CN1884371B - 生物降解性树脂组合物及薄膜或片材 - Google Patents
生物降解性树脂组合物及薄膜或片材 Download PDFInfo
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- CN1884371B CN1884371B CN2006100747157A CN200610074715A CN1884371B CN 1884371 B CN1884371 B CN 1884371B CN 2006100747157 A CN2006100747157 A CN 2006100747157A CN 200610074715 A CN200610074715 A CN 200610074715A CN 1884371 B CN1884371 B CN 1884371B
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Abstract
本发明提供一种具有透明性、柔软性、耐候性，无通过经时的防雾剂渗出的透明性阻碍，且具有优良防雾持续性的对环境负荷较小的生物降解性树脂组合物，及适用于农业、食品包装的薄膜或片材。所述生物降解性树脂组合物中，相对于100质量份的生物降解性聚酯树脂，含有0.1～5.0质量份的作为防雾剂的选自山梨糖醇、山梨糖醇酐、聚甘油的醇类(含脱水缩合醇类、多元醇的环氧烷加成物)与脂肪酸的酯、及0.05～2.5质量份的磺酸盐系表面活性剂。
Description
技术领域
本发明是关于透明性及防雾性优良的生物降解性树脂组合物及薄膜或片材，更详细为适合作为农业用或食物包装材料的生物降解性树脂组合物及薄膜或片材。
背景技术
现今日常生活中，聚乙烯、聚苯乙烯、聚丙烯或聚氯乙烯等塑料(合成树脂)广泛被利用于食品包装、建材材料或家电制品等各种领域中，于日常生活不可或缺。
作为塑料的主要特征，可举出耐久性，但使用后成为废弃物时，因其具有良好的耐久性，故于自然界中的分解性差，具有成为对生物系造成影响等环境破坏的原因的负面影响。
欲克服塑料所具有的这些缺点，焦点着重于生物降解性塑料(生物降解性树脂组合物)。近年来对于环境问题的意识逐渐提高使得塑料制品的回收成为法规化，可回收、重复使用的同时，环境中容易分解的所谓生物降解性塑料受到注目，政府民间皆致力于此研究、开发上。作为其用途，特别可期望于环境中所使用的农业用薄膜、片材、或要求高安全性的食品包装薄膜、片材的利用。
作为农业用薄膜，生物降解性塑料虽开始应用于农业用复合薄膜等，但对于农业用屋或被覆材料等薄膜、片材，追求一种可满足机械物性、透明性、耐候性及防雾性等性能的树脂。
欲改善柔软性、耐冲击性，已知有添加特定比率的聚乳酸与生物降解性聚酯的生物降解性农业用薄膜的制法(例如参照专利文献1、2)，但其透明性皆低，无法作为农业用屋或被覆材料利用。
农业用屋或被覆材料等用途中，欲防止于塑料表面的水滴附着所引起的日照阻碍或水滴脱落所引起的对农作物的伤害，一般添加畅流剂或防雾剂。以改善透明性、防雾性为目的，已知有生物降解性脂肪族芳香族聚酯树脂中加入少量的聚对苯二甲酸丁二醇酯树脂的方法(例如参照专利文献3)，同一专利文献中所记载的含有防雾剂的薄膜，防雾剂会严重渗出，薄膜制造后数日，薄膜会白浊化，实用困难。又，已知于聚乳酸系薄膜中并用润滑剂与作为防雾剂的非离子系表面活性剂(例如参照专利文献4)时并未能得到令人满意的防雾性。
[专利文献1]特开2004-147613公报
[专利文献2]特开2003-105183公报
[专利文献3]特开2004-352799公报
[专利文献4]特开平9-286908公报
发明内容
通过将本发明的特定防雾剂含于生物降解性聚酯树脂中，可提供一种不会产生因防雾剂的渗出所引起的透明性阻碍、初期防雾性或防雾持续性优良的透明且柔软的生物降解性树脂组合物、及经成型所成的适用于农业用薄膜、食品包装用的薄膜或片材。
本发明的目的为具有透明性、柔软性、耐候性，无经时的防雾剂渗出引起的透明性阻碍，且具有优良的防雾持续性的对环境负荷较小的生物降解性树脂组合物、及适用于农业、食品包装的薄膜或片材。
欲解决上述课题，本发明具有以下的构成。
1.一种生物降解性树脂组合物，其特征为，对于100质量份的生物降解性聚酯树脂而言，含有0.1～5.0质量份的作为防雾剂的选自山梨糖醇、山梨糖醇酐、聚甘油的醇类(含脱水缩合醇类、多元醇的环氧烷加成物)与脂肪酸的酯类、及0.05～2.5质量份的磺酸盐系表面活性剂。
2.如前述1的生物降解性树脂组合物，其中生物降解性聚酯树脂为缩聚含有乙二醇、1，4-丁二醇中至少一种的二醇、与含有对苯二甲酸、己二酸中至少一种的二羧酸所成的聚酯。
3.如前述1的生物降解性树脂组合物，其中生物降解性聚酯树脂为乳酸系聚酯。
4.如前述1至3中任一项的生物降解性树脂组合物，其中经脂肪酸酯化的羟基在多元醇的羟基中所占的比率作为酯化率时，该酯化率为10～90％。
5.一种薄膜或片材，其特征为由如前述1至4中任一项的生物降解性树脂组合物成型得到。
对本发明作更详细说明。
本发明将生物降解性聚酯系树脂作为对象。作为生物降解性聚酯树脂，可使用公知者。聚酯的结构可大致分为，作为单体使用二醇与二羧酸经交互聚合者、与羟基羧酸的聚合物。作为可使用于本发明的聚酯的单体的二醇，可举出乙二醇、丙二醇、1，3-丙二醇、1，3-丁二醇、1，4-丁二醇、新戊二醇、1，6-己二醇、1，4-苯二甲醇、这些的聚合物等。作为二羧酸，可举出琥珀酸、草酸、丙二酸、马来酸、富马酸、己二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、间苯二甲酸、对苯二甲酸等。作为羟基羧酸，可举出L-乳酸、D-乳酸、乙醇酸、3-羟基丁酸、4-羟基丁酸、3-羟基戊酸、4-羟基戊酸、6-羟基己酸等。这些可单独或组合2种以上使用。
这些单体只要具有生物降解性，可以并无特别限定地进行选择。本发明中，以使用时防止水滴附着引起的雾为目的，以透明性高的聚酯为佳。缩聚作为二醇含有乙二醇、1，4-丁二醇中至少一种、与作为二羧酸含有对苯二甲酸、己二酸中至少一种得到的物质，因平衡性良好地兼具机械物性、透明性、生物降解性，故较佳。
本发明的生物降解性聚酯树脂以乳酸系聚酯为佳，可为以聚乳酸为对象的物质。
所使用的聚乳酸树脂的聚合度或质量皆无限定。即使使用于聚乳酸树脂的乳酸单体为D异构物或L异构物，皆可无特别限定地使用。又，不仅为只是L-乳酸或D-乳酸所构成的聚合物，亦可并用乙二醇酸、ε-己内酯、碳酸1，3-亚丙酯或聚乙二醇等共聚物。又，在不损害聚乳酸树脂的物性范围内，可添加乙酸纤维素、聚己内酯、聚琥珀酸丁二酯、聚羟基丁酸酯与戊酸酯的共聚物、甲壳质、壳聚糖或淀粉等其它生物降解性高分子。
又，在不损害本发明的目的范围，可并用上述以外的共聚物。例如乙烯·甲基丙烯酸缩水甘油酯共聚物以相对聚乳酸为4∶1的比率混合，可提高耐冲击性。
作为本发明所使用的生物降解性聚酯树脂的制造方法，虽无特别限定，但可使用公知方法。例如可举出二醇与二羧酸的直接缩聚或羟基羧酸的直接缩聚、使用羟基羧酸的环状物或环状二聚体的开环聚合等。聚合时可共聚合甘油、聚甘油、季戊四醇、柠檬酸、酒石酸、苹果酸等多官能单体后导入支链。又，作为扩链剂，可使用异氰酸酯化合物、环氧化合物、氮杂环丙烷化合物、碳化二亚胺化合物、噻唑啉化合物、偶氮化合物、多价金属化合物、多官能磷酸酯、亚磷酸酯等。
本发明所使用的防雾剂由组合多元醇与脂肪酸所成的酯类与磺酸盐系表面活性剂构成。作为可使用于多元醇与脂肪酸所成的酯类的多元醇，可举出乙二醇、丙二醇、isosorbide(商品名)、甘油、三羟甲基丙烷、赤藓醇、季戊四醇、山梨糖醇酐、木糖醇、山梨糖醇、蔗糖等。又亦可使用这些多元醇的脱水缩合醇。作为脱水缩合醇，可举出聚甘油、聚季戊四醇等。
且，可使用对于这些多元醇加成环氧烷的醇类。这些多元醇可使用2种以上。其中山梨糖醇、山梨糖醇酐、聚甘油、山梨糖醇环氧乙烷加成物、山梨糖醇酐环氧乙烷加成物、山梨糖醇酐环氧丙烷加成物、聚甘油环氧乙烷加成物等与脂肪酸的酯类具有优良的初期防雾性、持续防雾性，透明性阻碍较少且安全性亦高，故较为佳。
作为可使用于多元醇与脂肪酸所成的酯类的脂肪酸虽无特别限定，但可使用辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸等饱和脂肪酸、油酸、亚油酸、亚麻酸、芥酸等不饱和脂肪酸。这些脂肪酸可使用2种类以上的混合脂肪酸。
作为多元醇与脂肪酸所成的酯类可通过公知酯反应制得。例如多元醇与脂肪酸的直接酯化反应或多元醇与油脂的酯交换反应制造。本发明中原料的多元醇的羟基中通过脂肪酸酯化的羟基比率以酯化率表示时，酯化率为10％～90％为佳。更优选为10％～50％。酯化率比该范围低时，与树脂的相溶性会较低，容易渗出。另外酯化率高于此范围时，亲水性降低，难以表现防雾性。
作为本发明所使用的磺酸盐系表面活性剂，例如可举出十二烷基苯磺酸钠、十二烷基苯磺酸钙、烷基萘磺酸钠、α-烯烃磺酸钠、二辛基磺基琥珀酸钠、二己基磺基琥珀酸钠、双(十三烷基)磺基琥珀酸钠、磺基琥珀酸月桂基二钠、直链烷基苯磺酸钠、烷基磺酸钠等。其中烷基磺酸钠以可达到本发明的目的之观点来看，特别优选。
本发明中，多元醇与脂肪酸所成的酯类相对生物降解性聚酯系树脂的添加量为，对于100质量份的树脂而言为0.1～5质量份，较佳为0.5～3质量份的范围。若比此范围低时，本发明目的的性能会不充分，若高时，成型品的透明性会较差，会见到防雾剂的渗出。
本发明中，磺酸盐系表面活性剂对生物降解性聚酯系树脂的添加量为，对于100质量份的树脂而言为0.05～2.5质量份的范围。若比此范围低时，本发明目的的性能会不充分，若高时，成型品的物性或透明性会较差，会见到防雾剂的渗出。
又，本发明的生物降解性树脂组合物中可并用稳定剂、增塑剂、防静电剂、抗氧剂、润滑剂、滑动剂、防雾剂等的添加剂，这些添加剂可以在不阻碍本发明的效果的范围并用。
本发明中生物降解性树脂组合物可使用一般使用于塑料混炼的挤出机、班伯里混炼机等将树脂与防雾剂等的添加物进行混炼。进行聚合物掺合时使用双螺杆挤出机为佳。又，另外可通过做成预先含有高浓度添加剂的树脂组合物的母炼胶法，将添加剂添加于生物降解性树脂组合物中。做成的混炼物或母炼胶依规定浓度调配，通过T形模、吹塑等成型为片材、薄膜。对于薄膜，进行拉伸或无拉伸皆可。
实施例
以下举出实施例对本发明作详细说明，但本发明的型态并不限于此。
各评估项目之评估方法如以下说明。
评估方法为：把下述所示温度的水放入水槽中，于评估用的具有30度倾斜的100×100mm的带窗试验箱中，被覆做成的薄膜，从透明胶带封住，在下述条件下进行防雾性、薄膜的渗出、薄膜的透明性随时间的评估。
表1
<防雾性>
◎：无水滴
○：一部份有水滴
△：小水滴显著
×：全面有雾
<薄膜的渗出>
◎：无渗出
×：渗出许多
<薄膜的透明性>
◎：通过薄膜可明了见到水槽底部
×：薄膜呈白浊现象，模模糊糊能见到水槽底部
<试验试样>
树脂1
聚对苯二甲酸己二酸丁二醇酯BASF公司制作Ecoflex
树脂2
聚乳酸三井化学公司制作レイシアH-440
多元醇脂肪酸酯1
山梨糖醇酐单棕榈酸酯理研维他命公司制“リケマ一ルSP-250”酯化率约25％
多元醇脂肪酸酯2
山梨糖醇酐20EO三油酸酯理研维他命公司制“リケマ一ル0-852”酯化率约75％
多元醇脂肪酸酯3
二甘油单硬脂酸酯理研维他命公司制“リケマ一ルS-71-D”酯化率约30％
多元醇脂肪酸酯4
二甘油单油酸酯理研维他命公司制“リケマ一ル0-71-DE”酯化率约30％
多元醇脂肪酸酯5
十甘油十二油酸酯酯化率约为95％
制造例
将95.4g的十甘油、400g的油酸装入具备水分离器、温度计、氮气导入管、搅拌棒的500ml的四口烧瓶中，于无触媒下边吹入氮气边于230℃下进行20小时的酯化反应至酸价为10以下。反应终了后，冷却后得到463g的淡黄色液体。
多元醇脂肪酸酯6
十甘油单月桂酸酯理研维他命研制“ポエムJ-0021”酯化率约8％
磺酸盐系表面活性剂1
烷基磺酸钠东邦化学公司制“アンステツクスHT-100”
磺酸盐系表面活性剂2
二辛基磺基琥珀酸钠和光纯药制造“エ一ロゾルOT”
〔实施例1～6、比较例1～5、参考例1～2〕
欲防止树脂1经由水解而降低分子量，施予80℃、5小时的加热干燥处理使水分除去后，添加对于100质量份的树脂1的下述试验试样规定量(如表2所示)于各实施例及比较例中，使用双螺杆挤出机于160℃下制成挤出颗粒。使用该颗粒通过具备T形模的单螺杆挤出机制成厚度80μm的薄膜，进行下述的各评估。
表2
评估结果如表3(高温防雾性)、表4(低温防雾性)所示。
表3
表4
〔实施例7～12、比较例6～10、参考例3～4〕
欲防止树脂2经由水解而降低分子量，施予80℃、5小时的加热干燥处理使水分除去后，添加对于100质量份的树脂2的下述试验试样的规定量(如表5所示)于各实施例及比较例中，使用双螺杆挤出机于180℃下制成挤出颗粒。使用该颗粒通过具备T形模的单螺杆挤出机制成厚度80μm的薄膜，进行下述的各评估。
表5
评估结果如表6(高温防雾性)、表7(低温防雾性)所示。
表6
表7
产业上可利用性
通过使用添加本发明的防雾剂的生物降解性聚酯树脂成型薄膜或片材，可制造出适用于农业用、食品包装材料用的低温下或高温下皆具有长期稳定的防雾性、透明性、柔软性的薄膜或片材。
Claims (5)
1. 一种生物降解性树脂组合物，其特征为，对于100质量份的生物降解性聚酯树脂而言，含有0.1～5.0质量份的作为防雾剂的选自山梨糖醇、山梨糖醇酐、聚甘油的醇(含脱水缩合醇、多元醇的环氧烷加成物)与脂肪酸的酯、及0.05～2.5质量份的磺酸盐系表面活性剂。
2. 如权利要求1的生物降解性树脂组合物，其中生物降解性聚酯树脂为缩聚含有乙二醇、1，4-丁二醇中至少一种的二醇、与含有对苯二甲酸、己二酸中至少一种的二羧酸而得到的聚酯。
3. 如权利要求1的生物降解性树脂组合物，其中生物降解性聚酯树脂为乳酸系聚酯。
4. 如权利要求1-3中任一项的生物降解性树脂组合物，其中，以经脂肪酸酯化的羟基在多元醇的羟基中所占的比率作为酯化率时，该酯化率为10～90％。
5. 一种薄膜或片材，其特征为由如权利要求1-4中任一项的生物降解性树脂组合物成型得到。
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| JP2011207987A (ja) * | 2010-03-29 | 2011-10-20 | Sumitomo Chemical Co Ltd | 樹脂用の加工安定化剤、該加工安定化剤を含む樹脂組成物、および樹脂の加工安定性を向上させる方法 |
| CN103025803A (zh) | 2010-07-30 | 2013-04-03 | 东丽株式会社 | 聚乳酸系树脂片和成型品 |
| CN102794965B (zh) * | 2012-08-06 | 2015-01-07 | 宁波长阳科技有限公司 | 一种防雾聚酯薄膜及其制备方法 |
| JP6108899B2 (ja) * | 2013-03-25 | 2017-04-05 | シーアイ化成株式会社 | 生分解性ハウス・トンネル用フィルム |
| CN104513401B (zh) * | 2014-11-03 | 2018-07-03 | 中国科学院宁波材料技术与工程研究所 | 强亲水性聚对苯二甲酸乙二醇酯透明薄膜及其制备方法 |
| MX2019008268A (es) | 2017-01-11 | 2019-09-09 | Bostik Inc | Resinas termosellables extrudibles de copoliester antivaho. |
| KR102102303B1 (ko) * | 2018-11-16 | 2020-05-29 | 주식회사 그린케미칼 | 내열성과 투명성이 개선된 생분해성 시트 조성물 및 그 제조방법 |
| CN110079068A (zh) * | 2019-05-31 | 2019-08-02 | 淄博中南医药包装材料股份有限公司 | 100％生物降解防雾片及其制备方法 |
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