CN106573411B - 双轴拉伸片材及包装用容器 - Google Patents
双轴拉伸片材及包装用容器 Download PDFInfo
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- CN106573411B CN106573411B CN201580040372.XA CN201580040372A CN106573411B CN 106573411 B CN106573411 B CN 106573411B CN 201580040372 A CN201580040372 A CN 201580040372A CN 106573411 B CN106573411 B CN 106573411B
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
本发明提供一种双轴拉伸片材,其是对丙烯腈‑苯乙烯共聚物进行双轴拉伸而成的,并且共聚物中的丙烯腈单元的含量为10~40质量%,共聚物的重均分子量为10万~25万,多分散度为2.0~2.5,双轴拉伸片材的双轴拉伸的面倍率为4~10倍,MD方向及TD方向的最大取向缓和应力分别为0.2~0.6MPa,MD方向的最大取向缓和应力(a)与TD方向的最大取向缓和应力(b)之差的绝对值(︱a‑b︱)为0.3MPa以下,双轴拉伸片材中的硫含量为0ppm以上且小于100ppm,挥发性物质的含量为200~2000ppm。
Description
技术领域
本发明涉及双轴拉伸片材及包装用容器。
背景技术
双轴拉伸聚苯乙烯树脂片材由于透明性优异且刚性较高,因此经热成形而被广泛地使用于食品包装容器领域。然而,聚苯乙烯的树脂与烯烃系树脂相比,耐油性较低,因实施双轴拉伸而耐油性进一步下降。例如,若使油附着于聚苯乙烯树脂双轴拉伸片材上并长时间地维持该状态,则片材表面发生白化。尤其在具有被称为铰链的将盖部与主体部连结的接合部的食品容器的情况下,因对该接合部施加应力,故而容易因油附着而产生破裂。
进而,在便当盖容器用途中,通过在填充食材中所用的酱料类附着的状态下进行微波炉加热,由此发生白化、开孔,故而采用如下应对方法:在食材与盖之间夹持OPP膜而使酱料类不与盖接触。
然而,利用手工作业设置膜所导致的人工费提高、使用后的废弃物增加等成为聚苯乙烯系拉伸片材的问题。
因此,正在研究如下片材的使用,该片材使用作为耐油性较高的树脂的聚丙烯、聚对苯二甲酸乙二醇酯。然而,与聚苯乙烯系片材相比,聚丙烯片材的透明性较低、内容物的可视性较差。另外,由于为低刚性,故而存在如下课题:无法于店面堆层陈列,在进行微波炉加热后变形而盖脱落等。另外,聚对苯二甲酸乙二醇酯片材由于树脂的耐热性较低且为低刚性,故而存在若于60℃以上使用则可见明显变形等问题。由于这些原因,聚苯乙烯系片材可以说是适于兼具透明性、刚性、耐热性的食品包装用容器的片材,但是尤其要求改善耐油性。
因此,正在进行以下相关的研究:利用树脂改性对双轴拉伸聚苯乙烯树脂片材赋予耐油性。例如,在专利文献1中记载了如下内容:利用以苯乙烯系共聚物作为主体而成的苯乙烯系双轴拉伸片材,具有100℃以上的实用耐热性、且即便与该温度的食物油接触也不发生白化现象,上述苯乙烯系共聚物系包含4~20重量%的丙烯酸、甲基丙烯酸、或马来酸酐中的任一成分的与苯乙烯的共聚物。
另外,在专利文献2、3、4中公开了利用如下方式实现的耐油性提高方法:进行表层使用维氏软化点较低的树脂的多层共挤出,以适于中芯层的拉伸温度进行双轴拉伸,由此制作仅表层的取向缓和应力下降的片材。
另外,在专利文献5、6中公开了如下耐油性提高方法:在聚苯乙烯双轴拉伸片材的食品接触面上,层压包含聚丙烯、丙烯酸类树脂、非晶质聚对苯二甲酸乙二醇酯树脂那样的耐油性树脂的膜,由此使油与聚苯乙烯片材不直接接触。
另外,在专利文献7中公开了利用如下片材实现的耐油性提高,该片材是由作为耐油性高于聚苯乙烯的树脂的丙烯腈均聚物及包含90质量%以上的丙烯腈成分的共聚物得到的。
现有技术文献
专利文献
专利文献1:日本特开昭62-25031号公报
专利文献2:日本特开2005-35208号公报
专利文献3:日本特开2005-349591号公报
专利文献4:日本特开2007-277428号公报
专利文献5:日本专利4217591号公报
专利文献6:日本专利4812072号公报
专利文献7:日本特开昭59-106922号公报
发明内容
发明要解决的问题
然而,专利文献1中所公开的技术中,使丙烯酸、甲基丙烯酸、马来酸酐单体进行共聚,由此在进行熔融混炼时容易因酸的脱水反应而引起交联反应,产生凝胶,引起片材的外观不良。另外,各单体使耐热性提高,相反地有树脂变脆的缺点,为了实用作食品容器,必须将取向缓和应力设计得高。因此,高取向的拉伸片材对于油、热的收缩较大,且使白化增长。另外,取向变得越高则容器成形越困难。
另外,专利文献2~6中所公开的技术中,由膜的层压导致材料费、加工费等成本提高,或由于膜为不相容聚合物故无法再利用于透明品。进而,在进行热成型时,于同一温度下将软化点不同的树脂成形,故而存在外观不良、残留成形应变等问题。
另外,专利文献7中所公开的技术中,树脂强度高于聚苯乙烯树脂故难以热成型;在溶解于DMSO溶剂中而制作流延膜后,在水槽内将DMSO溶剂置换成水而制成水凝胶膜,由此进行片材化等,为非常复杂的制膜工序,故而生产率较低;或者残留溶剂、树脂的吸水等的管理困难,片材物性容易变动。
本发明的课题在于提供一种使用丙烯腈-苯乙烯共聚物,透明性、刚性、实用强度、耐热性、油接触条件下的耐白化性、耐化学品性、耐收缩性的平衡优异的双轴拉伸苯乙烯系片材及包装用容器。
用于解决问题的方案
即,本发明如下。
(1)一种双轴拉伸片材,其是对丙烯腈-苯乙烯共聚物进行双轴拉伸而成的,并且共聚物中的丙烯腈单元的含量为10~40质量%,共聚物的重均分子量为10万~25万,多分散度为2.0~2.5,双轴拉伸片材的双轴拉伸的面倍率为4~10倍,MD方向及TD方向的最大取向缓和应力分别为0.2~0.6MPa,MD方向的最大取向缓和应力(a)与TD方向的最大取向缓和应力(b)之差的绝对值(︱a-b︱)为0.3MPa以下,双轴拉伸片材中的硫含量为0ppm以上且小于100ppm,挥发性物质的含量为200~2000ppm。
(2)根据(1)所述的双轴拉伸片材,其中,在双轴拉伸片材的至少一个表面上还设置有防雾剂层,防雾剂层的表面的水接触角为5~15°。
(3)一种包装用容器,其是将(1)或(2)所述的双轴拉伸片材成形而成的,具备主体部、盖部、及将主体部与盖部彼此连结的铰链部。
(4)一种包装用容器,其是将(2)所述的双轴拉伸片材成形而成的,具备主体部、盖部、及将主体部与盖部彼此连结的铰链部,防雾剂层的表面为内容物接触面。
(5)根据(3)或(4)所述的包装用容器,其中,主体部为收纳食品的主体部,盖部闭合的状态下的铰链部的曲率半径为2~10mm。
发明的效果
根据本发明,提供一种使用丙烯腈-苯乙烯共聚物且透明性、刚性、实用强度、耐热性、油接触条件下的耐白化性、耐化学品性、耐收缩性的平衡优异的双轴拉伸苯乙烯系片材及包装用容器。
附图说明
图1为表示包装用容器的一个实施方式的立体图。
图2为图1的包装用容器的侧视图。
具体实施方式
以下,对本发明的实施方式进行说明。
本实施方式的丙烯腈-苯乙烯共聚物含有丙烯腈系单体单元(丙烯腈单元)及苯乙烯系单体单元(苯乙烯单元),例如可通过本体连续聚合而获得。丙烯腈-苯乙烯共聚物中的丙烯腈系单体单元的含量以构成共聚物的单体单元总量基准计为10~40质量%,优选为18~32质量%。若丙烯腈系单体单元的含量超过40质量%,则色相、外观、片材制膜性变差,若丙烯腈系单体单元的含量小于10质量%,则耐油性、外观、强度变差。
作为丙烯腈系单体单元,可列举丙烯腈、甲基丙烯腈等单元,优选为丙烯腈单元。这些丙烯腈系单体单元可为单独一种,也可为两种以上。
作为苯乙烯系单体单元,可列举苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、乙基苯乙烯、对叔丁基苯乙烯等单元,优选为苯乙烯单元。这些苯乙烯系单体单元可为单独一种,也可为两种以上。丙烯腈-苯乙烯共聚物中的苯乙烯系单体单元的含量以构成共聚物的单体单元总量基准计,例如只要为60~90质量%即可。
丙烯腈-苯乙烯共聚物根据需要也可含有能够共聚的乙烯基系单体单元。作为乙烯基系单体单元,例如可列举:丙烯酸、甲基丙烯酸、马来酸酐、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、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甲基丙烯酸酯;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、丙烯酸癸酯等单元。相对于苯乙烯系单体单元与丙烯腈系单体单元的合计100质量份,乙烯基系单体单元的含量只要低于10质量份即可。
在丙烯腈-苯乙烯共聚物中,根据需要也可含有公知的加强橡胶、例如丁二烯橡胶、苯乙烯-丁二烯橡胶、甲基丙烯酸甲酯-丁二烯-苯乙烯橡胶、乙烯-丙烯橡胶等。相对于苯乙烯系单体单元与丙烯腈系单体单元的合计100质量份,加强橡胶的含量优选低于10质量份。若橡胶成分的含量为10质量份以上,则透明性下降而不优选。
丙烯腈-苯乙烯共聚物是通过使丙烯腈系单体与苯乙烯系单体聚合而获得的。作为聚合方法,并无特别限定,为了减少臭气,优选本体连续聚合。
作为本体连续聚合法,可采用公知的例子,优选如下方法:相对于苯乙烯系单体与丙烯腈系单体的合计100质量份,添加10~40质量份的乙基苯、甲苯、甲基乙基酮等溶剂而进行聚合。
在进行聚合时,也可添加过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯、1,1-双(叔丁基过氧化)-3,3,5-三甲基环己烷、1,1-双(叔丁基过氧化)-环己烷、2,2-双(4,4-二-丁基过氧化环己基)丙烷、过氧化异丙基单碳酸叔丁酯、过氧化二叔丁基、过氧化二枯基、3,3-二-(叔丁基过氧化)丁酸乙酯等公知的有机过氧化物,另外,也可添加4-甲基-2,4-二苯基-1-戊烯、叔十二烷基硫醇、正十二烷基硫醇等公知的分子量调节剂。
聚合温度优选为80~170℃,进一步优选为100~160℃。
丙烯腈-苯乙烯共聚物的利用SEC法而测定的聚苯乙烯换算的重均分子量优选为10万~25万,进一步优选为15万~20万。若重均分子量小于10万,则因树脂的强度下降而片材强度、耐折性下降。若重均分子量为25万以上,则因粘度上升而可见片材制膜性、容器成形性的下降。
作为重均分子量(Mw)与数均分子量(Mn)之比的多分散度(Mw/Mn)优选为2.0~2.5,进一步优选为2.1~2.5。在多分散度小于2.0时,需要变更聚合方法、设备,树脂的生产率下降。在多分散度为2.5以上时,因低分子量成分增加导致强度下降或因高分子量成分增加导致粘度上升,故而加工性、耐油性下降。
需要说明的是,SEC测定以如下条件实施。
装置:昭和电工公司制造的Shodex“SYSTEM-21”
柱:PLgel MIXED-B
温度:40℃
溶剂:四氢呋喃
流量:1.0ml/分钟
检测:RI
浓度:0.2质量%
注入量:100μl
标准曲线:使用标准聚苯乙烯(Polymer Laboratories制造),将洗脱时间与溶出量的关系转换成分子量而求出各种平均分子量(重均分子量、数均分子量等)。
在丙烯腈-苯乙烯共聚物中,可单独或组合使用紫外线吸收剂、光稳定剂、及抗氧化剂。
作为紫外线吸收剂,可列举:2-(5’-甲基-2’-羟基苯基)苯并三唑、2-(5’-叔丁基-2’-羟基苯基)苯并三唑、2-[2’-羟基-3’,5’-双(α,α-二甲基苄基)苯基]苯并三唑、2-(3’,5’-二-叔丁基-2’-羟基苯基)苯并三唑、2-(3’-叔丁基-5’-甲基-2’-羟基苯基)-5-氯苯并三唑、2-(3’,5’-二-叔丁基-2’-羟基苯基)-5-氯苯并三唑、2-(3’,5’-二-叔戊基-2’-羟基苯基)苯并三唑、2-[3’-(3”,4”,5”,6”-四氢邻苯二甲酰亚胺甲基)-5’-甲基-2’-羟基苯基]苯并三唑、2,2’-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并三唑-2-基)苯酚]等苯并三唑系紫外线吸收剂;2-乙氧基-2’-乙基草酰双苯胺、2-乙氧基-5-叔丁基-2’-乙基草酰双苯胺及2-乙氧基-4’-异癸基苯基草酰双苯胺等草酰苯胺系紫外线吸收剂;2-羟基-4-正辛氧基二苯甲酮、2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-5-磺基二苯甲酮、2,2’-二羟基-4-甲氧基二苯甲酮、2,2’-二羟基-4,4’-二甲氧基二苯甲酮、2-羟基-4-甲氧基-2’-羧基二苯甲酮等二苯甲酮系紫外线吸收剂;水杨酸苯酯、水杨酸对叔丁基苯酯、水杨酸对辛基苯酯等水杨酸系紫外线吸收剂;2-氰基-3,3’-二苯基丙烯酸-2-乙基己酯、2-氰基-3,3’-二苯基丙烯酸乙酯等氰基丙烯酸酯系紫外线吸收剂;金红石型二氧化钛、锐钛矿型二氧化钛以及经氧化铝、二氧化硅、硅烷偶合剂及钛系偶合剂等表面处理剂处理所得的氧化钛等氧化钛系紫外线稳定剂等。
作为光稳定剂,有癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯、癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯、琥珀酸二甲酯-1-(2-羟基乙基)-4-羟基-2,2,6,6-四甲基哌啶缩聚物、聚[[6,(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亚氨基]六亚甲基[(2,2,6,6-四甲基-4-哌啶基)亚氨基]]及1-[2-[3-(3,5-二-叔丁基-4-羟基苯基)丙酰氧基]乙基]-4-[3-(3,5-二-叔丁基-4-羟基苯基)丙酰氧基]-2,2,6,6-四甲基哌啶等。
作为抗氧化剂,可列举:三乙二醇-双[3-(3-叔丁基-5-甲基-4-羟基苯基)丙酸酯]、2,4-双(正辛硫基)-6-(4-羟基-3,5-二-叔丁基苯氨基)-1,3,5-三嗪、季戊四醇四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、十八烷基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯、2,2-硫代双(4-甲基-6-叔丁基苯酚)及1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯等酚系抗氧化剂;3,3’-硫代二丙酸二-十三烷基-酯、3,3’-硫代二丙酸二月桂酯、3,3’-硫代二丙酸二-十四烷基-酯、3,3’-硫代二丙酸二硬脂酯、3,3’-硫代二丙酸二辛酯等硫系抗氧化剂;亚磷酸三壬基苯酯、4,4’-亚丁基-双(3-甲基-6-叔丁基苯基-二-十三烷基)亚磷酸酯、(十三烷基)季戊四醇亚磷酸酯、双(十八烷基)季戊四醇二亚磷酸酯、双(二-叔丁基苯基)季戊四醇二亚磷酸酯、双(二-叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、磷酸二壬基苯基辛酯、四(2,4-二-叔丁基苯基)1,4-亚苯基-二-磷酸酯、四(2,4-二-叔丁基苯基)4,4’-亚联苯基-二-磷酸酯、10-癸氧基-9,10-二氢-9-氧杂-10-磷杂菲等磷系抗氧化剂。
在丙烯腈-苯乙烯共聚物中,也可根据用途而在不损及本发明目的的范围内配混润滑剂、增塑剂、着色剂、抗静电剂、阻燃剂、矿物油等添加剂,玻璃纤维、碳纤维及芳族聚酰胺纤维等加强纤维,滑石、二氧化硅、云母、碳酸钙等填充剂。
本实施方式的双轴拉伸片材是将丙烯腈-苯乙烯共聚物双轴拉伸而成的。作为双轴拉伸片材的制造方法,例如为如下制造方法:利用挤出机对丙烯腈-苯乙烯共聚物进行熔融混炼并自模头(特别是T模头)中挤出,接着沿双轴方向依次或同时拉伸。双轴拉伸片材的厚度并无特别限定,通常为0.05mm以上且小于0.6mm,优选为0.1mm以上且小于0.5mm。
在将双轴拉伸片材的MD(Machine Direction;片材流动方向)拉伸倍率设为A、将TD(Transverse Direction;垂直于片材流动方向的方向)拉伸倍率设为B时,以A×B表示的面倍率优选为4~10倍。需要说明的是,在该面倍率中,MD拉伸倍率及TD拉伸倍率均优选为1.5~3.5倍。在A、B、A×B中的任一者为上述范围外的情况下,片材产生厚度不均,对该片材进行热板成形而获得的容器存在压曲强度下降的担心而不优选。需要说明的是,更优选面倍率为4~8倍、且MD拉伸倍率及TD拉伸倍率分别为2.0~3.0倍。
本发明中的拉伸倍率是双轴拉伸片材的试验片在加热前后变化的比率,具体而言是指利用下式、即拉伸倍率=Y/Z(单位[倍])而算出的值。在该式中,Y表示在加热前对双轴拉伸片材的试验片于MD及TD上所描绘的直线的长度[mm],Z表示在温度与依据JIS K7206所测定的片材的维氏软化点温度相比高30℃的烘箱内,将上述试验片静置60分钟而使其收缩后的上述直线的长度[mm]。
在双轴拉伸片材中,在将MD方向的最大取向缓和应力设为a、将TD方向的最大取向缓和应力设为b时,a、b分别为0.2MPa~0.6MPa,MD方向的最大取向缓和应力与TD方向的最大取向缓和应力之差的绝对值︱a-b︱为0.3MPa以下,优选a、b为0.3MPa~0.5MPa且︱a-b︱为0.15MPa以下。在a、b小于0.2MPa时,片材强度下降,耐折性变差。另外,超过0.6MPa时,收缩力变高,故而容易引起油附着时的白化,成形性下降等而不优选。若︱a-b︱超过0.3MPa,则MD、TD方向的收缩力不同,故容易发生成形性不良、成形品的应变而不优选。
在双轴拉伸片材中,可含有源自链转移剂、抗氧化剂的硫化合物,该硫成分的含量(硫含量)为0ppm以上且小于100ppm,优选为10~95ppm,更优选为30~70ppm。若硫含量为100ppm以上,则在热成形时产生源自硫化合物的臭气,使作业环境下降。硫含量可利用ICP-MS(电感耦合等离子体质谱仪)而测定。
双轴拉伸片材中的挥发性物质的含量优选为200~2000ppm。挥发性物质是指食品卫生法中所规定的挥发性物质。作为挥发性物质的具体例,可列举苯乙烯、甲苯、乙基苯、正丙基苯、异丙基苯、丙烯腈,挥发性物质的含量为这些挥发成分的总量。挥发性物质的含量通过变更聚合时的脱挥步骤的温度或调整时间而调整。在挥发性物质的含量低于200ppm时,需要设定为引起树脂的分解、变色等那样的高温,故而不优选,调整时间延长需要使生产率大幅地下降,故而不优选。若挥发性物质的含量超过2000ppm,则与硫成分同样地,在热成形时产生臭气等使作业环境下降。挥发性物质的含量可利用气相色谱法而测定。
关于丙烯腈-苯乙烯共聚物双轴拉伸片材,为了实现片材化,可以在进行熔融混炼时或原料制造时,在不损及本发明目的的范围内根据需要而含有抗氧化剂、润滑剂、脱模剂、增塑剂、颜料、染料、发泡剂、发泡成核剂、无机填料、抗静电剂等公知的添加剂。
利用对与食品接触的片材表面涂覆亲水性的防雾剂,即于双轴拉伸片材的至少一表面上进一步设置防雾剂层,可提高耐油性。
作为防雾剂,可列举:非离子性表面活性剂,例如蔗糖脂肪酸酯、山梨糖醇酐单硬脂酸酯、山梨糖醇酐单棕榈酸酯、山梨糖醇酐单山嵛酸酯、山梨糖醇酐单褐煤酸酯等山梨糖醇酐脂肪酸酯系表面活性剂,甘油单月桂酸酯、甘油单棕榈酸酯、甘油单硬脂酸酯、二甘油二硬脂酸酯、三甘油单硬脂酸酯、四甘油单褐煤酸酯等甘油脂肪酸酯系表面活性剂,聚乙二醇单棕榈酸酯、聚乙二醇单硬脂酸酯等聚乙二醇系表面活性剂,烷基苯酚的环氧烷加成物、山梨糖醇酐/甘油缩合物与有机酸的酯;聚氧乙烯(2摩尔)硬脂胺、聚氧乙烯(2摩尔)月桂胺、聚氧乙烯(4摩尔)硬脂胺等聚氧乙烯烷基胺化合物、聚氧乙烯(2摩尔)硬脂胺单硬脂酸酯、聚氧乙烯(2摩尔)硬脂胺二硬脂酸酯、聚氧乙烯(4摩尔)硬脂胺单硬脂酸酯、聚氧乙烯(4摩尔)硬脂胺二硬脂酸酯、聚氧乙烯(8摩尔)硬脂胺单硬脂酸酯、聚氧乙烯(2摩尔)硬脂胺单山嵛酸酯、聚氧乙烯(2摩尔)月桂胺硬脂酸酯等聚氧乙烯烷基胺化合物的脂肪酸酯,聚氧乙烯(2摩尔)硬脂酰胺等聚氧乙烯烷基胺化合物的脂肪酸酰胺等胺系表面活性剂等。作为防雾剂,除此之外可列举:聚乙烯醇及其共聚物(例如与丙烯酰胺、聚乙烯基吡咯烷酮的共聚物)、聚乙烯基吡咯烷酮及其共聚物(例如与乙酸乙烯酯的共聚物)、纤维素系衍生物(羟甲基纤维素、羟乙基纤维素等)、淀粉衍生物、明胶、阿拉伯胶、酪蛋白、黄原酸胶、糖原、甲壳素、壳聚糖、琼脂糖、卡拉胶、肝素、透明质酸、果胶、木葡聚糖、聚环氧乙烷、聚环氧丙烷、水溶性醇酸树脂、水溶性环氧树脂、水溶性酚醛树脂、水溶性脲树脂、水溶性三聚氰胺树脂、水溶性氨基树脂、水溶性聚酰胺树脂、水溶性丙烯酸类树脂、水溶性聚羧酸盐、水溶性聚酯树脂、水溶性聚氨酯树脂、水溶性多元醇树脂、或者对这些聚合物进行化学修饰所得的物质等所代表的水溶性高分子等。
作为将防雾剂涂覆至双轴拉伸片材上的方法,并无特别限定,简便而言可列举使用辊式涂布机、刮刀涂布机、凹版辊式涂布机等进行涂覆的方法。另外,也可采用喷雾、浸渍等。
防雾剂涂覆后的水接触角、即双轴拉伸片材的防雾剂层的表面的水接触角优选为5~15°。在水接触角小于5°时,存在表面成为粘着状态而容易产生成形时的外观不良、污物附着等问题。在水接触角为15°以上时,亲油性变高,无法获得作为保护膜的效果。水接触角可依据JIS R 3257而测定。
接着,对本实施方式的包装用容器进行说明。图1是表示包装用容器的一个实施方式的立体图,图2是该包装用容器的侧视图。如图1、2所示,包装用容器1具备可收纳内容物的主体部2、盖部3、及将主体部2与盖部3彼此连结的铰链部4。包装用容器1是将上述双轴拉伸片材成形而成的。盖部3可如图2(a)、(b)所示那样开闭。通过主体部2与盖部3例如彼此嵌合,从而形成盖部3闭合的状态(图2(b))。在双轴拉伸片材上设置有防雾剂层的情况下,优选防雾剂层的表面成为内容物接触面(在主体部2及盖部3的内侧配置防雾剂层的表面)。
盖部3闭合的状态(图2(b))下的铰链部4的曲率半径(自铰链部4延伸的方向观察铰链部4时的(图2(b)的侧视时的)铰链部4的曲率半径)优选为2~10mm。在盖部3闭合的状态下的铰链部4的曲率半径小于2mm时,铰链部4的应变增大,片材容易白化。在盖部3闭合的状态下的铰链部4的曲率半径超过10mm时,因形状不良、铰链部4的薄壁化而发生闭合盖部3时的嵌合不良。另外,因薄壁化而成为评价耐油性时产生破裂的原因。
包装用容器1可适宜地使用于食品包装用途、即以食品作为内容物(主体部2收纳食品)的用途。在将包装用容器1用于食品包装用途时,作为用于双轴拉伸片材的材料,优选使用食品添加物公定书、聚烯烃卫生协议会的肯定列表(positive list)中注册等的卫生性、稳定性得到认可的材料。
为了获得包装用容器1,例如只要使用市售的普通的热板压空成形机即可。使用的成形机理想的是如下类型的成形机:可设定在热板上压接片材的时间、利用压空进行成形的时间、自片材压接切换成压空成形的时滞、成形周期等。这些方法例如记载于高分子学会编“塑料加工技术手册”日刊工业报社(1995)。
实施例
以下示出所使用的丙烯腈-苯乙烯共聚物的实验例。
实验例1{丙烯腈-苯乙烯共聚物(AS-1)的制造}
将作为容积约20L的完全混合型搅拌槽的第一反应器与作为容积约40L的带有搅拌机的塔式活塞流型反应器的第二反应器串联,进而串联2个带有预热器的脱挥槽而构成。对由丙烯腈10质量%、苯乙烯90质量%构成的单体溶液85质量份,混合乙基苯15质量份、过氧化异丙基单碳酸叔丁酯0.01质量份、叔十二烷基硫醇0.25质量份而制成原料溶液。将该原料溶液以每小时6.0kg导入至控制在125℃的第一反应器中。自第一反应器中连续地提取反应液,将该反应液导入至朝流动方向以形成125℃至160℃的梯度的方式调整的第二反应器中。接着,利用预热器加热至160℃后,导入至减压至67kPa的第一脱挥槽中,进而利用预热器加热至230℃后,导入至减压至1.3kPa的第二脱挥槽中而去除残留单体及溶剂。将其以绳状挤出并切断,由此获得颗粒形状的丙烯腈-苯乙烯系共聚物(AS-1)。(AS-1)的组成如表1所记载为丙烯腈单元10质量%、苯乙烯单元90质量%,重均分子量为150000,多分散度为2.3。
实验例2~16{丙烯腈-苯乙烯共聚物(AS-2~16)的制造}
调整实验例1的各种原料投入量,获得表1所记载的丙烯腈-苯乙烯树脂(AS-2~16)。
<实施例1>
对丙烯腈-苯乙烯共聚物(a)使用片材挤出机(T模头宽度500mm、φ40mm的挤压机(田边塑料机械公司制造)),在挤出温度230℃下获得厚度为1.2mm的未拉伸片材。利用批次式双轴拉伸机(东洋精机)将该片材预热至140℃,以应变速度0.1/秒、以MD方向2.4倍、TD方向2.4倍(面倍率5.8倍)进行拉伸,获得厚度为0.21mm的双轴拉伸片材。进而,利用棒式涂布机以5g/m2涂覆1%蔗糖月桂酸酯(RIKEMAL A(第一工业制药株式会社制造)),利用105℃的烘箱干燥1分钟。干燥后的涂覆表面的水接触角为10度。该双轴拉伸片材的硫含量为50ppm,挥发性物质含量为1000ppm。
对所获得的片材利用以下方法进行物性测定、评价。结果记载于表2。
[拉伸倍率]
对于双轴拉伸片材的试验片,在MD及TD上引100mm的直线Y,在温度比依据JISK7206所测定的片材的维氏软化点温度高30℃的烘箱内,将上述试验片静置60分钟而使其收缩后,测定上述直线的长度Z[mm],利用下式、即拉伸倍率=Y/Z、单位[倍]而算出。
[最大取向缓和应力(耐收缩性)]
自双轴拉伸片材获得20mm×200mm×0.2mm的试验片。将该试验片的两端固定,浸渍于130℃的油浴中后,算出负载成为最大时的应力值。将此时的MD方向的应力值设为最大取向缓和应力a,将TD方向的应力值设为最大缓和应力b而求出︱a-b︱。
[硫含量]
利用ICP-MS(电感耦合等离子体质谱仪)而测定。
[挥发性物质含量]
将双轴拉伸片材粉碎,准确称量其约0.5g,溶解于四氢呋喃50ml中,添加二乙基苯标准液1ml,以四氢呋喃进行稀释并定容成20ml,利用气相色谱进行测定。
[水接触角]
依据JIS R 3257,利用接触角计DM-701(协和界面化学),试验液使用蒸馏水,滴加量为2μL,对自滴加后30秒后的接触角进行测定。
[树脂的生产率]
对于聚合中所使用的各单体,利用气相色谱法算出共聚物中的未反应单体,根据下式求出单体实际上聚合的比率(聚合率),评价树脂的生产率。
聚合率(%)=聚合物质量÷(聚合物质量+未反应单体的质量)×100
○:聚合率为90.0%~100%
△:聚合率为80.0%以上且小于90.0%
×:聚合率小于80%
[片材制膜性]
对将双轴拉伸片材在MD方向及TD方向上以50mm的间隔设为格子状时的交点25点使用测微计测定厚度,算出平均厚度及其标准偏差σ,对于厚度以数值进行评价,对于厚度不均以下述基准评价标准偏差σ,作为制膜性的评价。
○:σ小于0.03mm
△:σ为0.03mm以上且小于0.07mm
×:σ为0.07mm以上
[片材强度]
依据JIS K-6251,将双轴拉伸片材切割成1号型试验片(test piece)形状,使用岛津制作所AGS-100D型拉伸试验机以拉伸速度500mm/min进行测定并进行评价。
○:超过60MPa
△:40~60MPa
×:小于40MPa
[耐折性]
依据ASTM D2176,测定片材挤出方向(纵向)及垂直于该方向的方向(横向)的耐弯折强度。求出纵横的平均值而进行评价。
○:10次以上
△:5次以上且小于10次
×:小于5次
[透明性]
依据JIS K-7361-1利用雾度计NDH5000(日本电色公司)进行测定。在进行测定时,使用利用上述操作制作的0.21mm厚的双轴拉伸片材。
○:小于1.0%
△:1.0~2.0%
×:超过2.0%
[色相]
将10张厚度为0.21mm的拉伸片材重叠,利用分光测色计CM-2500d(KonicaMinolta,INC.)的SCI测定(包括正反射光)而获得的b值进行评价。
○:小于3
△:3~5
×:超过5
[成形性]
利用热板成形机HPT-400A(WAKISAKA ENGINEERING Co.,Ltd.制造),以热板温度135℃、加热时间2.0秒的条件成形嵌合食品包装(主体部尺寸为长130×宽110×深28mm,盖部尺寸为长130×宽110×高25mm,铰链部的曲率半径为3mm),对外观进行评价。另外,对闭合成形品的盖时的嵌合状态进行评价。
○:良好
△:轻微的白化、轻微的水滴
×:明显的白化、明显的水滴、形状不良、嵌合不良(偏移、脱落、变形)(无法制品化)
[容器成型时的臭气]
利用热板成型机HPT-400A(WAKISAKA ENGINEERING Co.,Ltd.制造),以热板温度135℃、加热时间2.0秒的条件成形10张嵌合食品包装后,对热板成型机周边的气氛的臭味进行感官评价。
○:无特异性的臭味
△:稍许感觉到异臭
×:感觉到刺鼻程度的臭味
[耐油性(耐化学品性)]
利用热板成型机HPT-400A(WAKISAKA ENGINEERING Co.,Ltd.制造)成形具有铰链部的嵌合食品包装,将10×10mm的渗入有色拉油(日清制油公司制造)、蛋黄酱(味之素公司制造)的试验液的纱布贴附至铰链部,在60℃烘箱内静置24小时并进行附着部的表面观察。
○:无变化
△:稍许有白化
×:有明显的白化、开孔
[微波炉耐性]
在嵌合食品包装盖部的内侧中央以2×2cm附着蛋黄酱,向容器主体中加入100g的水,闭合盖容器并利用1500W的微波炉加热30分钟后,对附着蛋黄酱的部分的状态进行目视评价。
○:无变化
△:容器稍许变形
×:有白化、有开孔、容器明显变形(无法制品化)
<实施例2~29>
利用与实施例1相同的方法,以表2、表3中记载的树脂、拉伸条件制作片材并进行评价。结果示于表2、表3。
<比较例1~18>
利用与实施例1相同的方法,以表4、表5中记载的树脂、拉伸条件制作片材并进行评价。结果示于表4、表5。
[表1]
[表2]
[表3]
[表4]
[表5]
如表所示,实施例所示的片材是各性能均良好且实现了平衡的片材,但比较例所示的片材是片材强度、耐折性、耐油性等部分特性不充分、实用性较低的片材。
产业上的可利用性
本发明的双轴拉伸片材的透明性、刚性、实用强度、耐热性、油接触条件下的耐白化性、耐化学品性、耐收缩性的平衡优异,可适宜地用作包装食品等的包装用容器。
附图标记说明
1 包装用容器、2 主体部、3 盖部、4 铰链部。
Claims (5)
1.一种双轴拉伸片材,其是对丙烯腈-苯乙烯共聚物进行双轴拉伸而成的,并且
所述共聚物中的丙烯腈单元的含量为10~40质量%,
所述共聚物的重均分子量为10万~25万,多分散度为2.0~2.5,
所述双轴拉伸片材的双轴拉伸的面倍率为4~10倍,MD方向及TD方向的最大取向缓和应力分别为0.2~0.6MPa,MD方向的最大取向缓和应力(a)与TD方向的最大取向缓和应力(b)之差的绝对值(︱a-b︱)为0.3MPa以下,
所述双轴拉伸片材中的硫含量为0ppm以上且小于100ppm,挥发性物质的含量为200~2000ppm,其中,
MD方向的最大取向缓和应力(a)及TD方向的最大取向缓和应力(b)的测定方法为:自双轴拉伸片材获得20mm×200mm×0.2mm的试验片,将该试验片的两端固定,浸渍于130℃的油浴中后,算出负载成为最大时的应力值,将此时的MD方向的应力值设为MD方向的最大取向缓和应力(a),将TD方向的应力值设为TD方向的最大缓和应力(b)。
2.根据权利要求1所述的双轴拉伸片材,其中,在所述双轴拉伸片材的至少一个表面上还设置有防雾剂层,所述防雾剂层的表面的水接触角为5~15°。
3.一种包装用容器,其是将权利要求1或2所述的双轴拉伸片材成形而成的,
所述包装用容器具备主体部、盖部、及将所述主体部与所述盖部彼此连结的铰链部。
4.一种包装用容器,其是将权利要求2所述的双轴拉伸片材成形而成的,
所述包装用容器具备主体部、盖部、及将所述主体部与所述盖部彼此连结的铰链部,
所述防雾剂层的表面为内容物接触面。
5.根据权利要求3或4所述的包装用容器,其中,所述主体部为收纳食品的主体部,
所述盖部闭合的状态下的所述铰链部的曲率半径为2~10mm。
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