CN102066076A - 具有两层结构的复合成型品 - Google Patents

具有两层结构的复合成型品 Download PDF

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Publication number
CN102066076A
CN102066076A CN2009801197156A CN200980119715A CN102066076A CN 102066076 A CN102066076 A CN 102066076A CN 2009801197156 A CN2009801197156 A CN 2009801197156A CN 200980119715 A CN200980119715 A CN 200980119715A CN 102066076 A CN102066076 A CN 102066076A
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CN
China
Prior art keywords
resin
molded article
composite molded
thermoplastic resin
moulding product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2009801197156A
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English (en)
Inventor
冈村显
长井聪
滨田泰以
梁耀晖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyoto Institute of Technology NUC
Mitsubishi Gas Chemical Co Inc
Original Assignee
Kyoto Institute of Technology NUC
Mitsubishi Gas Chemical Co Inc
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Publication date
Application filed by Kyoto Institute of Technology NUC, Mitsubishi Gas Chemical Co Inc filed Critical Kyoto Institute of Technology NUC
Priority to CN201610899899.4A priority Critical patent/CN106863695A/zh
Publication of CN102066076A publication Critical patent/CN102066076A/zh
Pending legal-status Critical Current

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Abstract

本发明的课题在于，提供使具有极性的热塑性树脂、尤其是聚缩醛与其它树脂简单地复合粘接而成的成型品。根据本发明，可以提供使具有极性的热塑性树脂与以脂肪族酯结构为主要成分的树脂的至少两材料接触的面为熔融状态而复合粘接成的成型品。

Description

具有两层结构的复合成型品
技术领域
本发明涉及具有两层结构的复合成型品，所述两层结构为含有具有极性的热塑性树脂材料的层和含有以脂肪族酯结构为主要成分的树脂系材料的层的结构，进而，本发明的优选实施方式涉及具有上述两层结构、界面的粘接强度高、具有优异的机械物性的复合成型品。
背景技术
近年来，针对全球范围内的环境问题，为了防止产业废弃物污染环境，使用生物降解性(微生物降解性或自然降解性)的材料受到关注。进而，最近随着地球资源的枯竭、全球变暖，强烈要求对CO2排放量采取自我规范，其中，不是来源于石油而是来源于天然物质的材料、焚化处理时所需的热量、CO2产量少的材料受到关注。
一直以来，已知具有脂肪族酯结构的聚合物有生物降解性，代表性的物质有由微生物生产的聚-3-羟基丁酸酯(PHB)、作为合成高分子的聚己内酯(PCL)、以琥珀酸和丁二醇为主要成分的聚丁二酸丁二醇酯(PB S)或聚丁二酸/己二酸-丁二醇酯(PB SA)、聚酯碳酸酯(PEC)、以及以通过发酵生产的L-乳酸和/或D-乳酸为主要原料的聚乳酸(PLA)等。在这些当中，作为来源于天然物质的材料，例如，可列举出PLA。
除了PLA以外，这些具有脂肪族酯结构的聚合物通常是具有与聚乙烯类似的物性的、成型性和生物降解性良好的聚合物。然而，在要求刚性的领域、要求拉伸强度的领域，其不具有充分的强度。为了改善刚性，能够利用滑石等填充材料、纳米复合技术来实现改善，但还存在流动性降低等问题，期望对其进行改良。此外，对于PLA，强烈要求耐热性、韧性的提高以及耐水解性等。
对具有极性的热塑性树脂没有特别的限定，例如有聚缩醛，其是脂肪族醚型，或者是以脂肪族醚为主要成分的聚合物，其主要由不依赖于石油的原料即甲醇衍生，认为是环境负荷低的材料。其是作为机械性质、滑动特性、摩擦和磨耗特性、耐化学药品性等优异的工程塑料使用的材料，作为它的用途，多作为汽车、办公自动化机器等的关键部件使用，由于其显示出其规则的一次结构带来的高结晶性，因此，其用途以注射成型领域为中心逐渐扩大。
在与其它树脂复合化时，聚缩醛的高结晶性容易成为界面的粘接性的障碍，作为成功的例子而已知的组合，为聚缩醛与聚氨酯的聚合物合金材料这样的程度。此外，同样地，由于官能团实质上仅存在于聚合物末端，因此，存在成型片表面的反应活性也低、与其它材料的粘接强度、装饰性差的问题。因此，为了改良界面的粘接性，进行了如下尝试：使用各种增容剂，进行电晕放电处理、离子蚀刻处理等，以及进行聚合物的一级结构的改性。然而，这些操作大部分不一定能够充分地改良界面的粘接强度。
本申请人发现：通过使具有脂肪族酯结构的聚合物与具有氧化亚甲基结构的聚合物的相容性较高、并使得到的树脂组合物中的具有氧化亚甲基结构的聚合物的结晶度降低，得到了表现充分的生物降解性、并且机械特性优异的树脂组合物(专利文献1)，强烈期望具有优异的特征的由含有各成分的层构成的复合成型品的开发。此外，还公开了若干有关与生物降解性树脂层叠的层叠薄膜(专利文献2、3)，但它们实际上涉及的是将相同的聚酯彼此共挤出成型而得到的层叠薄膜，并且，没有关于提高界面粘接性的启示。
专利文献1：日本特开2000-17153号公报
专利文献2：日本特开2005-144726号公报
专利文献3：日本特开2005-219487号公报
发明内容
发明要解决的问题
本发明是鉴于这样的现有技术的问题而进行的，本发明的目的在于，提供使具有极性的热塑性树脂、尤其是聚缩醛与其它树脂通过简单地复合粘接而成的成型品。
用于解决问题的方案
本发明人等经过反复深入研究，结果发现，使用具有极性的热塑性树脂(A)和以脂肪族酯结构为主要成分的树脂(B)，并使至少两材料接触的面为熔融状态，能够表现高粘接强度，从而完成了本发明。
即，本发明涉及以下所示的多层薄膜、多层片、复合纤维，以及薄膜、片、注射成型品等的嵌件成型(insert molding)、嵌出成型(outsert molding)、以及夹层成型(sandwich molding)、类似形成焊缝(Weld)这样的复合成型品。
本发明包括以下的实施方案。
(1)一种复合成型品，其是具有两层结构的复合成型品：通过将含有具有极性的热塑性树脂(A)的成型品(a)配置在模具内部，将具有脂肪族酯结构的树脂(B)在高于该热塑性树脂(A)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(a)接触而得到，所述热塑性树脂(A)为聚缩醛树脂。
(2)一种复合成型品，其是具有两层结构的复合成型品：通过将含有具有脂肪族酯结构的树脂(B)的成型品(b)配置在模具内部，将具有极性的热塑性树脂(A)在高于该树脂(B)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(b)接触而得到，所述热塑性树脂(A)为聚缩醛树脂。
(3)根据上述(1)或(2)所述的复合成型品，其中，所述成型品(a)为薄膜、片或纤维复合体。
(4)根据上述(1)～(3)的任一项所述的复合成型品，其中，所述具有极性的热塑性树脂(A)预先含有一部分所述具有脂肪族酯结构的树脂(B)。
(5)根据上述(1)～(3)的任一项所述的复合成型品，其中，所述具有脂肪族酯结构的树脂(B)预先含有一部分所述具有极性的热塑性树脂(A)。
(6)根据上述(1)～(5)的任一项所述的复合成型品，其中，所述具有极性的热塑性树脂(A)为：相对于每100mol氧化亚甲基重复单元，含有0.2～15mol(DOL＝0.5～43phr)的下述(1)式所示的碳原子数2以上的氧化亚烷基重复单元的聚缩醛，
Figure BPA00001259679100041
式中，R0、R0’分别表示氢原子、烷基或具有烷基的有机基团、苯基或具有苯基的有机基团，m表示2～6的整数。
(7)根据上述(1)～(6)的任一项所述的复合成型品，其中，所述具有脂肪族酯结构的树脂(B)为选自聚乳酸(PLA)、聚酯碳酸酯(PEC)、聚丁二酸丁二醇酯(PBS)、聚丁二酸/己二酸-丁二醇酯(PBSA)以及它们的共聚物中的至少一种以上的树脂。
(8)一种复合成型品的制造方法，所述复合成型品的制造方法具有下述工序：
将含有具有极性的热塑性树脂(A)的成型品(a)配置在模具内部的工序；和，
将具有脂肪族酯结构的树脂(B)在高于该热塑性树脂(A)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(a)接触，形成两层结构的工序；
所述热塑性树脂(A)为聚缩醛树脂。
(9)一种复合成型品的制造方法，所述复合成型品的制造方法具有下述工序：
将含有具有脂肪族酯结构的树脂(B)的成型品(b)配置在模具内部的工序；和，
将具有极性的热塑性树脂(A)在高于该树脂(B)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(b)接触，形成两层结构的工序；
所述热塑性树脂(A)为聚缩醛树脂。
发明的效果
根据本发明，能够提供适合于具有极性的热塑性树脂与以脂肪族酯结构为主要成分的树脂的接触表面的改性、并且界面粘接强度高的优异的复合成型材料。
附图说明
图1表示在实施例1～4以及比较例1～6中进行的熔融状态下的粘接试验的示意图。
图2表示在实施例5～13以及比较例7～13中进行的薄膜与熔融树脂的粘接试验的示意图。
具体实施方式
以下，详细地说明本发明。
本发明的一个实施方式为一种复合成型品，其是具有两层结构的复合成型品，通过将含有具有极性的热塑性树脂(A)的成型品(a)配置在模具内部，将具有脂肪族酯结构的树脂(B)在高于该热塑性树脂(A)的熔点的温度下塑化并注入上述模具内部，使其与该成型品(a)接触而得到，上述热塑性树脂(A)为聚缩醛树脂。
此外，本发明的另一实施方式为一种复合成型品，其是具有两层结构的复合成型品，通过将含有具有脂肪族酯结构的树脂(B)的成型品(b)配置在模具内部，将具有极性的热塑性树脂(A)在高于该树脂(B)的熔点的温度下塑化并注入上述模具内部，使其与该成型品(b)接触而得到，上述热塑性树脂(A)为聚缩醛树脂。
本发明中使用的聚缩醛树脂是重复具有缩醛结构(-O-CRH-)(其中，R表示氢原子或有机基团。)的高分子，通常是以R为氢原子的氧化亚甲基(-CH2O-)为主要构成单元的物质。本发明中使用的聚缩醛树脂除了可以为仅由该重复结构构成的缩醛均聚物以外，还包括含有1种以上的上述氧化亚甲基以外的重复构成单元的共聚物(例如，嵌段共聚物)、三元共聚物等，进而，不限于线状结构，还可以具有分支、交联结构。
作为上述氧化亚甲基以外的构成单元，可列举出例如氧化亚乙基(-CH2CH2O-)、氧化亚丙基(-CH2CH2CH2O-)、氧化亚丁基(-CH2CH2CH2CH2O-)等碳原子数2～10的氧化亚烷基，尤其优选的是氧乙烯基。此外，这些氧化亚烷基可以具有碳原子数2～6的分支或交联结构。作为这样的氧化亚甲基以外的氧化亚烷基结构单元的含量，在聚缩醛中为0.2～15摩尔％是优选的。比该范围少时，聚缩醛的热稳定性降低，相反地，比该范围多时，熔点降低，有时实质上失去了优异的机械物性、耐化学药品性等。
本发明中优选的聚缩醛树脂为，相对于每100mol氧化亚甲基重复单元含有0.2～15mol(DOL＝0.5～43phr)下述(1)式所示的碳原子数2以上的氧化亚烷基重复单元的聚缩醛。
[化学式引
Figure BPA00001259679100071
式中，R0，R0’分别表示氢原子、烷基或苯基。m表示2～6的整数。作为上述烷基，可列举出例如甲基、乙基、丙基等。
聚缩醛树脂的制造方法可以是任意的，可以通过现有公知的任意的方法来制造。例如，作为以氧化亚甲基和碳原子数2～4的氧化亚烷基作为构成单元的聚缩醛树脂的制造方法，可以通过使甲醛的三聚体(三聚甲醛)、四聚体(四聚甲醛)等氧化亚甲基的环状低聚物与环氧乙烷、1，3-二氧杂环戊烷、1，3，6-三氧杂环辛烷、1，3-二氧杂环庚烷等含有碳原子数2～4的氧化亚烷基的环状低聚物共聚来制造。
作为本发明中使用的聚缩醛树脂，三聚甲醛、四聚甲醛等环状低聚物与环氧乙烷或1，3-二氧杂环戊烷的共聚物是优选的，其中，三聚甲醛与1，3-二氧杂环戊烷的共聚物是更优选的。此外，作为其熔融粘度，以基于ASTM-D 1238(190℃、2.16kg荷重下)的熔融指数(MI)计为0.01～150g/10分钟是优选的。
作为聚缩醛树脂中的添加剂，热稳定剂、抗氧化剂是公知的，也适合在本发明中使用。
作为添加和配合的热稳定剂，可列举出三聚氰胺、三聚氰胺树脂、羟甲基三聚氰胺、苯并胍胺(benzoguanamine)、双氰胺(cyanoguanidine)、N，N-二芳基三聚氰胺、CTU胍胺(3，9-双[2-(3，5-二氨基-2，4，6-三氮杂苯基)乙基]-2，4，8，10-四氧螺[5，5]十一烷)、CMTU胍胺(3，9-双[1-(3，5-二氨基-2，4，6-三氮杂苯基)甲基]-2，4，8，10-四氧螺[5，5]十一烷)等胺取代三嗪化合物、聚酰胺类、尿素衍生物、肼衍生物、氨基甲酸酯类等，三聚氰胺是特别优选的。通常该热稳定剂的添加量，相对于100重量份聚缩醛为0.01～5.0重量份，但在例如作为长丝(filament)材料使用时，尤其是在添加该胺取代三嗪化合物中的、与甲醛或甲醛共聚物的分子末端键合而生成交联结构的化合物时，需要注意其添加量。其添加量需要使获得的甲醛树脂组合物的热稳定性能够耐受加工条件，需要优选为0.05重量份以下。添加量多于该量时，成为拉伸性降低的原因。
作为抗氧化剂，可列举出例如位阻酚，作为一般市售的酚系抗氧化剂，具体地，可列举出1，6-己二醇-双[3-(3，5-二叔丁基-4-羟基苯基)丙酸酯]、三乙二醇-双-3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、季戊四醇-四-3-(3，5-二叔丁基-4-羟基苯基)丙酸酯、2，2’-亚甲基双(6-叔丁基-4-甲基苯酚)、3，9-双{2-[3-(3-叔丁基-4-羟基-5-甲基苯基]丙酰氧基)-1，1-二甲基乙基}-2，4，8，10-四氧螺[5，5]十一烷、N，N’-己烷-1，6-二基双[3-(3，5-二叔丁基-4-羟基苯基)丙酰胺]、3，5-双(1，1-二甲基乙基)-4-羟基苯丙酸1，6-己二基酯等。其中，特别优选使用三乙二醇-双-3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、季戊四醇-四-3-(3，5-二叔丁基-4-羟基苯基)丙酸酯、1，6-己二醇-双[3-(3，5-二叔丁基-4-羟基苯基)丙酸酯]。其添加量，相对于100重量份甲醛共聚物为0.01～5.0重量份，优选为0.01～2.0重量份，特别优选为0.02～1.0重量份。位阻酚的配合量少时，加工时的分解引起的树脂的分子量降低、分解气体的混入变得不能忽视，产生加工性降低的问题，相反，其配合量过多时，产生渗出增多、加工品的外观受损的问题。
进而，在不损害本发明的本来目的的范围内，可以添加公知的添加剂和/或填充剂。作为添加剂，可列举出例如结晶成核剂、上述以外的抗氧化剂、聚亚烷基二醇等增塑剂、消光剂、发泡剂、润滑剂、脱模剂、抗静电剂、紫外线吸收剂、光稳定剂、热稳定剂、消臭剂、阻燃剂、滑动剂、香料、抗菌剂等。此外，作为填充剂，可列举出玻璃纤维、滑石、云母、碳酸钙、钛酸钾、晶须等。进而，也可以加入颜料、染料以加工成所期望的色调。此外，也可以加入各种单体、偶联剂、末端处理剂、其它的树脂、木粉、淀粉等进行改性。
作为本发明中的具有脂肪族酯结构的树脂(B)，可列举出聚-3-羟基丁酸酯(PHB)、聚己内酯(PCL)、聚丁二酸丁二醇酯(PBS)、聚丁二酸/己二酸-丁二醇酯(PBSA)、聚乳酸(PLA)等脂肪族聚酯，聚酯碳酸酯(PEC)，以及它们的共聚物等。根据需要，可以进一步向这些聚合物中添加各种添加剂，例如抗氧化剂、水解防止剂、光稳定剂、热稳定剂、耐候剂、颜料、润滑剂。
此外，具有极性的热塑性树脂(A)与具有脂肪族酯结构的树脂(B)可以各自单独使用，也可以各自均匀熔融混合后再使用。其中，作为具有两层结构的复合材料，为了有效利用各层的材料特性，其中一层的材料的添加量应为50vol％以下，应特别优选为30vol％以下。
本发明的复合成型品以使用如上所述的具有极性的热塑性树脂(A)、尤其是聚缩醛树脂与具有脂肪族酯结构的树脂(B)这样的组合为特征，将含有具有极性的热塑性树脂(A)的成型品(a)配置在模具内部，将具有脂肪族酯结构的树脂(B)在高于该热塑性树脂(A)的熔点的温度下塑化并注入上述模具内部，使其与该成型品(a)接触，从而制造具有两层结构的复合成型品。
或者，将含有具有脂肪族酯结构的树脂(B)的成型品(b)配置在模具内部，将具有极性的热塑性树脂(A)在高于该树脂(B)的熔点的温度下塑化并注入上述模具内部，使其与该成型品(b)接触，从而制造具有两层结构的复合成型品。
本发明也包括例如通过共挤出得到的多层薄膜、多层片、复合纤维、或者在一个片、薄膜上熔融挤出另一材料得到的层叠薄膜、层叠片。本发明优选通过嵌件注射成型法制造复合成型品。
嵌件成型法是指，将已经赋形的不同种材料固定在注塑成型机的模具内部，并通过注塑成型而嵌入另一材料的嵌件成型法，尤其是有效利用金属、无机固体材料的一般的成型法。作为与其类似的成型法，有嵌出成型法，它也用于使不同种材料一体化。
在为夹层成型法的情况下，通常有两个具备使材料塑化的加热装置的装置，对此具有共同的模腔以及浇口。注入规定量的形成表皮层的材料，接着从同一浇口注入形成芯层的材料。由此，先注入的材料位于表皮侧、后注入的材料形成芯，从而形成表面被其它材料被覆的复合成型品。在具有共同的模腔，但浇口不同的情况下，在模腔内存在两材料接触的面(焊缝)，与此相对，在夹层成型法的情况，基本上是芯层整面与表皮接触而被覆盖。
使具有极性的热塑性树脂(A)与具有脂肪族酯结构的树脂(B)复合化时，需要使两者的成分的至少接触的部分为熔融状态。熔融状态不充分的情况下，不能获得充分的粘接强度。例如，为聚缩醛与具有脂肪族聚酯的树脂的组合的情况时，可以认为，只要熔融状态充分，通过设定适当的注入条件(被注入的树脂的温度、注入速度、保持压力、保持时间、模具温度)使界面附近的两成分混合、形成共晶，就可以表现高的界面强度。
例如，在嵌件成型的情况下，若被注入的树脂的温度过低，则预先插入模具内的成型品的表面没有充分地熔融，不能得到高的界面强度。本发明中，尤其优选的是，注入树脂温度为高于预先插入模具内的成型品的熔点的温度。然而，该温度过高时，会发生该成型品的形状走样、机械物性等降低，因此，上限的基准为高于熔点100℃左右。此外，被插入的成型品的结晶度高时，熔融所需的热量多，因此，需要将注入树脂温度设定得更高。可以认为，注入速度、保持压力、保持时间与界面处的相互侵入相关，在不影响成型效率、成型品概观的范围，尤其是保持压力、保持时间设定得越高越优选。
实施例
以下，通过实施例具体地说明本发明，但本发明不受它们的限定。
<实施例1～4、比较例1～6>
熔融状态下的粘接试验
按照图1所示的要点，在加热到190℃的热板上使表1记载的树脂材料分别为熔融状态，在保持该熔融状态下快速翻转叠合并热压(在5kg的荷重下进行10秒钟)，然后放冷。观察两成分间的粘接状态，分等级评价粘接强度。
可以确认，作为热塑性树脂(A)的聚缩醛树脂与具有脂肪族聚酯结构的树脂(B)的组合通过在熔融状态下接触而具有强的粘接强度。
表1熔融状态下的粘接试验
[表1]
 实施例1  实施例2  实施例3  实施例4  比较例1  比较例2  比较例3  比较例4  比较例5  比较例6
  熔融树脂(A)   POM   POM   POM   POM   POM   POM   POM   POM   PP   PE
  熔融树脂(B)   PLA   PBS   PBSA   PEC   PET   PBT   PE   PP   PLA   PLA
  粘接状态   ○   ○   ○   ○   ×   ×   ×   ×   △   ×
○：良好。即便撕裂薄膜也没有剥离。
△：若撕裂薄膜，则剥离。
×：没有粘接。
※P408(东洋纺制造的热塑性聚酯弹性体(Pelprene))
※聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)在300℃熔融
POM(聚缩醛、熔点155℃)：Mitsubishi Engineering-PlasticsCorporation制Iupital V20-HE
PLA(聚乳酸、熔点170℃)：UNITIKA制TERRAMACTE-2000
PB S(聚丁二酸丁二醇酯、熔点114℃)：昭和高分子制Bionolle#1001
PB SA(聚丁二酸/己二酸-丁二醇酯、熔点95℃)：昭和高分子制Bionolle#3001
PEC(聚酯碳酸酯、熔点106℃)：三菱瓦斯化学株式会社制IUPEC PEC350
P40B(热塑性聚酯弹性体、熔点180℃)：东洋纺制Pelprene
PET(聚对苯二甲酸乙二醇酯、熔点270℃)：钟纺合织制Bellpet IP 123A
PBT(聚对苯二甲酸丁二醇酯、熔点225℃)：Mitsubishi Engineering-Plastics Corporation制NOVADURAN 5010R5
PE(聚乙烯、熔点100℃)：Prime Polymer Co.，Ltd.制HI-ZEX1700J
PP(聚丙烯、熔点160℃)：Prime Polymer Co.，Ltd.制Prime polypro F113G
<实施例5～13、比较例7～13>
薄膜与熔融树脂的粘接试验
接着，在表2所示的薄膜与熔融树脂的组合中进行简易粘接试验。薄膜使用通过口径φ25mm的单螺杆挤出机和200mm宽的T模头(悬吊型，hanger type)制备的未拉伸薄膜、或者使用将颗粒热压制备的薄膜。同样地，按照图2中的要点，使薄膜与熔融树脂接触并加压。即，一方为薄膜、另一方的树脂为熔融状态，快速翻转叠合并热压(在约5kg的荷重下进行10秒钟)。观察薄膜上的粘接状态，并分级评价粘接强度。
通过使熔融树脂的温度为高于薄膜的熔点的温度，接触时，薄膜表面部分熔融，显示强的粘接强度。此外，使用结晶度高的聚缩醛薄膜时，需要将熔融树脂温度设定得更高。此外，如实施例7所示，通过在薄膜成分中添加不损害聚缩醛的特征的程度的PLA来降低结晶度，提高了粘接性。
表2薄膜与熔融树脂的粘接试验
[表2]
Figure BPA00001259679100131
Figure BPA00001259679100132
○：良好。即使撕裂薄膜也没有剥离。
△：若撕裂薄膜，则剥离。
×：没有粘接。
<实施例14～28>
薄膜嵌件成型
在表3所示的组合以及注入条件下进行薄膜嵌件成型。进行薄膜的90°剥离试验来测定薄膜的粘接状况。
表3薄膜嵌件成型
[表3]
  实施例14   实施例15   实施例16   实施例17   实施例18
  薄膜(A)   POM   POM   POM   POM   POM
  熔点   ℃   155   155   155   155   155
  基质(B)   PLA   PLA   PLA   PLA   PLA
  成型条件
  注入速度   mm/sec   300   300   300   300   500
  注入树脂温度   ℃   200   210   220   230   230
  ΔT   ℃   45   55   65   75   75
  保持压力   MPa   5   5   5   5   5
  保持时间   sec   20   20   20   20   20
  模具温度   ℃   30   30   30   30   30
  粘接强度   N/mm   0.04   0.05   0.12   0.12   0.13
  实施例19   实施例20   实施例21   实施例22   实施例23
  薄膜(A)   POM   POM   POM   POM   POM
  熔点   ℃   165   165   165   165   165
  基质(B)   PLA   PLA   PLA   PLA   PLA
  成型条件
  注入速度   mm/sec   300   300   300   300   500
  注入树脂温度   ℃   200   210   220   230   230
  ΔT   ℃   35   45   55   65   65
  保持压力   MPa   5   5   5   5   5
  保持时间   sec   20   20   20   20   20
  模具温度   ℃   30   30   30   30   30
  粘接强度   N/mm   0.02   0.03   0.04   0.07   0.08
Figure BPA00001259679100141
<实施例29、比较例14～17>
焊缝成形(weld formation)
按照表4所示组合进行焊缝成形，成型成哑铃片。进行拉伸试验并观察断裂的位置。
表4焊缝成形片的拉伸试验
[表4]
  实施例29   比较例14   比较例15   比较例16   比较例17
  (A)   POM   POM   PLA   POM   -
  (B)   PLA   POM   PLA   -   PLA
  拉伸强度[MPa]   51   51   71   50   67
  拉伸断裂伸长率[％]   68   13   3   26   4
  缩颈   有   无   无   无   无
实施例29中，焊缝强度以及拉伸率都没有降低，尤其是拉伸率，发生缩颈(necking)并维持高的拉伸率，在焊缝界面没有发生断裂。
<实施例30～32>
夹层成型
按照表5所示的组合进行夹层成型，成型成哑铃片。进行弯曲试验，弯曲模量、强度依赖于试验片截面中各成分的占有率，没有抵抗弯曲应力的界面剥离。
表5夹层成型片的弯曲试验结果
[表5]
Figure BPA00001259679100151
括号内，使用各单一成分的数据由截面的表皮芯面积计算得到的算术平均值。

Claims (9)

1.一种复合成型品，其是具有两层结构的复合成型品，通过将含有具有极性的热塑性树脂(A)的成型品(a)配置在模具内部，将具有脂肪族酯结构的树脂(B)在高于该热塑性树脂(A)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(a)接触而得到，所述热塑性树脂(A)为聚缩醛树脂。
2.一种复合成型品，其是具有两层结构的复合成型品，通过将含有具有脂肪族酯结构的树脂(B)的成型品(b)配置在模具内部，将具有极性的热塑性树脂(A)在高于该树脂(B)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(b)接触而得到，所述热塑性树脂(A)为聚缩醛树脂。
3.根据权利要求1或2所述的复合成型品，其中，所述成型品(a)为薄膜、片或纤维复合体。
4.根据权利要求1～3的任一项所述的复合成型品，其中，所述具有极性的热塑性树脂(A)预先含有一部分所述具有脂肪族酯结构的树脂(B)。
5.根据权利要求1～3的任一项所述的复合成型品，其中，所述具有脂肪族酯结构的树脂(B)预先含有一部分所述具有极性的热塑性树脂(A)。
6.根据权利要求1～5的任一项所述的复合成型品，其中，所述具有极性的热塑性树脂(A)为：相对于每100mol氧化亚甲基重复单元，含有0.2～15mol(DOL＝0.5～43phr)的下述(1)式所示的碳原子数2以上的氧化亚烷基重复单元的聚缩醛；
Figure FPA00001259679000011
式中，R0、R0’分别表示氢原子、烷基或具有烷基的有机基团、苯基或具有苯基的有机基团，m表示2～6的整数。
7.根据权利要求1～6的任一项所述的复合成型品，其中，所述具有脂肪族酯结构的树脂(B)为选自聚乳酸(PLA)、聚酯碳酸酯(PEC)、聚丁二酸丁二醇酯(PBS)、聚丁二酸/己二酸-丁二醇酯(PBSA)以及它们的共聚物中的至少一种以上的树脂。
8.一种复合成型品的制造方法，所述复合成型品的制造方法具有下述工序：
将含有具有极性的热塑性树脂(A)的成型品(a)配置在模具内部的工序；和，
将具有脂肪族酯结构的树脂(B)在高于该热塑性树脂(A)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(a)接触，形成两层结构的工序；
所述热塑性树脂(A)为聚缩醛树脂。
9.一种复合成型品的制造方法，所述复合成型品的制造方法具有下述工序：
将含有具有脂肪族酯结构的树脂(B)的成型品(b)配置在模具内部的工序；和，
将具有极性的热塑性树脂(A)在高于该树脂(B)的熔点的温度下塑化并注入所述模具内部，使其与该成型品(b)接触，形成两层结构的工序；
所述热塑性树脂(A)为聚缩醛树脂。
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