选为10万~25万。若重均分子量(Mw)为5万~30万的范围,则强度与成型性的平衡优异,因而优选。重均分子量(Mw)可通过聚合工序中的聚合温度和聚合时间、聚合引发剂的种类和添加量、链转移剂的种类和添加量、聚合时使用的溶剂种类和量等进行控制。应予说明,重均分子量(Mw)是采用凝胶渗透色谱法(GPC)测定的聚苯乙烯换算的值,是下述记载的测定条件下的测定值。
装置名:SYSTEM-21Shodex(昭和电工社制)
柱:将3根PL gel MIXED-B串联
温度:40℃
检测:差示折射率
溶剂:四氢呋喃
浓度:2质量%
校正曲线:使用标准聚苯乙烯(PS)(PL社制)制作。
苯乙烯系树脂(A)的聚合方法可采用公知的方法。从工艺简单且生产率优异的方面考虑,优选自由基聚合法。
作为苯乙烯系树脂(A)的制造方法,可采用公知方法。例如可采用溶液聚合、本体聚合等进行制造。另外,可适用连续法、间歇法中的任一者。苯乙烯系单体与不饱和二羧酸酐系单体的共聚中,由于交替共聚性高,所以可通过边分批添加不饱和二羧酸酐系单体边聚合而使共聚组成均匀,因此优选溶液聚合。从不易生成副产物且不良影响小的观点考虑,溶液聚合的溶剂优选为非聚合性,例如为丙酮、甲基乙基酮、甲基异丁基酮、苯乙酮等酮类;四氢呋喃、1,4-二恶烷等醚类;苯、甲苯、二甲苯、氯苯等芳香族烃、N,N-二甲基甲酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮等。
苯乙烯系树脂(A)的溶液聚合或本体聚合中,可适用聚合引发剂、链转移剂,聚合温度优选为70~180℃的范围。聚合引发剂例如为过氧化二苯甲酰、过氧化苯甲酸叔丁酯、1,1-双(叔丁基过氧化)-2-甲基环己烷、叔丁基过氧化异丙基单碳酸酯、过氧化2-乙基己酸叔丁酯、过氧化乙酸叔丁酯、过氧化二异丙苯、乙基-3,3-二(叔丁基过氧化)丁酸酯等公知的有机过氧化物;偶氮二异丁腈、偶氮二环己烷腈、偶氮二甲基丙腈、偶氮二甲基丁腈等偶氮化合物,可使用其中的1种或者将2种以上组合使用。这些聚合引发剂也可以将2种以上并用。其中,优选使用10小时半衰期温度为70~110℃的有机过氧化物。链转移剂例如有正辛基硫醇、正十二烷基硫醇、叔十二烷基硫醇、α-甲基苯乙烯二聚物、硫代乙醇酸乙酯、柠檬烯、异松油烯等。
从苯乙烯系树脂(A)的聚合结束后的溶液除去未反応单体、溶液聚合所使用的溶剂等挥发成分的脱挥方法可采用公知方法。例如可使用带有预热器的真空脱挥槽、带通风口的脱挥挤出机。经脱挥的溶融状态的苯乙烯系树脂(A)可被转移至造粒工序,从多孔模呈线状挤出,采用冷切方式、空中热切方式、水中热切方式加工成颗粒形状。
从透明性的观点考虑,优选本发明中的苯乙烯系树脂(A)依据ASTM D1003测定的2mm厚的总透光率为88%以上,雾度为0.5%以下,更优选总透光率为90%以上,雾度为0.3%以下。通过以共聚物组成分布变小的方式进行聚合,可得到透明性优异的苯乙烯系树脂(A)。
依据JIS K7206,以载荷50N、升温速度50℃/小时求出的苯乙烯系树脂(A)的维卡软化温度优选为115℃以上,更优选为125℃以上。维卡软化温度越高,改善甲基丙烯酸树脂耐热性的效果越高而优选。苯乙烯系树脂(A)的维卡软化温度可通过不饱和二羧酸酐系单体单元、(甲基)丙烯酸系单体单元等耐热性单体的含量进行调整。
透明树脂(B)为透明,且在熔融混炼和成型加工时的温度下与苯乙烯系树脂(A)相溶的树脂,例如为甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、苯乙烯-丙烯腈系共聚物等。其中,甲基丙烯酸树脂的光学特性优异,因而优选。甲基丙烯酸甲酯-苯乙烯系共聚物系共聚物的构成单元优选为甲基丙烯酸甲酯单元70~97质量%、苯乙烯3~30质量%。苯乙烯-丙烯腈系共聚物的构成单元优选为苯乙烯70~85质量%、丙烯腈15~30质量%。甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、苯乙烯-丙烯腈系共聚物可使用市售的一般品。形状可以是颗粒状也可以是珠状,优选粒度分布均匀的形状。
从透明性的观点考虑,优选本发明中的透明树脂(B)依据ASTM D1003测定的2mm厚的总透光率为88%以上,雾度为0.5%以下,更优选总透光率为90%以上、雾度为0.3%以下。
苯乙烯系树脂(A)和透明树脂(B)需要分别使用各自的定量给料机供给至挤出机。对于挤出机的原料投入口,只要针对各种树脂分别使用各自的定量给料机,则可以为1处或者可以根据定量给料机数而设置多处。在将苯乙烯系树脂(A)和透明树脂(B)干混后,一次供给至于1处原料投入口设置有漏斗的挤出机的方法;或者将干混后的树脂一次供给至仅设置有1台定量给料机的挤出机的方法中,将得到的树脂组合物进行注射成型时,成型体的内部产生起伏而导致外观不良。该起伏是因折射率的不均匀性而引起的,因此当树脂组合物中苯乙烯系树脂(A)与透明树脂(B)的配合比例发生变动时就会产生起伏。在注射成型中,从浇口流入的溶融树脂一边像气球一样在流动方向上扩展一边填充于模具内,因此若配合比例发生变动,则会呈层状产生折射率不同的部分而观察到起伏。若起伏明显,则有时可看到条纹形状。另外,该条纹有时也被称为脈理。在干混后一次供给至挤出机的方法中,因苯乙烯系树脂(A)与透明树脂(B)间的形状差异、密度差异等,会产生偏析,从而配合比例发生变动。
苯乙烯系树脂(A)或透明树脂(B)在相溶的范围内可以使用2种以上,但需要分别使用各自的给料机。苯乙烯系树脂(A)与透明树脂(B)的供给比例只要在两者相溶的范围内,任意确定即可。
给料机是将颗粒状或珠状的原料树脂供给至挤出机的装置,可使用公知的挤出机,但必须定量供给原料,因此需要使用定量给料机。作为定量给料机,可例示失重式给料机、容积式给料机、重量式传送带给料机等,特别优选失重式给料机,供给精度优选为±1%以内。各给料机优选联动控制,优选相对于主给料机的供给量,其它给料机的供给量成为恒定比例的方式进行控制的方法。
供给至挤出机的原料树脂在挤出机内被连续熔融混炼,经多孔模呈线状挤出,采用冷切方式、空中热切方式、水中热切方式得到颗粒形状的树脂组合物。挤出机可使用公知装置,例如可举出双螺杆挤出机、单螺杆挤出机、多螺杆挤出机、带双轴转子的连续混炼机等。
在不损害透明性的范围内,树脂组合物中也可以配合抗氧化剂、紫外线吸收剂、光稳定剂、增塑剂、润滑剂、染料、阻燃剂等添加剂。
树脂组合物中的苯乙烯系树脂(A)、透明树脂(B)的含量分别优选为5~50质量%、95~50质量%,更优选为15~50质量%、85~50质量%,进一步优选为15~35质量%、85~65质量%。通过使苯乙烯系树脂(A)、透明树脂(B)的含量分别为5~50质量%、95~50质量%,可得到耐热性与表面硬度的平衡优异的透明树脂组合物。
从透明性的观点考虑,本发明中的树脂组合物依据ASTM D1003测得的2mm厚的总透光率为88%以上,雾度为0.3%以下。总透光率优选为90%以上。雾度优选为0.2%以下。苯乙烯系树脂(A)与透明树脂(B)彼此相溶,采用本发明的方法制造,由此可得到透明性优异的树脂组合物。
依据JIS K7206,以载荷50N、升温速度50℃/小时求出的树脂组合物的维卡软化温度优选为110℃以上,更优选为113℃以上,进一步优选为115℃以上。维卡软化温度越高,可应用的构件越多。
树脂组合物的成型方法可采用公知方法。例如可举出注射成型、加压成型、薄片成型等。特别是在注射成型中,成型体内部不会产生起伏状的成型不良,因此优选。起伏状的成型不良在厚度大的注射成型体中尤为显著,但本发明的树脂组合物即使厚度大的注射成型体也不会发生外观不良。
[实施例]
以下,使用实施例对详细内容进行说明,但本发明并不限定于以下实施例。
<苯乙烯系树脂(A)>
<苯乙烯系树脂(A-1)的制造例>
预先制备马来酸酐以成为20质量%浓度的方式溶解于甲基异丁基酮的20%马来酸酐溶液,以及过氧化2-乙基己酸叔丁酯以成为2质量%的方式稀释于甲基异丁基酮的2%过氧化2-乙基己酸叔丁酯溶液,用于聚合。向具备搅拌机的120升的高压釜中加入20%马来酸酐溶液3.6kg、苯乙烯24kg、甲基丙烯酸甲酯8.8kg、叔十二烷基硫醇20g,用氮气置换气相成分后,边搅拌边用40分钟升温至88℃。升温后保持88℃,同时以20%马来酸酐溶液2.7kg/小时,以及2%过氧化2-乙基己酸叔丁酯溶液375g/小时的分添速度,分别连续地用8小时持续添加。其后,停止2%过氧化2-乙基己酸叔丁酯溶液的分添,添加过氧化异丙基单碳酸叔丁酯40g。对于20%马来酸酐溶液,边维持2.7kg/小时的分添速度边以8℃/小时的升温速度用4小时升温至120℃。在分添量累积达到32.4kg的时刻停止20%马来酸酐溶液的分添。升温后,保持120℃1小时结束聚合。聚合液使用齿轮泵连续供给至双轴脱挥挤出机,对甲基异丁基酮和微量未反应单体等进行脱挥处理,呈线状挤出并切割,得到颗粒形状的苯乙烯系树脂(A-1)。将所得A-1采用C-13NMR法进行组成分析。进一步用GPC装置进行分子量测定。实施组成分析的结果是,A-1的构成单元为苯乙烯单体单元60质量%、甲基丙烯酸甲酯单体单元22%、马来酸酐单体单元18质量%。另外,重均分子量(Mw)为16万,与数均分子量(Mn)的比Mw/Mn为2.4。注射成型中成型的2mmt镜面板的总透光率为91%、雾度为0.2%。依据JIS K7206,以载荷50N、升温速度50℃/小时求出的维卡软化温度为133℃。
<苯乙烯系树脂(A-2)的制造例>
20%马来酸酐溶液和2%过氧化2-乙基己酸叔丁酯溶液与A-1同样地制备。向具备搅拌机的120升的高压釜中加入20%马来酸酐溶液2.8kg、苯乙烯25.6kg、甲基丙烯酸甲酯8.8kg、叔十二烷基硫醇20g,用氮气置换气相成分后,边搅拌边用40分钟升温至88℃。升温后边保持88℃,边以20%马来酸酐溶液2.1kg/小时,以及2%过氧化2-乙基己酸叔丁酯溶液500g/小时的分添速度分别连续地用8小时持续添加。其后,停止2%过氧化2-乙基己酸叔丁酯溶液的分添,添加过氧化异丙基单碳酸叔丁酯40g。对于20%马来酸酐溶液,维持2.1kg/小时的分添速度,同时以8℃/小时的升温速度用4小时升温至120℃。在分添量累积达到25.2kg的时刻停止20%马来酸酐溶液的分添。升温后,保持120℃1小时结束聚合,将所得聚合液使用齿轮泵连续供给至双轴脱挥挤出机,对甲基异丁基酮和微量未反应单体等进行脱挥处理,呈线状挤出并切割,得到颗粒形状的苯乙烯系树脂(A-2)。对所得A-2与A-1同样地进行组成分析,测定分子量和总透光率。实施组成分析的结果是,A-2的构成单元为苯乙烯单体单元64质量%、甲基丙烯酸甲酯单体单元22%、马来酸酐单体单元14质量%。另外,重均分子量(Mw)为17万,与数均分子量(Mn)的比Mw/Mn为2.6。注射成型中成型的2mmt镜面板的总透光率为91%,雾度为0.2%。依据JIS K7206,以载荷50N、升温速度50℃/小时求出的维卡软化温度为126℃。
<苯乙烯系树脂(A-3〉的制造例>
预先制备马来酸酐以成为25质量%浓度的方式溶解于甲基异丁基酮的25%马来酸酐溶液,用于聚合。2%过氧化2-乙基己酸叔丁酯溶液与(A-1)的制造例同样地制备,用于聚合。向具备搅拌机的120升的高压釜中加入25%马来酸酐溶液3.52kg、苯乙烯24kg、甲基丙烯酸甲酯7.2kg、叔十二烷基硫醇20g,用氮气置换气相成分后,边搅拌边用40分钟升温至92℃。升温后保持92℃,同时分别开始连续添加25%马来酸酐溶液、2%过氧化2-乙基己酸叔丁酯溶液。25%马来酸酐溶液按如下方式分阶段改变分添速度:从开始分添至第4小时为3.96kg/小时、第4小时~第7小时为3.17kg/小时、第7小时~第10小时为1.58kg/小时、第10小时~第13小时为0.54kg/小时,合计添加31.71kg。2%过氧化2-乙基己酸叔丁酯溶液按如下方式分阶段改变分添速度:从开始分添至第7小时为0.24kg/小时、第7小时~第13小时为0.39kg/小时,合计添加4.02kg。聚合温度从分添开始到第7小时保持92℃,其后以4℃/小时的升温速度用6小时升温至116℃,再保持116℃1小时结束聚合。聚合液使用齿轮泵连续供给至双轴脱挥挤出机,对甲基异丁基酮和微量未反应单体等进行脱挥处理,呈线状挤出并切割,得到颗粒形状的苯乙烯系树脂(A-3)。对所得A-3与A-1同样地测定组成分析、分子量、和总透光率。实施组成分析的结果是,A-3的构成单元为苯乙烯单体单元60质量%、甲基丙烯酸甲酯单体单元18%、马来酸酐单体单元22质量%。另外,重均分子量(Mw)为16万,与数均分子量(Mn)的比Mw/Mn为2.4。注射成型中成型的2mmt镜面板的总透光率为90%,雾度为0.2%。依据JIS K7206,以载荷50N、升温速度50℃/时间求出的维卡软化温度为142℃。
<透明树脂(B)>
<透明树脂(B-1)>
作为透明树脂(B-1),使用甲基丙烯酸树脂(三菱丽阳株式会社制ACRYPET VH)。依据JIS K7206,以载荷50N、升温速度50℃/小时求出的维卡软化温度为108℃。
<透明树脂(B-2)>
作为透明树脂(B-2)使用甲基丙烯酸甲酯单元80质量%、苯乙烯单元20质量%的甲基丙烯酸甲酯-苯乙烯系共聚物。依据JIS K7206,以载荷50N、升温速度50℃/小时求出的维卡软化温度为104℃。
<实施例1~6、比较例1~6>
使用挤出机按表1所示的组成对苯乙烯系树脂(A)和透明树脂(B)进行熔融混炼,得到树脂组合物。在实施例1~6中,分别使用各自的定量给料机将苯乙烯系树脂(A)和透明树脂(B)供给至挤出机。透明树脂(B)的供给量在实施例1~3设定为15kg/hr、实施例4中设定为19kg/hr、实施例5中设定为10kg/hr、实施例6中设定为15kg/hr,控制苯乙烯系树脂(A)的供给量为表1的配合比例(合计供给量为20kg/hr)。定量给料机使用失重式给料机(株式会社久保田制CE-W-1)。在比较例1~6中,将苯乙烯系树脂(A)和透明树脂(B)的颗粒按表1的配合比例干混后,使用同一给料机供给至挤出机。干混后的颗粒的供给量设定为20kg/hr。挤出机使用双螺杆挤出机(东芝机械株式会社制TEM-26SX),料筒温度设定为240℃,螺杆转速设定为250rpm。在挤出机中熔融混炼后,经多孔模呈线状挤出,采用冷切方式得到颗粒形状的树脂组合物。对所得树脂组合物进行以下评价。将评价结果示于表1。
(维卡软化点)
维卡软化点依据JIS K7206:1999,采用50法(载荷50N、升温速度50℃/小时),使用10mm×10mm、厚4mm的试验片测定。应予说明,测定机使用株式会社东洋精机制作所制的HDT&VSPT试验装置。
(总透光率、雾度)
关于总透光率和雾度,依据ASTM D1003,使用雾度计(日本电色工业株式会社制NDH-1001DP型),对使用注射成型机(东芝机械株式会社制IS-50EPN),在料筒温度240℃、模具温度70℃的成型条件下成型得到的纵90mm、横55mm、厚2mm的镜面板进行测定。
(有无外观不良)
使用注射成型机(株式会社日本制钢所制J140AD-180H),在料筒温度250℃、模具温度70℃的成型条件下将纵127mm、横127mm、厚6mm的镜面板成型,确认有无起伏状的外观不良。
[表1]
在将苯乙烯系树脂(A)和透明树脂(B)分别给料的实施例中,没有起伏状的外观不良,外观、透明性和耐热性优异。但在以干混一次给料的比较例中,产生起伏状的外观不良。
产业上的可利用性
本发明的树脂组合物透明且外观优异、耐热性优异,所以对于家电制品的部件、汽车部件、建材、光学构件、食品容器等有用。特别是没有注射成型中的外观不良,可优选使用。
Claims (11)
1.一种树脂组合物,其含有苯乙烯系树脂(A)和所述苯乙烯系树脂(A)以外的透明树脂(B),所述苯乙烯系树脂(A)包括含有不饱和二羧酸酐系单体单元的共聚物,所述树脂组合物依据ASTM D1003测得的2mm厚度的总透光率为88%以上,雾度为0.3%以下。
2.根据权利要求1所述的树脂组合物,其特征在于,所述苯乙烯系树脂(A)是含有苯乙烯系单体单元45~90质量%,以及选自不饱和二羧酸酐系单体单元、(甲基)丙烯酸系单体单元、(甲基)丙烯酸酯系单体单元和可与它们共聚的其它乙烯基系单体单元中的至少1种单体单元10~55质量%的共聚物。
3.根据权利要求1或2所述的树脂组合物,其特征在于,所述透明树脂(B)含有选自甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、和苯乙烯-丙烯腈系共聚物中的至少1种。
4.根据权利要求1~3中任一项所述的树脂组合物,其特征在于,所述苯乙烯系树脂(A)的含量为5~50质量%,所述透明树脂(B)的含量为95~50质量%。
5.根据权利要求1~4中任一项所述的树脂组合物,其特征在于,依据JISK7206,以载荷50N、升温速度50℃/小时求出的所述苯乙烯系树脂(A)的维卡软化温度为110℃以上。
6.一种成型体,是将权利要求1~5中任一项所述的树脂组合物注射成型而得到的。
7.一种树脂组合物的制造方法,具备如下工序:
分别使用各自的定量给料机将包括含有不饱和二羧酸酐系单体单元的共聚物的苯乙烯系树脂(A)和所述苯乙烯系树脂(A)以外的透明树脂(B)供给至挤出机,进行熔融混炼。
8.根据权利要求7所述的树脂组合物的制造方法,其特征在于,所述苯乙烯系树脂(A)是含有苯乙烯系单体单元45~90质量%,以及选自不饱和二羧酸酐系单体单元、(甲基)丙烯酸系单体单元、(甲基)丙烯酸酯系单体单元和可与它们共聚的其它乙烯基系单体单元中的至少1种单体单元10~55质量%的共聚物。
9.根据权利要求7或8所述的树脂组合物的制造方法,其特征在于,所述透明树脂(B)含有选自甲基丙烯酸树脂、甲基丙烯酸甲酯-苯乙烯系共聚物、以及苯乙烯-丙烯腈系共聚物中的至少1种。
10.根据权利要求7~9中任一项所述的树脂组合物的制造方法,其特征在于,所述苯乙烯系树脂(A)的含量为5~50质量%,所述透明树脂(B)的含量为95~50质量%。
11.根据权利要求7~10中任一项所述的树脂组合物的制造方法,其特征在于,依据JISK7206,以载荷50N、升温速度50℃/小时求出的所述苯乙烯系树脂(A)的维卡软化温度为110℃以上。
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TW200936671A (en) * | 2007-12-28 | 2009-09-01 | Jsr Corp | Injection molded body and polymer composition |
JP2009282146A (ja) * | 2008-05-20 | 2009-12-03 | Asahi Kasei E-Materials Corp | 機械強度に優れた光学フィルム |
JP2010070646A (ja) * | 2008-09-18 | 2010-04-02 | Asahi Kasei Chemicals Corp | 光学材料用樹脂組成物 |
CN104540860A (zh) * | 2012-07-30 | 2015-04-22 | 电气化学工业株式会社 | 用于提高甲基丙烯酸类树脂耐热性的共聚物 |
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