CN116348535A - 生物降解性树脂水系分散体及其制造方法和使用了生物降解性树脂水系分散体的食品包装用纸 - Google Patents
生物降解性树脂水系分散体及其制造方法和使用了生物降解性树脂水系分散体的食品包装用纸 Download PDFInfo
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- CN116348535A CN116348535A CN202180068290.1A CN202180068290A CN116348535A CN 116348535 A CN116348535 A CN 116348535A CN 202180068290 A CN202180068290 A CN 202180068290A CN 116348535 A CN116348535 A CN 116348535A
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- biodegradable resin
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Abstract
本发明提供一种具有稳定的分散性,且不降低生物降解性,并能够提高纸制品等的热封性的生物降解性树脂水系分散体及其制造方法。本发明的生物降解性树脂水系分散体为含有生物降解性树脂和阴离子性化合物的生物降解性树脂水系分散体,且所述阴离子性化合物在1质量%的水溶液中的pH为7以上。
Description
技术领域
本发明涉及一种生物降解性树脂水系分散体及其制造方法和使用了生物降解性树脂水系分散体的食品包装用纸。
背景技术
根据以往文献可知具有耐油性和热封性的食品包装用纸。具体而言,在现有的食品包装用纸中,例如,通过实施利用聚丙烯(PP)或聚乙烯(PE)的层压加工,从而对纸赋予耐油性或热封性。
另一方面,在近年来将环境意识提高和海洋塑料垃圾问题作为背景下,塑料替代材料的需求不断增加。其中,要求在塑料使用比例多的食品包装用途中进行替代,且即使在食品包装用纸中,也正在进行着具有生物降解性、可替代PP或PE的材料的开发。
例如,作为具有生物降解性的材料,提出了生物降解性树脂水系分散体(例如,专利文献1~5)。在这些生物降解性树脂水系分散体中,作为分散剂,使用静电相互作用更优异的阴离子性化合物。
现有技术文献
专利文献
专利文献1:日本特开平10-101911号公报
专利文献2:日本特开2004-035811号公报
专利文献3:日本特开2004-168927号公报
专利文献4:日本特开2004-323640号公报
专利文献5:国际公开第2016/080530号。
发明内容
发明要解决的课题
但是,在生物降解性树脂水系分散体中,如果不使用适当的pH区域的阴离子性化合物,则生物降解性树脂的分散性变差,生物降解性树脂的粒径不会变小,因此,在涂布到纸制品上时,存在有难以确保充分的热封性的问题。而且,在专利文献1~5那样的现有的生物降解性树脂水系分散体中,由于没有被着眼于阴离子性化合物的pH区域,而使用了不适当的pH区域的阴离子性化合物,所以难以得到稳定的分散体,在热封性方面尚有改善的余地。
进一步,为了将生物降解性树脂水系分散体用于食品包装,必须是满足基于食品卫生法的食品、添加物等的判断标准、或登录在FDA(美国食品药品管理局)的使用许可列表中的物质。因此,在开发食品包装用的新的生物降解性树脂水系分散体的情况下,也需要考虑到对可能使用的材料会有限制。
本发明为鉴于上述情况而提出的发明,其课题在于,提供一种具有稳定的分散性、不降低生物降解性、且能够提高纸制品等的热封性的生物降解性树脂水系分散体及其制造方法。另外,本发明的课题还在于,提供一种具有生物降解性且热封性优异的食品包装用纸。
解决课题的技术方案
为解决上述问题,本发明的生物降解性树脂水系分散体,其特征在于,
其为含有生物降解性树脂和阴离子性化合物的生物降解性树脂水系分散体,所述阴离子性化合物在1质量%的水溶液中的pH为7以上。
在该生物降解性树脂水系分散体中,优选为所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠、聚磷酸钠、羧甲基纤维素钠、烷基苯磺酸钠和聚丙烯酸钠中的至少一种。
在该生物降解性树脂水系分散体中,优选为所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠、聚磷酸钠、羧甲基纤维素钠和聚丙烯酸钠中的至少一种。
在该生物降解性树脂水系分散体中,优选为所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠和聚丙烯酸钠中的至少一种。
在该生物降解性树脂水系分散体中,优选为所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐和聚丙烯酸钠中的至少一种。
在该生物降解性树脂水系分散体中,优选为所述阴离子性化合物的重均分子量为1万~2000万。
在该生物降解性树脂水系分散体中,优选的是,
含有:作为分散稳定剂的皂化度为70~90%的聚乙烯醇;以及选自作为粘度调节剂的瓜尔胶、阿拉伯树胶、黄原胶中的至少一种,
所述聚乙烯醇(B)相对于所述阴离子性化合物(A)的质量比(A/B)为在1/2~1/99的范围内,
相对于所述生物降解性树脂,所述粘度调节剂的添加量为0.05~1.0质量%。
在该生物降解性树脂水系分散体中,所述生物降解性树脂为聚乳酸。
本发明的食品包装用纸的特征在于,使用了所述生物降解性树脂水系分散体。
本发明的生物降解性树脂水系分散体的制造方法,其特征在于,
所述制造方法为含有生物降解性树脂和阴离子性化合物的生物降解性树脂水系分散体的制造方法,
所述制造方法包括分散工序,该分散工序至少使溶解的所述生物降解性树脂和所述阴离子性化合物分散在溶剂中而得到分散液,
所述阴离子性化合物在1质量%水溶液中的pH为7以上,
所述分散工序的所述分散液的pH为4~9。
本发明的生物降解性树脂水系分散体可以通过上述制造方法而得到。
发明效果
本发明的生物降解性树脂分散体具有稳定的分散性,不使生物降解性降低,且能够提高纤维制品或纸制品等的热封性。本发明的生物降解性树脂分散体的制造方法能够可靠地得到所述生物降解性树脂分散体。本发明的食品包装用纸具有生物降解性,且热封性优异。
具体实施方式
以下,对本发明的生物降解性树脂水系分散体及其制造方法、以及食品包装用纸的一实施方式进行说明。
本发明的生物降解性树脂水系分散体(以下有时记载为“水系分散体”)含有生物降解性树脂和阴离子性化合物(分散剂)。
另外,本发明的生物降解性树脂水系分散体的制造方法包括分散工序,该分散工序至少使溶解的生物降解性树脂和阴离子性化合物分散在溶剂中而得到分散液。
对生物降解性树脂没有特别的限定,可列举出例如,聚乳酸、乳酸与其他羟基羧酸的共聚物;聚丁二酸丁二醇酯、聚丁二酸-己二酸丁二酯、聚丁二酸乙二醇酯、聚己二酸丁二醇酯等二元酸聚酯;聚己内酯、己内酯与其他羟基羧酸的共聚物;聚羟基丁酸酯、聚羟基丁酸酯与其他羟基羧酸的共聚物;聚羟基丁酸、聚羟基丁酸与其他羟基羧酸的共聚物等。它们可以单独使用或可以将2种以上混合使用。其中,从树脂的耐热性、耐水性、耐溶剂性、光泽等观点考虑,生物降解性树脂优选为聚乳酸、乳酸与其他羟基羧酸的共聚物;聚丁二酸丁二醇酯、聚丁二酸-己二酸丁二酯;聚己内酯,更优选为聚乳酸。
作为聚乳酸,其D-乳酸含有率优选为1~30摩尔%、更优选为5~20摩尔%。
生物降解性树脂的数均分子量优选为在5000~100万的范围内、更优选为在1万~30万的范围内。
关于乳酸与其他羟基羧酸的共聚物,作为其他羟基羧酸,可列举出乙醇酸、2-羟基丁酸、2-羟基戊酸、2-羟基己酸、2-羟基庚酸、2-羟基辛酸、2-羟基-2-甲基丙酸、2-羟基-2-甲基丁酸、2-羟基-2-乙基丁酸、2-羟基-2-甲基戊酸、2-羟基-2-乙基戊酸、2-羟基-2-丙基戊酸、2-羟基-2-丁基戊酸、2-羟基-2-甲基己酸、2-羟基-2-乙基己酸、2-羟基-2-丙基己酸、2-羟基-2-丁基己酸、2-羟基-2-戊基己酸、2-羟基-2-甲基庚酸、2-羟基-2-乙基庚酸、2-羟基-2-丙基庚酸、2-羟基-2-丁基庚酸、2-羟基-2-甲基辛酸、3-羟基丙酸、4-羟基丁酸、5-羟基戊酸、6-羟基己酸、7-羟基庚酸等。
乳酸和羟基羧酸有时为D型、L型、D/L型等形态,但也可以为任意一种形态,对其没有限制。
阴离子性化合物在1质量%水溶液中的pH为7以上。具体而言,阴离子性化合物在1质量%水溶液中的pH优选为7~11、pH更优选为8~10、pH进一步优选为9~10。如果选择满足该范围的阴离子性化合物,则通过适当地调整在分散工序中的分散液的pH,电动电位容易成为适宜的值,其结果,能够进一步提高分散稳定性等。因此,能够提高使用生物降解性树脂水系分散液而得到的纸制品等的耐水性、热封性。另一方面,如果阴离子性化合物的1质量%水溶液中的pH小于7,则由于电动电位从适宜的值的范围偏离,从而导致粒子间的排斥力变弱而凝聚,分散液的稳定性降低。
对阴离子性化合物没有特别的限定,可列举出例如,构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠、聚磷酸钠、羧甲基纤维素钠、烷基苯磺酸钠、聚丙烯酸钠等。其中,从分散稳定性优异的观点出发,优选为十四碳烯磺酸钠、聚磷酸钠、羧甲基纤维素钠、烷基苯磺酸钠、聚丙烯酸钠,更优选为聚丙烯酸钠。
从提高使用生物降解性树脂水系分散液而得到的纸制品等的热封性的观点考虑,优选为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠、聚磷酸钠、羧甲基纤维素钠、聚丙烯酸钠中的至少一种,更优选为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠、聚丙烯酸钠中的至少一种,进一步优选为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐和聚丙烯酸钠中的至少一种。
阴离子性化合物的重均分子量可以例示为100~2500万的范围,但从生物降解性树脂水系分散体的分散稳定性和抑制增稠的观点考虑,优选为1万~2000万、更优选为10万~1000万。需要说明的是,重均分子量可以通过例如凝胶渗透色谱(GPC),且由分子量与已知的标准物质进行比较来求出。
相对于生物降解性树脂的含量,阴离子性化合物的含量优选为0.01~5.0质量%、更优选为0.01~2.0质量%、进一步优选为0.01~1.0质量%、特别优选为0.01~0.8质量%。如果阴离子性化合物的含量为0.01质量%以上,则分散稳定性等效果能够进一步提高,如果阴离子性化合物的含量为5.0质量%以下,则水系分散体的稳定的粘度控制变得容易,同时还可以提高使用该生物降解性树脂水系分散液所得到的纸制品等的耐水性、热封性。
根据需要,可以在生物降解性树脂水系分散体中添加上述阴离子性化合物以外的表面活性剂、增塑剂、粘度调节剂等。
作为所述阴离子性化合物以外的表面活性剂,可列举出阴离子性表面活性剂、阳离子性表面活性剂、非离子表面活性剂、两性表面活性剂、高分子表面活性剂等。
作为阴离子性表面活性剂,没有特别的限定,可列举出例如,脂肪酸盐、高级醇硫酸酯盐、液体脂肪油硫酸酯盐、脂肪族胺和脂肪族酰胺的硫酸盐、脂肪醇磷酸酯盐、烷基苯磺酸盐、脂肪族酰胺磺酸盐、二元脂肪酸酯的磺酸盐等。
作为阳离子性表面活性剂,可列举出例如,烷基胺盐类、季铵盐类、烷基吡啶鎓盐、脂肪酸三乙醇胺单酯盐、烷基聚氧乙烯胺等。
作为非离子型表面活性剂,可列举出例如,聚氧乙烯烷基醚、聚氧乙烯烷基酚醚、聚氧乙烯烷基酯、脱水山梨糖醇烷基酯、聚氧乙烯脱水山梨糖醇烷基酯等。
作为高分子表面活性剂,可列举出阴离子性高分子、阳离子性高分子、非离子高分子、两性高分子等。这些高分子表面活性剂可以为水溶性的,可列举出例如,聚丙烯酸盐、聚甲基丙烯酸盐、聚丙烯酰胺、丙烯酸—甲基丙烯酸烷基酯共聚物、丙烯酸盐—丙烯酰胺共聚物、甲基丙烯酸盐—丙烯酰胺共聚物、二异丁烯—马来酸共聚物、烷基乙烯基醚—马来酸共聚物、马来化聚丁烯、马来化聚丁二烯、聚甲基乙烯基醚、聚乙烯吡咯烷酮、聚苯乙烯磺酸盐、阳离子化纤维素、羧甲基纤维素、藻酸盐、聚乙烯醇等。其中,从安全性、供给面的观点考虑,优选为非离子高分子。
生物降解性树脂水系分散体,作为分散稳定剂优选含有作为非离子高分子的聚乙烯醇。所述聚乙烯醇优选为皂化度为70~90%,数均分子量优选为5万~30万。聚乙烯醇的皂化度可由聚乙烯醇的羟基值来计算。通过配合聚乙烯醇,可使生物降解性树脂粒子稳定地分散在溶剂中。
(A)阴离子性化合物(分散剂)与(B)聚乙烯醇(分散稳定剂)的质量比(A/B),优选为在1/2~1/99的范围内、更优选在1/5~1/99的范围内、进一步优选为在1/10~1/99的范围内。由于如果质量比(A/B)在该范围内,分散变得容易,分散后的稳定性也得以提高,因此能够提高使用生物降解性树脂水系分散液所得到的纸制品等的耐水性、热封性。
另外,相对于生物降解性树脂的质量,(A)阴离子性化合物(分散剂)和(B)聚乙烯醇(分散稳定剂)的总质量优选为在0.1~20质量%的范围内、更优选为0.5~20质量%的范围内、进一步优选为在1~20质量%的范围内。如果(A)阴离子性化合物和(B)聚乙烯醇的合计质量为0.1质量%以上,则均匀的搅拌/分散变得容易,另外,如果(A)阴离子性化合物和(B)聚乙烯醇的合计质量为20质量%以下,则能够减少由过量添加分散剂所引起的低效率,同时能够减少对耐水性的影响。
而且,作为(A)阴离子性化合物(分散剂)、(B)聚乙烯醇(分散稳定剂)和生物降解性树脂的总质量相对于水的质量比,优选为在2/8~/6/4的范围内。当该质量比为2/8以上时,由于生物降解性树脂的含量高,则为有效,当该质量比为6/4以下时,则均匀地搅拌、分散变得容易,水系分散体的稳定性也得以提高。因此,能够提高使用生物降解性树脂水系分散液所得到的纸制品等的耐水性、热封性。
作为增塑剂,可列举出柠檬酸三乙酯、柠檬酸三丁酯、乙酰柠檬酸三乙酯、乙酰柠檬酸三丁酯等柠檬酸衍生物;二甘醇二乙酸酯、三甘醇二乙酸酯、三甘醇二丙酸酯等醚酯衍生物;甘油三乙酸酯、甘油三丙酸酯、甘油三丁酸酯等甘油衍生物;乙基邻苯二甲酰羟乙酸乙酯(ethyl phthalyl ethyl glycolate)、乙基邻苯二甲酰羟乙酸丁酯(ethyl phthalylbutyl glycolate)、丁基邻苯二甲酰羟乙酸丁酯(butyl phthalyl butyl glycolate)等邻苯二甲酸衍生物;己二酸和2-(2乙氧基甲氧基)乙醇和苯甲醇的混合酯;己二酸和1,4-丁二醇的缩合物等己二酸衍生物;聚己内酯、聚丙内酯等聚羟基羧酸等。其中,从造膜性提高效果佳的观点考虑,特别优选为使用己二酸衍生物、邻苯二甲酸衍生物。增塑剂的添加量为相对每生物降解性树脂100重量份优选为5~40重量份。如果增塑剂的添加量为5重量份以上,则能够进一步发挥增塑效果,如果增塑剂的添加量为40重量份以下,则能够抑制增塑剂渗出的发生。
作为粘度调节剂,可列举出甲基纤维素、羧甲基纤维素、羟乙基纤维素、羟乙基甲基纤维素、羟丙基甲基纤维素等纤维素衍生物;阳离子化淀粉、醚化淀粉等淀粉衍生物;阿拉伯树胶、瓜尔胶、黄原胶等植物胶;酪蛋白,壳聚糖、几丁质等动物性高分子等。其中,优选为瓜尔胶、阿拉伯树胶和黄原胶。相对于生物降解性树脂,粘度调节剂的添加量优选为0.05~1.0质量%。如果粘度调节剂的添加量在0.05质量%以上,则能够提高粘度调整效果,如果粘度调节剂的添加量在1.0质量%以下,则水系分散体的稳定粘度的控制会变得容易。
在优选的一实施方式中,生物降解性树脂水系分散体含有:作为分散稳定剂的皂化度为70~90%的聚乙烯醇;以及选自作为粘度调节剂的瓜尔胶、阿拉伯树胶、黄原胶中的至少一种,聚乙烯醇(B)与阴离子性化合物(A)的质量比(A/B)在1/2~1/99的范围内,相对于所述生物降解性树脂,粘度调节剂的添加量为0.05~1.0质量%。关于聚乙烯醇(B)的优选例为如上所述。
生物降解性树脂水系分散体的粘度优选为在0.1~10Pa·s的范围内,即优选为0.1Pa·s以上且10Pa·s以下。例如,在生物降解性树脂水系分散体的粘度低于0.1Pa·s时,由于相分离、树脂粒子的不均匀化或沉降等,难以维持良好的分散状态,有可能需要使用均质混合机或高压乳化机等分散装置等进行强烈地搅拌。在该强烈的搅拌中,由于施加强烈的剪切力,已吸附在分散粒子上的分散剂分子发生剥离,其结果是粒径分布加大,分散本身有可能变得困难。另一方面,由于如果生物降解性树脂水系分散体的粘度超过10Pa·s,则溶液粘度过高,因此有可能不能进行良好的分散。
需要说明的是,为了改善表面平滑性、拒水性、脱模性等,也可以在本发明的生物降解性树脂水系分散体中含有天然蜡、合成蜡等蜡类。作为天然蜡,可列举出例如,小烛树蜡、巴西棕榈蜡、米糠蜡、木蜡和霍霍巴固体蜡等植物系天然蜡;蜜蜡、羊毛脂和鲸蜡等动物天然蜡;褐煤蜡、地蜡和纯地蜡等矿物系天然蜡;石蜡、微晶石蜡、矿脂蜡等石油系天然蜡等。另外,作为合成蜡,可列举出费-托蜡、聚乙烯蜡等合成烃类;褐煤蜡衍生物、石蜡衍生物、微晶石蜡衍生物等改性蜡;固化蓖麻油、固化蓖麻油衍生物等氢化蜡;12-羟基硬脂酸、硬脂酸酰胺、邻苯二甲酸酐酰亚胺等。
生物降解性树脂水系分散体中所含有的生物降解性树脂为粒子状,粒子的平均粒径优选在0.1~500μm的范围内、更优选在0.5~50μm的范围内、进一步优选在0.5~10μm的范围内。
接下来,对本发明的生物降解性树脂水系分散体的制造方法的一实施方式进行说明。
本发明的生物降解性树脂水系分散体的制造方法包括分散工序,该分散工序至少使溶解的生物降解性树脂和阴离子性化合物分散在溶剂中而得到分散液。
如上所述,阴离子性化合物在1质量%水溶液中的pH为7以上。
分散工序的分散液例如,可通过将溶剂、生物降解性树脂、阴离子性化合物以及根据需要与其他材料同时进行混合且搅拌而得到。
具体而言,第1,可例示出例如使用具有搅拌装置的密闭槽,同时加入生物降解性树脂、阴离子性化合物、聚乙烯醇、粘度调节剂和水,一边加热搅拌一边加压,使生物降解性树脂分散的加压分散法。
第2,可例示出将含有生物降解性树脂、阴离子性化合物、根据需要的聚乙烯醇以及粘度调节剂的熔融物添加到被保持在加压下的热水中并搅拌使其分散的直接分散法。
第3,可例示出将生物降解性树脂加热熔融,在其中添加含有阴离子性化合物、根据需要的聚乙烯醇以及粘度调节剂的水溶液并进行搅拌,从而使生物降解性树脂分散在水中的相转化法。
第4,可例示出添加有机溶剂、水、生物降解性树脂、阴离子性化合物、根据需要的聚乙烯醇以及粘度调节剂并搅拌使其分散后,除去有机溶剂的方法。
第5,可例示出将包含阴离子性化合物、根据需要的聚乙烯醇以及粘度调节剂的水溶液添加到生物降解性树脂的有机溶剂溶液中进行搅拌并使其分散后,除去有机溶剂的方法。
只要是能够得到生物降解性树脂的水系分散体的方法即可,即使是第1~第5种方法以外的方法也可以适当地采用。
更具体而言,关于可适用于广泛种类的生物降解性树脂这一点,若考虑进行水解等,作为得到分散液的方法,优选为例如,将有机溶剂、水、生物降解性树脂、阴离子性化合物、根据需要的聚乙烯醇以及粘度调节剂加入到具有搅拌装置的密闭槽中,边搅拌边进行升温,在使固体原料溶解、分散后进行冷却,然后,在减压下除去有机溶剂的方法。
另外,作为得到分散液的方法,优选的是,将有机溶剂、生物降解性树脂加入到具有搅拌装置的密闭槽中进行搅拌升温而形成溶解的生物降解性树脂溶解溶液,将在其他搅拌槽中加入水、阴离子性化合物、根据需要的聚乙烯醇以及粘度调节剂进行了溶解的水溶液添加到密闭槽中进行搅拌,在边升温至树脂溶解温度以上边使其分散后,进行冷却,然后,在减压下除去有机溶剂的方法。
在这些方法中,作为有机溶剂,可列举出甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯等甲酸酯类,乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯等乙酸酯类的酯系有机溶剂;氯仿、四氯化碳等氯系有机溶剂;苯、甲苯和二甲苯等芳香族烃等,优选为树脂溶解性良好的酯系有机溶剂,特别优选为甲酸酯类和乙酸酯类。
在本发明的生物降解性树脂水系分散体的制造方法中,分散工序的分散液的pH为4~9、pH优选为4~6。通过使pH在该范围内,电动电位容易形成为适宜的值,聚合物粒子可彼此适度地进行排斥等,其结果,能够得到具有稳定分散性的生物降解性树脂水系分散体。具体而言,生物降解性树脂水系分散体的电动电位优选为-30mV以下、更优选为-40mV以下。基本上,如果是这些值以下的电动电位,则经时稳定性会变得更加良好。对电动电位的下限没有特别的限定,但在通常的制备中例如为-50mV以上。另外,优选为在转相乳化后除去有机溶剂,使溶剂残余量为1000ppm以下。
本发明的生物降解性树脂分散体具有稳定的分散性,且不降低生物降解性,从而能够提高在涂布到纤维制品或纸制品等时的纸制品等的热封性。因此,在工业上,在各种用途上非常有用,且能够实用性地进行使用。
对本发明的生物降解性树脂分散体的使用用途没有特别的限定,可列举出例如,食品包装用纸。除此以外,本发明的生物降解性树脂分散体还可用于例如液晶显示装置用间隔物、调色剂用添加剂;电子照相显影用调色剂;涂料等流变改性剂/添加剂;粉体涂料用材料、汽车材料、建筑材料等成型品的机械特性改性剂;薄膜、纸、纤维等机械特性改性剂;快速成型、快速制造等树脂成型体用原料、闪光成型用材料、塑料溶胶用糊状树脂、粉末堵料、粉体的流动性/平滑性改进剂;润滑剂;橡胶配合剂;研磨剂;增稠剂;过滤剂和助滤剂;胶凝剂;凝聚剂;吸油剂;脱模剂;塑料薄膜/片材的滑动性改进剂;防粘连剂;光泽调节剂;糙面精整剂;光扩散剂;表面高硬度改进剂;韧性改进剂;色谱用填充剂;微胶囊用助剂;药物释放系统/诊断剂等医疗用材料;医疗用诊断检查剂;香料/农药的保持剂;化学反应用催化剂及其载体;气体吸附剂;离子交换树脂;陶瓷加工用烧结材料;测定/分析用的标准粒子和食品工业领域用的粒子等。
本发明的生物降解性树脂水系分散体及其制造方法、以及使用生物降解性树脂水系分散体的食品包装用纸,并不被限定于以上的实施方式。
实施例
以下,连同实施例,对本发明的生物降解性树脂水系分散体等详细地进行说明,但本发明不被限定于以下的实施例。
1.生物降解性树脂分散体的制备
在实施例和比较例中,作为生物降解性树脂、在1质量%水溶液中的pH为7以上的阴离子性化合物(分散剂(A))、或所述阴离子性化合物以外的表面活性剂(分散剂(A))、聚乙烯醇(分散稳定剂(B))、粘度调节剂,使用了以下物质。
(生物降解性树脂)
生物降解性树脂A:聚乳酸
生物降解性树脂B:聚丁二酸丁二醇酯
生物降解性树脂C:聚丁二酸-己二酸丁二酯
生物降解性树脂D:聚己内酯
(在1质量%水溶液中的pH为7以上的阴离子性化合物)
阴离子性化合物A:聚丙烯酸钠(重均分子量为50万)
阴离子性化合物B:聚丙烯酸钠(重均分子量为300万~500万)
阴离子性化合物C:脂肪酸(C12、14、16)钠
阴离子性高分子化合物D:十四碳烯磺酸钠
阴离子性化合物E:聚磷酸钠
阴离子性化合物F:羧甲基纤维素钠
阴离子性化合物G:烷基苯磺酸钠
[所述阴离子性化合物以外的表面活性剂(阴离子性化合物)]
阴离子性化合物H:聚丙烯酰胺-丙烯酸钠(重均分子量为1600万~1700万)
阴离子性化合物I:丙烯酰胺-甲基丙烯酸共聚物(重均分子量为2000万)
阴离子性化合物J:甲基丙烯酸-丙烯酰胺(重均分子量为400万)
阴离子性化合物K:海藻酸钠
(聚乙烯醇)
聚乙烯醇A:皂化度80%,数均分子量为10万
聚乙烯醇B:皂化度99%,数均分子量为9万
(粘度调节剂)
粘度调节剂A:黄原胶(DSP Gokyo Food&Chemical Co.,Ltd.制造,ECHO GUM)
粘度调节剂B:瓜尔胶(San-Ei Gen F.F.I.,Inc.制造,VISTOP D20)
粘度调节剂C:阿拉伯树胶(日本三荣药品贸易株式会社制造,Arabic KORU SS)
<实施例1~15、比较例1~4>
以在表1、表2所示的成分比例将各成分装入到密闭分散槽中,在使用生物降解性树脂A、C、D的情况下加热到65℃,在使用生物降解性树脂B的情况下加热到120℃,并通过使用给定的搅拌分散装置的分散方法进行分散1小时后,再急冷至40℃。然后,在减压下除去乙酸乙酯,从而得到了生物降解性树脂水系分散体。
另外,按以下方法,对制备生物降解性树脂水系分散体时的分散工序中(在混合搅拌时的加热分散、冷却后)和水系分散体(在除去乙酸乙酯后)的粘度、稳定性进行了测定和评价。
(pH)
使用日本株式会社堀场制作所制造的玻璃电极式氢浓度计、pH METER 9615S-10D,在25℃条件下测定了pH。
(电动电位(mV))
使用马尔文仪器(Malvern)公司制造的Zetasizer Nano ZS测定装置,对向各生物降解性树脂水系分散体中添加水而稀释至固体成分1质量%的物质,测定了电动电位。需要说明的是,在25℃条件下进行了所述测定。
(平均粒径(μm))
使用激光衍射型粒度分布测定装置(日本岛津制作所株式会社制造,SALD-2300型,折射率1.45-0.00i),对粒子的平均粒径进行了测定。
(离心分离)
使用KUBOTA制造的台式离心机Model 4000,以3500rpm进行了20分钟的离心分离。然后,按以下◎:分离低于10%、○:分离在10%以上~低于30%、△:分离在30%以上~低于50%、×:50%以上的4个等级,对得到的样品的分离状况进行了评价。
(稳定性试验:在25℃条件下静置)
将各生物降解性树脂水系分散体分别加入到100ml玻璃容器中,在25℃恒温槽中进行了保管。按以下◎:分离低于10%、○:分离在10%以上~低于30%、△:分离在30%以上~低于50%、×:50%以上的4个等级,对保管14天后的分离状态况进行了评价。
(稳定性试验:在40℃条件下静置)
将各生物降解性树脂水系分散体分别加入到100ml玻璃容器中,在40℃恒温槽中进行了保管。按以下◎:分离低于10%、○:分离在10%以上~低于30%、△:分离在30%以上~低于50%、×:50%以上的4个等级,对保管14天后的分离状态况进行了评价。
(热封性:剥离强度(N/m))
使用棒涂机No.20,将上述实施例1~15和比较例1~4的水系分散体分别涂布在切成25mm×200mm的小片的牛皮纸(基重70g/m2)的25mm×150mm的部分上,且在25℃、40%RH条件下干燥24小时后,以使涂布面贴合的方式将2片试验片夹在铁板中,且在180℃、300g/cm2的条件下,使用日本株式会社羽岛制造的全自动转移压力机HP-84,按压3分钟,从而得到了试验片。在将得到的试验片静置1天后,按照JISK6854-3标准,使用日本株式会社东洋精机制造的拉伸试验机STROGRAPH E3,以拉伸速度10mm/分钟,测定了各实验片的剥离强度(N/m)。
(耐水性试验)
使用棒涂机No.20,将上述实施例1~15和比较例1~4的水系分散体分别涂布在切成130mm×130mm的小片的牛皮纸(基重70g/m2)上,且在25℃、40%RH条件下干燥24小时后,且在180℃、300g/cm2的条件下,使用日本株式会社羽岛制造的全自动转移压力机HP-84,按压3分钟,从而得到了试验片。耐水性的评价按照JIS-P-8140标准,以吸水量(g/m2)进行了判断。
评价标准:◎:0~5、○:5~10、△:10~20、×:20以上。
将结果分别表示在表1A~1C、表2和表3。
[表1A]
[表1B]
[表1C]
[表2]
[表3]
如表1A、表1B所示,在为含有在1质量%水溶液中的pH为7以上的阴离子性化合物的生物降解性树脂水系分散体、且分散工序的分散液的pH为4以上的实施例1~15中,被确认为稳定性、热封性优异。
另一方面,在为含有在1质量%水溶液中的pH小于7的阴离子性化合物的生物降解性树脂水系分散体、且分散工序的分散液的pH小于4的比较例1~4中,被确认为稳定性、热封性不充分。
另外,如表3所示,即使在含有在1质量%水溶液中的pH为7以上的阴离子性化合物的生物降解性树脂水系分散体中,在涂布了含有聚丙烯酸钠的生物降解性树脂水系分散体的牛皮纸中,也被确认为耐水性得以提高。
Claims (10)
1.一种生物降解性树脂水系分散体,其特征在于,
其为含有生物降解性树脂和阴离子性化合物的生物降解性树脂水系分散体,所述阴离子性化合物在1质量%的水溶液中的pH为7以上。
2.根据权利要求1所述的生物降解性树脂水系分散体,其特征在于,
所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠、聚磷酸钠、羧甲基纤维素钠、烷基苯磺酸钠和聚丙烯酸钠中的至少一种。
3.根据权利要求1所述的生物降解性树脂水系分散体,其特征在于,
所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠、聚磷酸钠、羧甲基纤维素钠和聚丙烯酸钠中的至少一种。
4.根据权利要求1所述的生物降解性树脂水系分散体,其特征在于,
所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐、十四碳烯磺酸钠和聚丙烯酸钠中的至少一种。
5.根据权利要求1所述的生物降解性树脂水系分散体,其特征在于,
所述阴离子性化合物为选自构成脂肪酸的碳原子数为12~16的脂肪酸盐和聚丙烯酸钠中的至少一种。
6.根据权利要求1所述的生物降解性树脂水系分散体,其特征在于,
所述阴离子性化合物的重均分子量为1万~2000万。
7.根据权利要求1~5中任一项所述的生物降解性树脂水系分散体,其特征在于,
含有:作为分散稳定剂的皂化度为70~90%的聚乙烯醇;以及选自作为粘度调节剂的瓜尔胶、阿拉伯树胶、黄原胶中的至少一种,
所述聚乙烯醇(B)相对于所述阴离子性化合物(A)的质量比A/B为在1/2~1/99的范围内,
相对于所述生物降解性树脂,所述粘度调节剂的添加量为0.05~1.0质量%。
8.根据权利要求1~7中任一项所述的生物降解性树脂水系分散体,其特征在于,
所述生物降解性树脂为聚乳酸。
9.一种食品包装用纸,其中,
使用了权利要求1~8中任一项所述的生物降解性树脂水系分散体。
10.一种生物降解性树脂水系分散体的制造方法,其特征在于,
所述制造方法为含有生物降解性树脂和阴离子性化合物的生物降解性树脂水系分散体的制造方法,
所述制造方法包括分散工序,该分散工序至少使溶解的所述生物降解性树脂和所述阴离子性化合物分散在溶剂中而得到分散液,
所述阴离子性化合物在1质量%水溶液中的pH为7以上,
所述分散工序的所述分散液的pH为4~9。
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