CN109312098A - 发泡成形体用组合物及其制造方法、发泡成形体及其制造方法和发泡成形体用含改性纤维素树脂组合物 - Google Patents
发泡成形体用组合物及其制造方法、发泡成形体及其制造方法和发泡成形体用含改性纤维素树脂组合物 Download PDFInfo
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- CN109312098A CN109312098A CN201780036407.1A CN201780036407A CN109312098A CN 109312098 A CN109312098 A CN 109312098A CN 201780036407 A CN201780036407 A CN 201780036407A CN 109312098 A CN109312098 A CN 109312098A
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- foam molding
- modified cellulose
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- unsaturated bond
- rubber
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Abstract
本发明目的在于提供一种在如热塑性树脂或橡胶那样的疏水性高的发泡成形材料用树脂中纤维素纤维均匀分散的含过氧化物和发泡剂的发泡成形体用组合物、和一种使该发泡成形体用组合物在发泡成形中反应而得到的机械物性优异的发泡体。发泡成形体用组合物含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D)。
Description
技术领域
本发明涉及发泡成形体用组合物及其制造方法、使用了发泡成形体用组合物的发泡成形体及其制造方法和发泡成形体用含改性纤维素树脂组合物。
背景技术
聚乙烯或聚丙烯等发泡成形材料用树脂价格便宜,柔软性和耐药品性优异,出于这一观点,广泛利用于容器、配管、薄膜、医疗用途等。而且,以往人们都知道:为了赋予轻量化、隔热性和冲击吸收性,使发泡成形材料用树脂发泡而得到发泡体。发泡成形材料用树脂的发泡体,同未发泡状态的比较,相同体积下重量轻,隔热性和冲击吸收性优异,但另一方面,存在着随着发泡倍率增加机械物性降低的问题。为了提高这种发泡成形材料用树脂的机械物性,迄今,实行着配合填料等强化材的措施。
譬如专利文献1中,使用碳纤维或玻璃纤维作填料来实现强化效果,以提高发泡成形体的机械物性。然而,碳纤维难燃,不便于热回收,而且价格高。另外,玻璃纤维虽然价格比较便宜,但是热回收时存在废弃处理问题。
另一方面,由植物纤维得到的微纤丝化纤维素(microfibrillated cellulose)价格比较便宜,而且热回收性优异。而且,因以仅是钢铁五分之一的轻度即能达到其同等以上的强度、刚性(弹性模量),故作为发泡成形材料用树脂的强化剂为人所重视。譬如,专利文献2中,记载了将对微纤丝化纤维素部分羟基用多元酸酐作疏水改性剂而得到的疏水改性纤维素纤维用作发泡成形材料用树脂的强化材料。
虽然,使用上述方法也可实现强化效果、提高成形体的机械物性,但是人们还是期望机械物性有进一步提高。
已有技术文献
专利文献
专利文献1:日本专利特开2014-172915
专利文献2:日本发明专利第5865128号(特开2013-185085)
发明内容
技术问题
本发明目的就在于提供一种在如热塑性树脂或橡胶那样的疏水性高的发泡成形材料用树脂中纤维素纤维均匀分散的含过氧化物和发泡剂的发泡成形体用组合物、和一种使该发泡成形体用组合物在发泡成形中反应而得到的机械物性优异的发泡体。
技术方案
为解决上述问题,本发明人经反复锐意研究的结果,注意到:通过一边将具有不饱和键的改性纤维素纤维和如热塑性树脂或橡胶那样的发泡成形材料用树脂均匀混合一边在过氧化物和发泡剂的存在下发泡成形,可得到机械物性优异的发泡成形体,遂完成本发明。另外,还注意到:作为本发明其它形态,使用发泡成形体用含改性纤维素树脂组合物(其中,具有不饱和键的改性纤维素纤维为特定含羧基改性纤维素与具有不饱和键及缩水甘油基的化合物的反应物)时,即使用过氧化物以外的交联剂、通过其它发泡方法进行发泡成形,也与上述发明一样,可得到机械物性优异的发泡成形体。
即,本发明的技术方案如下:
(1)一种发泡成形体用组合物,其中,含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D)。
(2)如上述(1)所述的发泡成形体用组合物,其特征在于,改性纤维素纤维(A)是纳米纤丝化物(nanofibrillated material)。
(3)如上述(1)所述的发泡成形体用组合物,其特征在于,改性纤维素纤维(A)是含羧基改性纤维素(E)与具有不饱和键和缩水甘油基(glycidyl group)的化合物(F)的反应物。
(4)如上述(3)所述的发泡成形体用组合物,其特征在于,含羧基改性纤维素(E)是纤维素与多元酸酐(G)的反应物。
(5)如上述(4)所述的发泡成形体用组合物,其特征在于,多元酸酐(G)是碳数8以上的多元酸酐。
(6)如上述(1)所述的发泡成形体用组合物,其特征在于,上述(B)的热塑性树脂是从聚烯系树脂、聚酯系树脂、丙烯系树脂、苯乙烯树脂选出的至少1种。
(7)如上述(1)所述的发泡成形体用组合物,其特征在于,改性纤维素纤维(A)/热塑性树脂和/或橡胶(B)/过氧化物(C)/发泡剂(D)=1~40/40~99/0.05~5/0.1~20质量比。
(8)一种发泡成形体,其中,以上述(1)~(7)中任一项所述的发泡成形体用组合物为原料。
(9)一种发泡成形体用组合物的制造方法,该发泡成形体用组合物含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D),其特征在于,上述具有不饱和键的改性纤维素纤维(A)是通过使含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)反应而得到的。
(10)如上述(9)所述的发泡成形体用组合物的制造方法,其特征在于,改性纤维素纤维(A)是这样得到的改性纤维素纤维:使纤维素与多元酸酐(G)反应而成含羧基改性纤维素(E),然后,进一步使具有不饱和键和缩水甘油基的化合物(F)与之反应。
(11)如上述(10)所述的发泡成形体用组合物的制造方法,其特征在于,多元酸酐(G)是碳数8以上的多元酸酐。
(12)一种发泡成形体的制造方法,其特征在于,在过氧化物(C)和发泡剂(D)存在下,将具有不饱和键的改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)发泡成形,据此,使改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)反应。
(13)如上述(12)所述的发泡成形体的制造方法,其中,具备以下工序:
(工序I)将改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)加热熔融混炼而将改性纤维素纤维(A)纳米纤丝化的工序;
(工序II)工序I后添加过氧化物(C)、发泡剂(D)的工序;
(工序III)工序II后发泡成形的工序。
(14)一种发泡成形体用含改性纤维素树脂组合物,是含有具有不饱和键的改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)的组合物,其特征在于,上述具有不饱和键的改性纤维素纤维(A)是含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)的反应物;上述含羧基改性纤维素(E)是纤维素与碳数8以上的多元酸酐(G)的反应物。
(15)如上述(14)所述的发泡成形体用含改性纤维素树脂组合物,其特征在于,改性纤维素纤维(A)是纳米纤丝化物。
(16)如上述(14)所述的发泡成形体用含改性纤维素树脂组合物,其特征在于,热塑性树脂是从聚烯系树脂、聚酯系树脂、丙烯系树脂、苯乙烯树脂选出的至少1种。
(17)如上述(14)所述的发泡成形体用含改性纤维素树脂组合物,其特征在于,改性纤维素纤维(A)/热塑性树脂和/或橡胶(B)=1~40/40~99质量比。
(18)一种发泡成形体,其中,以上述(14)~(17)中任一项所述的发泡成形体用含改性纤维素树脂组合物为原料。
发明的效果
本发明,通过用含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D)的发泡成形体用组合物发泡成形,能得到机械物性高的发泡成形体。另外,使用由特定的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)构成的发泡成形体用含改性纤维素树脂组合物时,过氧化物(C)、发泡剂(D)均不必要,无论以什么样的发泡方法都同样能得到机械物性高的发泡成形体。
具体实施方式
以下详细描述本发明发泡成形体用组合物及其制造方法、和发泡成形体及其制造方法。
<发泡成形体用组合物>
本发明发泡成形体用组合物含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D)。
<改性纤维素纤维(A)>
本发明发泡成形体用组合物所用具有不饱和键的改性纤维素纤维(A),无特别限定,只要是能导入不饱和键的即可,但从提高机械物性观点,以不饱和键导入达能适度地具有与发泡成形材料用树脂的键合点这种程度(即比没有不饱和键导入时能看到机械物性提高)为佳。关于是否在纤维素纤维有不饱和键导入,可通过碘值测定来确认。改性纤维素纤维(A)的碘值以5~130为佳,20~50则更好。
碘值可按如下步骤测定。使试样在N-甲基吡咯烷酮(以下有时简记作NMP)膨润后,添加一氯化碘溶液,放置于阴暗处。其后,添加碘化钾和水,然后用硫代硫酸钠溶液滴定。在溶液颜色变成浅黄色的时候,添加淀粉溶液,滴定,直到蓝色消失为止,据此,可求碘值。具体是按实施例采用的方法求。
另外,具有不饱和键的改性纤维素纤维(A)优选为纳米纤丝化物(微纤丝化纤维素)。只要混合后发泡成形用材料中被充分微纤丝化即可,故没有必要在混合前即被微纤丝化。关于微纤丝化纤维素的纤维口径,其平均值通常为4~800nm,优选10~550nm,尤其优选20~400nm。
作为为获得上述改性纤维素纤维(A)而使用的纤维素纤维的原料,可例举在木材、竹、麻、黄麻、洋麻、绵、甜菜等含有的源自植物的纤维(以下有时记作植物纤维)。作为优选的植物纤维,可例举木材,譬如松、杉、桧、桉属植物、金合欢属植物等,而且也能使用以这些为原料得到的纸或旧纸等。植物纤维,既可单独使用1种也可从中选出2种以上使用。纤维素纤维,可例举从含上述植物纤维的材料得到的纸浆,或作了丝光化(mercerization)的纤维素纤维,但以含人造纤维、赛璐玢(cellophane)或Lyocell等再生纤维素纤维的为佳。
作为上述纸浆,譬如可举出以化学方式或机械方式或者两者并用方式将植物纤维纸浆化而得到的机械纸浆(未漂白牛皮纸浆(UKP)、漂白牛皮纸浆(BKP)、亚硫酸纸浆(SP)、半化学纸浆(SCP)、化学细磨纸浆(Chemi Ground Pulp)(CGP)、化学机械纸浆(chemi-mechanical pulp)(CMP)、杂木纸浆(GP)、盘磨机械浆(refiner mechanical pulp)(RMP)、热磨机械纸浆(TMP)、化学热磨机械纸浆(chemi-thermomechanical pulp)(CTMP))等。这些纸浆当中尤其优选由来于纤维强度大的针叶树的各种牛皮纸浆。另外,根据本发明的纤维素纤维也可含有半纤维素(hemicellulose)、木质素(lignin)等其它成分。
制造具有不饱和键的改性纤维素纤维(A)之际对纤维素纤维导入不饱和键的方法无特别限定。譬如可例举出让具有不饱和键的多元酸酐、具有不饱和键的异氰酸酯化合物、具有不饱和键的硅烷化合物与纤维素纤维中的羟基反应而导入的方法。另外,作为其它方法,也可考虑这样的方法:将具有与纤维素纤维中羟基反应效率良好的官能基(譬如羧酸酐基、异氰酸酯基、硅烷醇基(silanol group))和其它1以上的官能基的化合物,在与纤维素纤维反应前或与纤维素纤维反应后,与具有同上述化合物反应的官能基和不饱和键的化合物反应,以在纤维素纤维中导入不饱和键。其中,具有不饱和键的改性纤维素纤维(A)优选为含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)的反应物。
作为含羧基改性纤维素(E),譬如可例举羧甲基纤维素、羧乙纤维素、TEMPO氧化纤维素等。本发明中,其制造方法无特别限定,但是为了后续反应较容易调整所导入不饱和键的导入量、容易制造,优选使多元酸酐(G)与纤维素纤维的羟基反应而得到的含羧基改性纤维素(E)。
多元酸酐(G),无特别限定,可例举出马来酸酐、富马酸酐、琥珀酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、烷基或链烯基琥珀酸酐等。从与树脂的相溶性的观点,以碳数8以上的多元酸酐为佳,更优选四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、烷基或链烯基琥珀酸酐。特别优选辛烯基琥珀酸酐、十二碳烯基琥珀酸酐、十六碳烯琥珀酸酐、十八碳烯琥珀酸酐。
使多元酸酐(G)反应的纤维素纤维的置换度(纤维素每葡萄糖单位置换1个羟基时记作置换度1。以下有时简记为DS。)以0.05~2.0为佳,优选0.1~1.0,更优选0.1~0.8。通过将DS设为0.05~2.0,则进一步使具有不饱和键和缩水甘油基的化合物(F)反应而导入的不饱和键的导入量就发泡成形而得到的发泡成形体的机械强度而言就处于较佳范围。
须指出,本发明中,DS是通过清洗除去用作原料的多元酸酐(G)或其水解物等副产物后从质量増加率换算求出的。
作为具有不饱和键和缩水甘油基的化合物(F),可例举出苯基缩水甘油醚(phenylglycidyl ether)、烯丙基缩水甘油醚(allyl glycidyl ether)、苯乙烯化氧(styreneoxide)、邻甲苯基缩水甘油醚(cresyl glycidyl ether)、甲基丙烯酸缩水甘油酯(glycidyl methacrylate)、环氧丙烯酸酯(epoxy acrylate)、丁基缩水甘油醚丙烯酸酯(butyl glycidyl ether acrylate)等。其中优选甲基丙烯酸缩水甘油酯。
只要不妨碍本发明效果,除了上述具有不饱和键和缩水甘油基的化合物(F)而外,还可并用不带不饱和键的具有缩水甘油基的化合物(F’)。至于其使用量,只要是将导入化合物(F)而剩余的羧基全部消费掉这种程度即可。作为化合物(F’),可例举环氧辛烷(octylene oxide)、甲基缩水甘油醚(methyl glycidyl ether)、丁基缩水甘油醚(butylglycidyl ether)等。
用化合物(F)、化合物(F’)屏蔽羧基,降低改性纤维素纤维(A)的羧残基量时,制造发泡成形体之际的热稳定性会提高,故最好尽可能地减少改性纤维素纤维(A)的羧残基。
<热塑性树脂和/或橡胶(B)>
本发明发泡成形体用组合物所用的可塑性树脂和/或橡胶(B)无特别限定,只要是通常作发泡成形材料用树脂使用的即可。作为热塑性树脂,可例举出:尼龙等聚酰胺树脂;聚乙烯、聚丙烯、乙烯丙烯共聚物、乙烯-醋酸乙烯共聚物等聚烯树脂;聚对苯二甲酸乙二醇酯(polyethylene terephthalate)、聚对苯二甲酸丁二醇酯(polybutylene terephthalate)等聚酯树脂;聚甲基丙烯酸甲酯(polymethyl methacrylate)、聚甲基丙烯酸乙酯(polyethyl methacrylate)等丙烯树脂;聚苯乙烯、(甲基)丙烯酸酯-苯乙烯树脂等苯乙烯树脂;树脂离聚物树脂(ionomer resins)、纤维素树脂等热塑性树脂和聚烯系弹性体、聚氯乙烯系弹性体、苯乙烯系弹性体、聚氨酯系弹性体、聚酯系弹性体、聚酰胺系弹性体等热塑性弹性体等树脂以及这些当中二种以上的混合物。优选聚烯树脂、聚酯树脂、丙烯树脂、苯乙烯树脂。
作为橡胶成分可例举二烯系橡胶成分的,具体可例举出:天然橡胶、丁二烯橡胶(butadiene rubber)、苯乙烯-丁二烯共聚物橡胶(styrene-butadiene
copolymer rubber)、异戊二烯橡胶(isoprene rubber)、丁基橡胶(butyl rubber)、丙烯腈-丁二烯橡胶(acrylonitrile-butadiene rubber)、丙烯腈-苯乙烯-丁二烯共聚物橡胶(acrylonitrile-styrene-butadiene copolymer rubber)、氯丁二烯橡胶(chloroprenerubber)、苯乙烯-异戊二烯共聚物橡胶(styrene-isoprene copolymer rubber)、苯乙烯-异戊二烯-丁二烯共聚物橡胶(styrene-isoprene-butadiene copolymer rubber)、异戊二烯-丁二烯共聚物橡胶(isoprene-butadiene copolymer rubber)、氢化天然橡胶(hydrogenated natural rubber)、脱蛋白质天然橡胶(deproteinized natural rubber)等。另外,作为二烯系橡胶成分以外的橡胶成分,可例举乙烯丙烯共聚物橡胶、腈橡胶、丙烯橡胶、环氧氯丙烷橡胶(epichlorohydrin rubber)、多硫化橡胶、硅橡胶、含氟橡胶、聚氨酯橡胶以及这些当中二种以上的混合物。优选天然橡胶、丁二烯橡胶、苯乙烯-丁二烯共聚物橡胶、异戊二烯橡胶、乙烯丙烯共聚物橡胶、腈橡胶。
<过氧化物(C)>
本发明发泡成形体用组合物所用过氧化物(C)只要是通常如乙烯化合物加成聚合所用的那种有机过氧化物即可。作为有机过氧化物,可使用烷系过氧化物、酰系过氧化物,譬如可例举二烷基过氧化物(dialkyl peroxides)、二酰基过氧化物(diacyl peroxide)、过氧酯(peroxy esters)等,具体还可例举出:过氧化特戊酸叔丁酯(t-butyl peroxypivalate)、二月桂酰过氧化物(dilauroyl peroxide)、过氧化2-乙基己酸1,1,3,3-四甲基丁酯(1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate)、过氧化2-乙基己酸叔丁酯(t-butylperoxy-2-ethylhexanate)、过氧化二苯甲酰(dibenzoyl peroxide)、过氧化月桂酸叔丁酯(t-butylperoxy laurate)、过氧化二异丙苯(dicumyl peroxide)、叔已基过氧化物(di-t-hexyl peroxide)等。优选过氧化二异丙苯。
<发泡剂(D)>
本发明发泡成形体用组合物所用发泡剂(D)为热解型发泡剂,可例举有机系发泡剂或无机系发泡剂。
作为有机系发泡剂,可例举出亚硝基化合物、偶氮化合物、磺酰肼化合物(sulfonyl hydrazide compounds)、叠氮化合物(azide compounds)等。作为亚硝基化合物,譬如可例举出:N,N-二甲基-N,N-二亚硝基对苯二甲酰胺(N,N’-dimethyl-N,N’-dinitrosoterephthalamide)、N,N-二亚硝基五亚甲基四胺(N,N’-dinitrosopentamethylenetetramine)等。作为偶氮化合物,譬如可例举出:偶氮甲酰胺(azodicarbonamide)(ADCA)、偶氮二甲酰胺(azobisformamide)、偶氮二异丁腈(azobisisobutyronitrile)、偶氮环己腈(azocyclohexylnitrile)、偶氮二氨基苯(azodiamino benzene)、偶氮二羧酸钡(barium azodicarboxylate)等。作为磺酰肼化合物,譬如可例举出:4,4-氧代双苯磺酰肼(4,4-oxybis(benzenesulfonylhydrazide))、苯磺酰肼(benzenesulfonylhydrazide)、甲苯磺酰肼(toluenesulfonylhydrazide)、二苯砜-3,3’-二磺酰肼(diphenylsulfone-3,3’-disulfonylhydrazide)等。作为叠氮化合物,譬如可例举出:叠氮化钙(calcium azide)、4,4-二苯二磺酰叠氮(4,4’-diphenyl disulfonyl azide)、对甲基苯磺酰叠氮(p-toluenesulfonyl azide)等。
作为无机系发泡剂,譬如可例举出:碳酸氢钠(小苏打)、碳酸钠、碳酸氢铵、碳酸铵、亚硝酸铵等。本发明优选有机系发泡剂。发泡剂通常用1种,但含2种以上也可。作为优选的发泡剂,可例举偶氮甲酰胺(ADCA)。
须指出,偶氮甲酰胺,室温下稳定,达到大约210℃以上时,放出以氮气、二氧化碳气体和一氧化碳气体为主要成分的起泡性气体,使树脂发泡。除了该偶氮甲酰胺而外,也可使用其它偶氮甲酰胺系发泡剂。作为偶氮甲酰胺系发泡剂的市售品,具体可例举出产品名“Cell Mike CE”、“Cell Mike C22”、“Cell Mike CAP-250”(以上为三协化成株式会社制)、产品名“VINYFOR AC#3”(永和化成工业株式会社制)等。这些可使用1种或2种以上。发泡剂含量可根据其种类、所期望发泡倍率等调整。
只要不妨碍本发明效果,除了上述过氧化物(C)而外,还可并用硫和硫给予体(sulfur donor)。作为硫和硫给予体的种类,可例举出:粉末硫、表面处理硫、沉淀硫、胶体硫、二硫代双吗啉(dithiodimorpholine)、二硫化烷基酚(alkylphenol disulfide)、二硫化秋兰姆(thiuram disulfide)、多硫化秋兰姆(thiuram polysulfide)等。
另外,只要在不妨碍本发明效果的范围内,除了上述(A)~(D)以外,还可添加其它添加剂。作为其它添加剂,譬如可例举出发泡助剂、相容剂、无机充填剂、颜料、防氧化剂、难燃剂、热稳定剂、封装有烃系发泡剂的热膨胀性微胶囊、含浸了烃系发泡剂的珠球等,可在不妨碍本发明效果的范围内根据需要配合于发泡体成形用组合物。
作为发泡助剂,譬如可例举出具有脲键的化合物、锌化合物。作为具有脲键的化合物,可例举出脲、亚肼基二甲酰胺(hydrazodicarbonamide)、双缩脲(biuret)、尿唑(urazole)等具有脲键(譬如-NHCONH 2、-NRCONH 2、-NHCONHR、-NRCONHR等;其中,R为任意基,优选有机基,更优选碳数1~10个的有机基,特别优选碳数1~10个的烷基)的化合物。
作为锌化合物,可例举出锌的氧化物、氢氧化物、碳酸盐、碱基性碳酸盐、硫酸盐、硝酸盐、亚磷酸盐、羧酸盐等。从提高发泡速度的观点,以添加锌化合物为佳。作为构成羧酸盐的羧酸,譬如可例举出:乙酸、丙酸、2-乙基己酸、壬酸、异壬酸、异癸酸、新癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、油酸、12-羟基硬脂酸、蓖麻油酸、山嵛酸等脂肪族酸;苯甲酸、对叔丁基苯甲酸(p-tert-butylbenzoic acid)、甲苯甲酸(toluic acid)、水杨酸、萘酸等芳香族酸。使用这些羧酸的锌的羧酸盐可以为正盐、酸性盐、碱性盐中任何一种形态。构成锌的羧酸盐的羧酸,虽然上面所列皆可使用,但是从降低VOC(挥发性有机化合物)的观点,优选使用了碳数12以上的脂肪酸的、常温下为粉体之物,譬如硬脂酸锌或月桂酸锌等。这些,与使用了其它羧酸的情况不同,不是液态,不必为了改善手操性而溶解于有机溶媒,故可优先使用。
作为相容剂,譬如可例举出马来酸酐、马来酸酐改性聚乙烯树脂、马来酸酐改性聚丙烯树脂或含环氧基树脂(甲基丙烯酸缩水甘油酯及乙烯的共聚物等),使用市售的各种相容剂也可。
本发明发泡成形体用组合物,优选改性纤维素纤维(A)/热塑性树脂和/或橡胶(B)/过氧化物(C)/发泡剂(D)=1~40/40~99/0.05~5/0.1~20的质量比。
另外,往本发明发泡成形体用组合物添加上述任意的硫和硫给予体或其它添加剂时,相对上述质量比的发泡成形体用组合物100质量份,其使用上限是10质量份。
<发泡成形体的制造方法>
本发明发泡成形体通过使上述发泡成形用组合物发泡成形而得到。具体而言,在过氧化物(C)和发泡剂(D)存在下,将具有不饱和键的改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)发泡成形,据此,使改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)反应。最好是通过以下工序得到成形体。
(工序I)将改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)加热熔融混炼的工序;
(工序II)工序I后添加过氧化物(C)、发泡剂(D)的工序;
(工序III)工序II后发泡成形的工序。
工序I中,使用单轴或多轴混炼机、混炼挤出机(Kneader)等,混合上述(A)和上述(B),使纤维成分均匀地微细分散于树脂成分中。即使混合前上述(A)没有预先纤丝化,纤维成分在该混合工序也被充分纤丝化。混合上述(A)和上述(B)之前,也可预先将上述(A)和粉末化的上述(B)混合。通过预先混合,混合时可更容易将上述(A)分散于上述(B)。预先将上述(A)和粉末化的上述(B)混合之际,既可以用混合机(mixer)等将干燥的上述(A)和干燥粉末化的上述(B)混合,也可将粉末化的上述(A)和上述(B)分散于与上述(A)和上述(B)均不反应的溶剂中,将该分散液过滤、干燥。虽然本发明制造方法中使用单轴或多轴混炼机、混炼挤出机等进行混合,但是混合中原料的配合顺序、混合温度、熔融时机等无特别限定。譬如,既可将上述(A)和上述(B)熔融而混炼,也可预先使上述(B)熔融,混炼时再与上述(A)混合。关于熔融混炼中混炼温度,考虑到加工性、改性纤维素纤维(A)与可塑性树脂和/或橡胶(B)的分散、劣化等,温度以70~240℃为佳。另外,单轴或多轴混炼机的螺杆转速以整个工序均在25~400rpm之范围为佳。
工序II为调制发泡体成形体用组合物的工序。工序I后,添加过氧化物(C)和发泡剂(D)可得到发泡体成形用组合物。须指出,只要在不妨碍本发明效果之范围内,也可在工序II或后述工序III添加树脂组合物或上述其它添加剂。
若从发泡体成形体用组合物的加工适性(分散性、混炼时间缩短、发泡剂分解抑制等)考虑,混合以采用混炼为佳,特别优选熔融混炼。另外,本发明制造方法中,虽然使用双辊等进行混合,但是混合中原料的配合顺序、混合温度、熔融时机等无特别限定。关于熔融混炼中混炼温度,考虑到发泡体形成体用组合物的加工适性(分散性、混炼时间缩短、发泡剂分解抑制等),温度以70~180℃为佳。
工序III中,将由上述工序II所得到的发泡体成形体用组合物投入金属模具等内,加热、加压下加以保持,据此,发泡体成形体用组合物中的具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)和过氧化物(C)反应。于是,更进一步地,发泡剂(D)因热而进行分解,产生的分解物呈溶解于发泡体成形用组合物中的状态。其后,通过解压,溶解了的发泡剂(D)的分解物气化,据此能得到发泡成形体。
关于上述加压发泡工序中温度,从发泡体形成用组合物的加工适性(发泡剂的分解温度、纤维的劣化抑制等)考虑,温度以140~180℃为佳。
另外,除了如上述工序III那样的加压发泡工序而外,也可用以下方法制造发泡体。
·挤出成形法:一边用挤出机将发泡成形体用组合物加压下熔融一边通过在挤出机最前端安装的模头(die)于大气压下挤出,据此,一边发泡一边得到连续形状的成形体。
·欠注法(short shot method):包括将量不满金属模具腔容积的熔融状态发泡成形体用组合物注射充填于金属模具腔的注射工序、和藉发泡剂产生的膨胀压力来充填金属模具腔空隙的发泡工序。
·退芯法(core back method):金属模具由固定模和可前进后退的活动模构成,包括往具有比与最终产品形状位置相当的金属模具腔芯头间隙(clearance)小的金属模具腔芯头间隙的金属模具腔注射充填熔融状态的发泡成形体用组合物的注射工序、和让活动模后退至金属模具腔芯头间隙而藉发泡剂产生的膨胀压力来充填金属模具腔空隙的发泡工序。
<发泡成形体用含改性纤维素树脂组合物>
下面描述得到本发明发泡成形体的其它方式。设改性纤维素纤维(A1)是含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)的反应物,而上述含羧基改性纤维素(E)是纤维素与碳数8以上的多元酸酐(G)的反应物。用改性纤维素纤维(A1)作改性纤维素纤维(A)时,就不必用过氧化物(C)和发泡剂(D)成分,对于含有上述改性纤维素纤维(A1)与热塑性树脂和/或橡胶(B)的发泡成形体用含改性纤维素树脂组合物,即使用硫和硫给予体取代过氧化物(C),或者不用发泡剂(D),而代之以采用气体作发泡剂往成形机注入的物理发泡,也能得到机械物性优异的发泡成形体,与使用含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D)的发泡成形体用组合物来发泡成形而得到的发泡成形体一样。
本发明发泡成形体用含改性纤维素树脂组合物由改性纤维素纤维(A1)与热塑性树脂和/或橡胶(B)构成。若从发泡成形体用含改性纤维素树脂组合物的加工适性(分散性、混炼时间缩短、造粒等)或成形体机械强度考虑,以按上述(A1)/上述(B)=1~40/40~99的质量比混合来制造发泡成形体用改性纤维素纤维含有树脂组合物为佳。本发明制造方法中,上述(A1)与上述(B)的混合最好是熔融混炼。
这样制造出的发泡成形体可使用于汽车零部件、建材部件、工业部件、玩具和杂货部件、体育保健部件等各种成形品、各种片材、薄膜、其它工业用品、缓冲材料、包装材料等。
实施例
以下描述本发明实施例。须指出,本发明并非受这些实施例所限定。另外,实施例中“%”,除非特别强调,均指“质量%”。
<物性值测定法>
这些实施例中的部分实施例所采用的物性值测定法如下。
<1>含羧基改性纤维素(E)的羟基置换度(DS)的计算
关于含羧基改性纤维素(E)的置换度DS计算,是在对反应物通过清洗除去作为原料使用的改性剂或其水解物等副产物后通过反应前后质量増加率来求出的,按如下公式计算。
DS=(a/b)/(c/d)
a:(含羧基改性纤维素(E)的干燥质量)-(纤维素纤维的干燥质量)
b:多元酸酐(G)的分子量
c:纤维素纤维的干燥质量
d:构成纤维素的葡萄糖单元分子量(分子量162)
<2>具有不饱和键的改性纤维素纤维的双键含量(碘值)的计算
设对每100g具有不饱和键的改性纤维素纤维起反应的碘量为碘值[I2(g)/纤维(100g)],按如下步骤作了测定。
(1)精确秤量试样5g放入三角烧瓶。
(2)添加NMP50g并搅拌,再加入韦氏(wijs)试剂(一氯化碘的醋酸水溶液)10mL和离子交换水50g。
(3)时常搅拌下静置于常温阴暗处30分钟。
(4)加入10质量%的碘化钾20mL和离子交换水20mL,然后用0.1N硫代硫酸钠滴定。
(5)在溶液颜色变浅时添加淀粉指示剂,继续滴定,淀粉指示剂显色消失时,读取此时的0.1N硫代硫酸钠滴定量作终值。
(6)不加试样,进行同样的试验,作为空白试验。
(7)按如下公式计算碘值。
纤维碘值[I2(g)/纤维(100g)]=(空白试验滴定量-滴定量)×1.269/绝干纤维量
<3>含改性纤维素树脂组合物中改性纤维素数均纤维口径计算
将含改性纤维素树脂组合物用325mesh不锈钢网包裹,二甲苯回流下,140℃处理5小时,据此,溶解除去树脂,得到改性CNF。用电子显微镜观察之,通过计测纤维宽而算出改性CNF的数均纤维口径。
<4>拉伸强度测定
将在上述<发泡体制造方法>的工序(III)所得到的发泡成形体切割,制成长60mm、宽10mm、厚4mm的试片。对所得到的试片,用Orientec Co.,Ltd.公司制拉伸试验机“TENSILONRTM-50”作了拉伸强度测定。
<5>密度测定
测定在上述<发泡体制造方法>的工序(III)所得到的发泡成形体在空气中的质量和在水中的质量,用阿基米德(Archimedes)法求密度,除以水密度值而算出密度。
<6>比强度计算
将上述(2)求出的拉伸强度值用上述(4)求出的密度除而算出比强度。
<改性纤维素纤维的制造>
[含羧基改性纤维素(E-1)的制造例]
往容器投入含水针叶树漂白牛皮纸浆(NBKP)500质量份(固含量100质量份)和N-甲基吡咯烷酮(NMP)150质量份,通过减压脱水而蒸馏除去水分,投入十六碳烯琥珀酸酐19.9质量份,80℃反应4小时。反应后减压蒸馏除去NMP,得到含羧基改性纤维素(E-1)。多元酸酐的置换度(DS)为0.11,碘值为8。须指出,(E-1)本身也是具有不饱和键的改性纤维素纤维(A)。
[含羧基改性纤维素(E-2)的制造例]
往容器投入含水NBKP500质量份(固含量100质量份)和NMP150质量份,通过减压脱水而蒸馏除去水分,投入琥珀酸酐6.2质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到含羧基改性纤维素(E-2)。多元酸酐的置换度(DS)为0.12,碘值为0。
[含羧基改性纤维素(E-3)的制造例]
往容器投入含水NBKP500质量份(固含量100质量份)和NMP150质量份,通过减压脱水而蒸馏除去水分,投入十六碳烯琥珀酸酐59.7质量份,80℃反应4小时。反应后减压蒸馏除去NMP,得到含羧基改性纤维素(E-3)。多元酸酐的置换度(DS)为0.29,碘值为15。须指出,(E-3)本身也是具有不饱和键的改性纤维素纤维(A)。
[含羧基改性纤维素(E-4)的制造例]
往容器投入含水NBKP500质量份(固含量100质量份)和NMP150质量份,通过减压脱水而蒸馏除去水分,投入1,2,3,6-四氢邻苯二甲酸酐9.5质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到含羧基改性纤维素(E-4)。多元酸酐的置换度(DS)为0.11,碘值为7。
[含羧基改性纤维素(E-5)的制造例]
往容器投入含水NBKP500质量份(固含量100质量份)和NMP150质量份,通过减压脱水而蒸馏除去水分,投入六氢邻苯二甲酸酐9.6质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到含羧基改性纤维素(E-5)。多元酸酐的置换度(DS)为0.12,碘值为0。
[表1]
纸浆种类 | 多元酸酐 | 多元酸酐的置换度(DS) | |
E-1 | NBKP | 十六碳烯琥珀酸酐 | 0.11 |
E-2 | NBKP | 琥珀酸酐 | 0.12 |
E-3 | NBKP | 十六碳烯琥珀酸酐 | 0.29 |
E-4 | NBKP | 1,2,3,6-四氢邻苯二甲酸酐 | 0.11 |
E-5 | NBKP | 六氢邻苯二甲酸酐 | 0.12 |
[具有不饱和键的改性纤维素纤维(A-1)的制造例]
往容器投入含羧基改性纤维素(E-1)100质量份(固含量)和NMP150质量份,投入丁基缩水甘油醚6.7质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到具有不饱和键的改性纤维素纤维(A-1)。碘值为7。
[具有不饱和键的改性纤维素纤维(A-2)的制造例]
往容器投入含羧基改性纤维素(E-1)100质量份(固含量)和NMP150质量份,投入甲基丙烯酸缩水甘油酯7.3质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到改性纤维素纤维(A-2)。碘值为48。
[具有不饱和键的改性纤维素纤维(A-3)的制造例]
往容器投入含羧基改性纤维素(E-2)100质量份(固含量)和NMP150质量份,投入甲基丙烯酸缩水甘油酯8.3质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到具有不饱和键的改性纤维素纤维(A-3)。碘值为53。
[具有不饱和键的改性纤维素纤维(A-4)的制造例]
往容器投入含羧基改性纤维素(E-3)100质量份(固含量)和NMP150质量份,投入甲基丙烯酸缩水甘油酯16.5质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到改性纤维素纤维(A-4)。碘值为120。
[具有不饱和键的改性纤维素纤维(A-5)的制造例]
往容器投入含羧基改性纤维素(E-4)100质量份(固含量)和NMP150质量份,投入甲基丙烯酸缩水甘油酯8.0质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到改性纤维素纤维(A-5)。碘值为47。
[具有不饱和键的改性纤维素纤维(A-6)的制造例]
往容器投入含羧基改性纤维素(E-1)100质量份(固含量)和NMP150质量份,投入甲基丙烯酸缩水甘油酯1.5质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到改性纤维素纤维(A-6)。碘值为17。
[具有不饱和键的改性纤维素纤维(A-7)的制造例]
往容器投入含羧基改性纤维素(E-1)100质量份(固含量)和NMP150质量份,投入甲基丙烯酸缩水甘油酯3.7质量份,130℃反应3小时。反应后减压蒸馏除去NMP,得到改性纤维素纤维(A-7)。碘值为26。
[具有不饱和键的改性纤维素纤维(A-8)的制造例]
往容器投入含羧基改性纤维素(E-1)100质量份(固含量)和NMP150质量份,投入甲基丙烯酸缩水甘油酯3.7质量份和丁基缩水甘油醚3.4质量份(摩尔比计,甲基丙烯酸缩水甘油酯:丁基缩水甘油醚=1:1),130℃反应3小时。反应后减压蒸馏除去NMP,得到改性纤维素纤维(A-8)。碘值为16。
[表2]
<发泡成形体用含改性纤维素树脂组合物的制造:工序(I)>
[发泡成形体用含改性纤维素树脂组合物(R-1)的制造例]
将改性纤维素纤维(E-1)40质量份与低密度聚乙烯(Prime Polymer Co.,Ltd.公司制:ULTZEX4020L)60质量份的混合物用Technovel公司制二轴混炼机(KZW;螺杆口径:15mm;L/D:45;螺杆转数:300rpm;处理速度200g/小时)140℃下混炼,将所得熔融混炼物用造粒机(pelletizer;井本制作所制)造粒,得到所含改性纤维素纤维被纳米纤丝化的发泡成形体用含改性纤维素树脂组合物(R-1)。须指出,数均纤维口径为220纳米。
[发泡成形体用含改性纤维素树脂组合物(R-2~9)的制造例]
除了上述发泡成形体用含改性纤维素树脂组合物(R-1)制造中所用改性纤维素纤维(E-1)如表3所示作了变更以外,都与(R-1)一样地进行制造。
[表3]
<发泡体成形用组合物的制造:工序(II)>
[发泡体成形用组合物(M-1)的制造例]
将由改性纤维素纤维(A-1)6.0质量份、低密度聚乙烯(Prime Polymer Co.,Ltd.公司制:ULTZEX4020L)83.0质量份、偶氮甲酰胺(ADCA;永和化成工业株式会社制:VINYFOR AC#3)5.0质量份、氧化锌(和光纯药工业株式会社制)5.0质量份和过氧化二异丙苯(日油株式会社制:Percumyl D)1.0质量份构成的组合物在130℃下用辊(roll)混炼,据此,得到所含改性纤维素纤维尚未被纳米纤丝化的发泡体成形用组合物(M-1)。
[发泡体成形用组合物(M-2)的制造例]
将发泡成形体用含改性纤维素树脂组合物(R-1)15.0质量份、低密度聚乙烯(PrimePolymer Co.,Ltd.公司制:ULTZEX4020L)74.0质量份、偶氮甲酰胺(ADCA;永和化成工业株式会社制:VINYFOR AC#3)5.0质量份、氧化锌(和光纯药工业株式会社制)5.0质量份和过氧化二异丙苯(日油株式会社制:Percumyl D)1.0质量份构成的组合物在130℃下用辊混炼,据此,得到发泡体成形用组合物(M-2)。
[发泡体成形用组合物(M-3~11)的制造例]
除了上述发泡体成形用组合物(M-2)制造中所用发泡成形体用含改性纤维素树脂组合物如表4所示作了变更以外,都与(M-2)一样,这样得到发泡体成形用组合物(M-3)~(M-11)。
[表4]
发泡体成形用组合物(M-1)~(M-11)的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D)和其它添加剂的质量比如表5所示。
[表5]
[发泡体成形用组合物(RM-1)的比较制造例]
将低密度聚乙烯(Prime Polymer Co.,Ltd.公司制:ULTZEX4020L)89.0质量份、偶氮甲酰胺(ADCA;永和化成工业株式会社制:VINYFOR AC#3)5.0质量份、氧化锌(和光纯药工业株式会社制)5.0质量份和过氧化二异丙苯(日油株式会社制:Percumyl D)1.0重量部构成的组合物在130℃下用辊混炼,据此,得到发泡体成形用组合物(RM-1)。
[发泡体成形用组合物(RM-2)的比较制造例]
将NBKP5.0质量份、低密度聚乙烯(Prime Polymer Co.,Ltd.公司制:ULTZEX4020L)84.0质量份、偶氮甲酰胺(ADCA;永和化成工业株式会社制:VINYFOR AC#3)5.0质量份、氧化锌(和光纯药工业株式会社制)5.0质量份和过氧化二异丙苯(日油株式会社制:PercumylD)1.0质量份构成的组合物在130℃下用辊混炼,据此,得到发泡体成形用组合物(RM-2)。
[发泡体成形用组合物(RM-3)的比较制造例]
将含羧基改性纤维素(E-5)5.6质量份、低密度聚乙烯(Prime Polymer Co.,Ltd.公司制:ULTZEX4020L)83.4质量份、偶氮甲酰胺(ADCA;永和化成工业株式会社制:VINYFOR AC#3)5.0质量份、氧化锌(和光纯药工业株式会社制)5.0质量份和过氧化二异丙苯(日油株式会社制:Percumyl D)1.0质量份构成的组合物在130℃下用辊混炼,据此,得到发泡体成形用组合物(RM-3)。
[发泡体成形用组合物(RM-4)的制造例]
将发泡成形体用含改性纤维素树脂组合物(R-1)15.0质量份、低密度聚乙烯(PrimePolymer Co.,Ltd.公司制:ULTZEX4020L)75.0质量份、偶氮甲酰胺(ADCA;永和化成工业株式会社制:VINYFOR AC#3)5.0质量份和氧化锌(和光纯药工业株式会社制)5.0质量份构成的组合物在130℃下用辊混炼,据此,得到发泡体成形用组合物(RM-4)。
[表6]
<加压发泡:工序(III)>
[实施例1]
将用上述发泡体成形用组合物(M-1)得到的发泡体成形用组合物充填于被加热于160℃的压力机内的金属模具,加压下保持25分钟,据此,得到发泡成形体。密度为0.10g/cm3。
[实施例2~11、参考例1、比较例1~3]
除了将上述发泡体(实施例1)的发泡体成形用组合物(M-1)如表7所示改变了种类而外,都与实施例1一样,这样得到发泡成形体。比较例3中,在无过氧化物的条件下进行发泡成形,具有不饱和键的改性纤维素纤维(A)不是含羧基改性纤维素(E)与仅有不饱和键及缩水甘油基的化合物(F)的反应物。此时,发泡成形时发泡剂的分解物即气体跑掉了,没能得到发泡体(因此没进行密度测定)。
[表7]
[发泡成形体的物性评价]
实施例1~11、参考例1、比较例1、2所得到的发泡成形体的物性(拉伸试验中的比强度)如表8所示。
[表8]
从实施例的表8可知,使用了符合本发明的发泡成形体的实施例1~11,同不符合的比较例1、2相比,所得发泡成形体的比强度提高。另外,从实施例1和2可知,通过使用发泡成形体用含改性纤维素树脂组合物,比强度提高。从实施例2和4可知,通过将含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)的反应物作改性纤维素纤维(A),比强度提高。从对实施例4和5的比较可知,通过多元酸酐(G)采用碳数8以上的多元酸酐,比强度提高。
Claims (18)
1.一种发泡成形体用组合物,其特征在于,含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D)。
2.如权利要求1所述的发泡成形体用组合物,其特征在于,改性纤维素纤维(A)是纳米纤丝化物。
3.如权利要求1所述的发泡成形体用组合物,其特征在于,改性纤维素纤维(A)是含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)的反应物。
4.如权利要求3所述的发泡成形体用组合物,其特征在于,含羧基改性纤维素(E)是纤维素与多元酸酐(G)的反应物。
5.如权利要求4所述的发泡成形体用组合物,其特征在于,多元酸酐(G)是碳数8以上的多元酸酐。
6.如权利要求1所述的发泡成形体用组合物,其特征在于,上述(B)的热塑性树脂是从聚烯系树脂、聚酯系树脂、丙烯系树脂、苯乙烯树脂选出的至少1种。
7.如权利要求1所述的发泡成形体用组合物,其特征在于,改性纤维素纤维(A)/热塑性树脂和/或橡胶(B)/过氧化物(C)/发泡剂(D)=1~40/40~99/0.05~5/0.1~20质量比。
8.一种发泡成形体,其中,以权利要求1~7中任一项所述的发泡成形体用组合物为原料。
9.一种发泡成形体用组合物的制造方法,该发泡成形体用组合物含有具有不饱和键的改性纤维素纤维(A)、热塑性树脂和/或橡胶(B)、过氧化物(C)、发泡剂(D),其特征在于,上述具有不饱和键的改性纤维素纤维(A)是通过使含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)反应而得到的。
10.如权利要求9所述的发泡成形体用组合物的制造方法,其特征在于,改性纤维素纤维(A)是这样得到的改性纤维素纤维:使纤维素与多元酸酐(G)反应而成含羧基改性纤维素(E),然后,进一步使具有不饱和键和缩水甘油基的化合物(F)与之反应。
11.如权利要求10所述的发泡成形体用组合物的制造方法,其特征在于,多元酸酐(G)是碳数8以上的多元酸酐。
12.一种发泡成形体的制造方法,其特征在于,在过氧化物(C)和发泡剂(D)存在下,将具有不饱和键的改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)发泡成形,据此,使改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)反应。
13.如权利要求12所述的发泡成形体的制造方法,其特征在于,具备以下工序:
(工序I)将改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)加热熔融混炼而将改性纤维素纤维(A)纳米纤丝化的工序;
(工序II)工序I后添加过氧化物(C)、发泡剂(D)的工序;
(工序III)工序II后发泡成形的工序。
14.一种发泡成形体用含改性纤维素树脂组合物,是含有具有不饱和键的改性纤维素纤维(A)与热塑性树脂和/或橡胶(B)的组合物,其特征在于,上述具有不饱和键的改性纤维素纤维(A)是含羧基改性纤维素(E)与具有不饱和键和缩水甘油基的化合物(F)的反应物;上述含羧基改性纤维素(E)是纤维素与碳数8以上的多元酸酐(G)的反应物。
15.权利要求14所述的发泡成形体用含改性纤维素树脂组合物,其特征在于,改性纤维素纤维(A)是纳米纤丝化物。
16.如权利要求14所述的发泡成形体用含改性纤维素树脂组合物,其特征在于,热塑性树脂是从聚烯系树脂、聚酯系树脂、丙烯系树脂、苯乙烯树脂选出的至少1种。
17.如权利要求14所述的发泡成形体用含改性纤维素树脂组合物,其特征在于,改性纤维素纤维(A)/热塑性树脂和/或橡胶(B)=1~40/40~99质量比。
18.一种发泡成形体,其中,以权利要求14~17中任一项所述的发泡成形体用含改性纤维素树脂组合物为原料。
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CN112334525A (zh) * | 2019-04-05 | 2021-02-05 | 星光Pmc株式会社 | 发泡体和其制造方法 |
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JP6917032B2 (ja) * | 2018-07-18 | 2021-08-11 | 理研化学工業株式会社 | 樹脂成形品およびその製造方法 |
US11945927B2 (en) | 2019-04-05 | 2024-04-02 | Seiko Pmc Corporation | Foam and method for producing same |
JP7429517B2 (ja) * | 2019-11-01 | 2024-02-08 | Psジャパン株式会社 | スチレン系樹脂発泡体 |
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