CN107108784B - 改性乙烯系聚合物、粘接性树脂组合物、叠层体及其用途 - Google Patents

改性乙烯系聚合物、粘接性树脂组合物、叠层体及其用途 Download PDF

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CN107108784B
CN107108784B CN201580062369.8A CN201580062369A CN107108784B CN 107108784 B CN107108784 B CN 107108784B CN 201580062369 A CN201580062369 A CN 201580062369A CN 107108784 B CN107108784 B CN 107108784B
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ethylene polymer
modified ethylene
laminate
modified
resin composition
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CN107108784A (zh
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前田峻宏
松本浩德
佐久间孝
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Mitsui Chemicals Inc
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Abstract

本发明的课题在于提供一种燃料阻隔性高、粘接性、机械强度优异的改性乙烯系聚合物及其用途。本发明的改性乙烯系聚合物的特征在于，乙烯系聚合物的至少一部分被不饱和羧酸或其衍生物接枝改性，接枝改性量在0.15重量％～0.40重量％的范围，并且，交叉分级色谱测得的80℃以下时的洗脱量为10重量％以下。

Description

改性乙烯系聚合物、粘接性树脂组合物、叠层体及其用途
技术领域
本发明涉及改性乙烯系聚合物及其用途。具体而言，涉及能够提供燃料阻隔性高、粘接性和机械强度优异的粘接性树脂组合物的改性乙烯系聚合物、和使用了聚合物的叠层体。
背景技术
聚乙烯树脂近年来作为汽车用燃料箱被广泛使用。聚乙烯树脂由于燃料的透过性大，因此，有在聚乙烯树脂上叠层气体阻隔性优于聚乙烯树脂的树脂，例如乙烯-乙酸乙烯酯共聚物皂化物(以下称为“EVOH”。)等的方法。此时，由于聚乙烯和EVOH的粘接性非常低，因此，使用将聚乙烯用羧酸类接枝改性而得到的改性物等的粘接性树脂进行粘接，得到了多层燃料箱(专利文献1)。
另外，对于与安装于燃料箱上部的外部管体连接的管接头，也期望密封性优异并且机械强度和耐冲击性优异。作为这样的管接头，提出了具有聚酰胺和聚乙烯树脂的2层构造的管接头(专利文献2)。
现有技术文献
专利文献
专利文献1：日本特开平10－156978号公报
专利文献2：日本特开2004－293324号公报
发明内容
发明所要解决的课题
对于上述那样的阀、管接头等箱周边部件，使用包含气体阻隔树脂和改性乙烯系聚合物的叠层体，将改性乙烯系聚合物部加热、再熔融(熔接)，由此，经由改性乙烯系聚合物部，箱周边部件熔接于聚乙烯制汽油箱。但是，随着对于抑制塑料燃料箱的燃料透过的要求变得更加严格，现有的技术逐渐变得难以满足要求。
因此，本发明的课题在于提供与构成汽油箱等的聚乙烯等的粘接力优异、且机械强度优异、并且具有良好的燃料阻隔性的改性乙烯系聚合物和使用其的叠层体。
用于解决课题的方法
本发明的发明人进行了深入研究，结果发现，使用了具有特定的物性的改性乙烯系聚合物的粘接性树脂组合物、和由该粘接性树脂组合物得到的叠层体能够实现解决上述课题的优异效果，从而完成了本发明。
即，本发明的构成如下所示。
[1]一种改性乙烯系聚合物，其为乙烯系聚合物的至少一部分被不饱和羧酸或其衍生物接枝改性得到的改性乙烯系聚合物，接枝改性量在0.15重量％～0.40重量％的范围，并且，交叉分级色谱测得的80℃以下时的洗脱量为10重量％以下。
[2]如[1]所述的改性乙烯系聚合物，其中，上述洗脱量为80℃以下时的向邻二氯苯的洗脱量。
[3]如[1]或[2]所述的改性乙烯系聚合物，其中，上述乙烯系聚合物的至少一部分是在茂金属催化剂的存在下进行聚合得到的。
[4]含有上述[1]～[3]所述的改性乙烯系聚合物的粘接性树脂组合物。
[5]一种叠层体，其包括由上述[4]所述的粘接性树脂组合物形成的粘接层、和设置于该粘接层的至少一个面的树脂层。
[6]如[5]所述的叠层体，其中，上述树脂层包含选自聚酰胺和乙烯-乙烯醇共聚物中的至少1种。
[7]如[5]或[6]所述的叠层体，其为由共挤出成型法制得的。
[8]如[5]或[6]所述的叠层体，其为由注射成型法制得的。
[9]使用了上述[5]～[8]所述的叠层体的塑料燃料箱用的燃料阀。
发明的效果
本发明的改性乙烯系聚合物进行规定的接枝改性而成，并且将作为结晶性评价的尺度之一的CFC(交叉分级色谱)测得的洗脱量调整为规定的范围以下，因此，粘接性和机械强度优异，并且显示良好的燃料阻隔性。因此，将这样的改性乙烯系聚合物用于粘接性树脂组合物而构成叠层体的粘接层时，可以得到与聚乙烯等的粘接强度高、长期的耐久性和耐冲击性优异的叠层体。
另外，如果将本发明的粘接性树脂组合物用于箱周边部件用叠层体，则与汽油箱部件的粘接性高，即使与高温的汽油、轻油接触，也能够保持充分的粘接强度，并且长期的耐久性优异。因此，本发明涉及的叠层体能够合适地用于阀等箱周边部件用途。
附图说明
图1是表示实施例中的聚酰胺粘接力评价方法的概略图。
具体实施方式
[改性乙烯系聚合物]
本发明的改性乙烯系聚合物中，乙烯系聚合物的一部分或全部被不饱和羧酸或其衍生物接枝改性。
作为不饱和羧酸或其衍生物，例如，可以列举丙烯酸、马来酸、富马酸、四氢邻苯二甲酸、衣康酸、柠康酸、巴豆酸、异巴豆酸、降冰片烯二酸(内顺－双环[2,2,1]庚－5－烯－2,3－二羧酸)等不饱和羧酸；或其衍生物例如酰卤、酰胺、酰亚胺、酸酐、酯等。
作为这样的衍生物的具体例，例如，可以列举丙二酰氯、马来酰亚胺、马来酸酐、柠康酸酐、马来酸单甲酯、马来酸二甲酯、马来酸甘油酯等。
这些之中，不饱和羧酸或其酸酐是合适的，特别优选使用马来酸、降冰片烯二酸或这些的酸酐。
本发明涉及的改性乙烯系聚合物能够通过各种公知的方法得到。作为具体的方法，可以列举：将乙烯系聚合物溶解于有机溶剂，接着在得到的溶液中添加不饱和羧酸或其衍生物和根据需要的有机过氧化物等自由基引发剂，通常以60～350℃、优选80～190℃的温度使其反应0.5～15小时、优选1～10小时的方法；或者，使用挤出机等，在无溶剂下，在乙烯系聚合物中添加不饱和羧酸或其衍生物和根据需要的有机过氧化物等自由基引发剂，通常以乙烯系聚合物的熔点以上、优选120～350℃的温度使其反应0.5～10分钟的方法等。
作为本发明涉及的改性乙烯系聚合物的原料的改性前的乙烯系聚合物，为乙烯的均聚物或乙烯与α－烯烃的共聚物。与乙烯共聚的α－烯烃为碳原子数3以上、优选3～10的α－烯烃，具体而言，能够列举丙烯、1－丁烯、1－戊烯、1－己烯、1－辛烯、1－癸烯、4－甲基－1－戊烯和这些的2种以上的组合等。α－烯烃的共聚量没有特别限定，通常为10摩尔％以下。改性前的乙烯系聚合物只要是所得到的改性乙烯系聚合物的密度在后述的范围内即可，没有特别限定，希望密度在930～980kg/m3的范围内且MFR在0.1～50g/10分钟的范围内。
改性前的乙烯系聚合物能够使用公知的菲利普斯型催化剂(铬系)、齐格勒型催化剂(钛系)或茂金属系催化剂通过公知的方法制造。其中，由于在茂金属催化剂的存在下聚合得到的乙烯系聚合物满足本发明的规定的洗脱量，因而是合适的。
改性乙烯系聚合物的密度在920～960kg/m3的范围，根据ASTM D1238(190℃、2160g负荷)测得的熔体流动速率(MFR)在0.1～10g/10分钟、优选0.1～1.0g/10分钟的范围。通过使用这样范围的密度的改性乙烯系聚合物，容易得到耐热粘接性优异的组合物。另外，通过使MFR在上述范围内，可以得到成型性良好的组合物。
另外，改性乙烯系聚合物根据ASTM D1238(190℃)测得的10kg负荷的熔体流动速率(＝I10)与2.16kg负荷的熔体流动速率(＝I2)之比(＝I10/I2)在I10/I2≤20的范围。
熔体流动速率、密度和I10/I2在上述范围时，作为汽油箱周边的多层成型部件用粘接性树脂组合物具有充分的机械强度，且对于长时间的低应力的耐裂性优异，注塑成型性和吹塑成型性优异。
改性乙烯系聚合物优选接枝单体相对于改性前的乙烯系聚合物的重量在0.15～0.40重量％的范围、优选在0.15～0.30重量％的范围、进一步优选在0.15～0.25重量％的范围，一部分或全部被不饱和羧酸或其衍生物接枝改性。接枝单体的重量当量在上述范围时，作为汽油箱周边的多层成型部件用粘接性树脂组合物具有对于气体阻隔性树脂的充分的粘接强度，且在对于长时间的汽油浸渍也能够保持粘接力方面是优异的。
改性乙烯系聚合物在CFC测定中的80℃以下时的洗脱量、优选80℃以下时的向邻二氯苯的洗脱量为10重量％以下。满足这样的洗脱量的改性乙烯系聚合物由于环境变化引起的结晶性的变化小，并且对于汽油等的膨润也少，机械强度高，并且高温时的粘接强度也高，气体阻隔性长期稳定。该理由并不明确，但是可以认为，乙烯系聚合物不是由均一的结晶性构成的，存在结晶性分布，洗脱量大的乙烯系聚合物中，厚的结晶和薄的结晶混合存在，随着环境温度的上升，从薄的结晶开始丧失结晶性，担负燃料阻隔性的结晶成分减少，因此阻隔性降低。
本领域技术人员能够适当调整在CFC测定中的80℃以下时的洗脱量，例如，能够通过调整密度、组成分布(MFR)和接枝量等来调整。为了使洗脱量为10重量％以下，例如，能够通过使用在茂金属系催化剂的存在下制造的具有窄的组成分布的乙烯系聚合物来调整。
如果洗脱量变多，在用于多层构造体时，存在相对于汽油等的燃料油的膨润量变多、容易失去机械强度、并且高温时的粘接强度也变差的担心。
改性乙烯系聚合物基于JIS K6774在5.5MPa/80℃温水中的全切口式蠕变试验测得的直至破裂的时间在100hr以上的范围。蠕变试验测得的直至破裂的时间在上述范围时，关于因伴随聚乙烯制汽油箱的变形而作用于箱周边部件的长期低应力所产生的改性聚烯烃中的裂缝，具有很高的耐裂性。
改性乙烯系聚合物用于与聚乙烯制汽油箱接合的气体阻隔树脂制周边部件的构成材料。更详细而言，利用注塑成型、管式挤出成型、吹塑成型等将包含气体阻隔树脂和改性乙烯系聚合物的箱周边部件成型后，将改性乙烯系聚合物部加热、再熔融，由此，经由改性乙烯系聚合物部将箱周边部件与聚乙烯制汽油箱熔接接合。
[粘接性树脂组合物]
本发明的粘接性树脂组合物含有上述改性乙烯系聚合物。期望本发明的粘接性树脂组合物的洗脱量与本发明的改性乙烯系聚合物的洗脱量为同等程度。
另外，本发明的粘接性树脂组合物可以含有密度为930～980kg/m3的未改性乙烯系聚合物。含有未改性乙烯系聚合物时，相对于改性乙烯系聚合物和未改性乙烯系聚合物的合计量100重量％，优选未改性乙烯系聚合物的量为30重量％以下。作为上述未改性乙烯系聚合物，出于将本发明的粘接性树脂组合物的洗脱量调整为所期望的范围的目的，优选使用在茂金属催化剂的存在下聚合得到的未改性乙烯系聚合物。添加未改性乙烯系聚合物时，能够同样适用上述的调整方法。
本发明的粘接性树脂组合物中，在不损及本发明的目的的范围内，能够根据需要配合通常使用的抗氧化剂、耐候稳定剂、抗静电剂、防雾剂、防粘连剂、增滑剂、成核剂、颜料等添加剂或其它的聚合物、橡胶等。
本发明的粘接性树脂组合物优选根据ASTM D256在－40℃气氛下测得的Izod冲击强度为10kJ/m2以上、优选为12kJ/m2以上。－40℃气氛下的Izod冲击强度在该范围时，用于多层构造体时，低温落下冲击强度高。
本发明的粘接性树脂组合物能够通过各种公知的方法来制备，例如，将上述改性乙烯系聚合物在上述范围通过亨舍尔混炼机、转鼓混合机、V型混合机等进行干式混合的方法或在干式混合后通过单螺杆挤出机、多螺杆挤出机、班伯利混炼机等进行熔融混炼的方法；或者，在溶剂的存在下进行搅拌混合。
[叠层体]
本发明的叠层体具有由上述粘接性树脂组合物形成的粘接层(A)和形成于该粘接层(A)的至少一个面的树脂层(B)。另外，在粘接层(A)的另一个面也可以形成与树脂层(B)相同或不同的树脂层(C)。
树脂层(B)由气体阻隔树脂构成。这里，气体阻隔树脂是指汽油透过性低于聚烯烃的树脂。具体而言，可以列举聚酰胺树脂和乙烯-乙烯醇共聚物。
上述聚酰胺树脂具体而言可以优选使用尼龙6、尼龙66、尼龙610、尼龙11、尼龙12、MXD尼龙、无定形尼龙、对苯二甲酸/己二酸/六亚甲基二胺共聚物等。
另外，作为上述乙烯-乙烯醇共聚物，优选使用乙烯含量为20～50摩尔％的共聚物。
树脂层(C)中也能够使用聚乙烯树脂等，例如乙烯的均聚物或乙烯与α－烯烃的无规共聚物。α－烯烃的共聚量只要使聚乙烯树脂的密度在下述范围内即可，没有特别限定，通常，优选为10摩尔％以下，更优选为5摩尔％以下。作为α－烯烃，优选碳原子数3～10的α－烯烃，具体而言，例如，能够列举丙烯、1－丁烯、1－己烯、4－甲基－1－戊烯、1－辛烯、1－癸烯等。
聚乙烯树脂的熔体流动速率(MFR)〔ASTM D 1238(温度：190℃、负荷：2160g负荷)〕优选在0.01～3.0g/10分钟、更优选在0.05～1.5g/10分钟的范围，密度优选在0.940～0.980g/cm3、更优选在0.950～0.970g/cm3的范围。将这样的聚乙烯树脂用于树脂层(C)时，形成大型的多层构造体时的冲击强度高，成型性也优异。
构成本发明的叠层体的上述层(A)、(B)、(C)中，在不损及本发明的目的的范围内，能够配合填充剂、稳定剂、增滑剂、抗静电剂、阻燃剂、发泡剂等自身公知的添加剂。
本发明的叠层体的制造方法只要是公知的手法即可，能够没有特别限制地采用，例如，能够通过共挤出成型法进行。共挤出成型法没有特别限定，例如，能够列举使用多台挤出机进行熔融挤出的共挤出多层模具法、分流器(feed block)法等公知的共挤出成型法。
关于共挤出成型时的条件，也没有特别限定，将构成层(A)和层(B)的树脂加热到熔融温度以上，使用上述的挤出机熔融挤出，冷却到规定的温度即可。
本实施方式中，通过利用共挤出成型制造叠层体，层(A)与层(B)的粘接变强。另外，通过共挤出成型制造的叠层体能够通过一个工序制造，因此生产率优异。
另外，叠层方法有以下方法：利用带有衣架模头、T模头、I模头等口模的挤出机边挤出膜边进行覆盖、即所谓挤出层压方法；使用预先制膜得到的粘接膜(A)，在加热到膜(A)的软化温度以上的树脂膜(B)上用轧辊进行热压粘的方法；在模具中设置粘接膜(A)或树脂膜(B)之后，导入构成上述树脂层(B)或粘接层(A)的树脂，经由加温、冷却工序得到叠层体的注射成型等。这样的注射成型法在本发明中也能够合适地采用。
构成本发明的叠层体的改性乙烯系聚合物进行规定的接枝改性而成，并且在CFC测定中的80℃以下时的洗脱量调整为规定范围以下，因此，粘接性、机械强度优异，并且显示良好的燃料阻隔性。特别是可以认为粘接力不仅来自于粘接剂与被粘接体的分子间相互作用，还来自于原料树脂的机械强度。改性率变高时，分子间相互作用变强，但是作为原料树脂的机械强度的根源的结晶的构造的变化大，推测有时候粘接层的机械强度降低。在本发明的改性乙烯系聚合物中的接枝单体的重量范围中，令人惊奇的是，相比于改性率，原料树脂构造的机械强度对粘接强度的贡献更大，因此，可以推定，即使改性率低，也能够使粘接强度相对较高。因此，将该改性乙烯系聚合物用于粘接性树脂组合物而构成叠层体的粘接层时，可以得到粘接强度和与汽油或轻油接触后的粘接强度高、长期的耐久性和耐冲击性优异的叠层体。
在聚合物熔接中，大多数时候，结合的表面通常相互接触、推挤。在很多用途中，要使不同种的聚合物熔接时，通常存在不同种的部件间的接合不足或者不接合的问题。
但是，本发明的叠层体中，特定的改性乙烯系聚合物构成叠层体的粘接层，因此可以得到良好的接合。不仅它们的接合强，而且泄露(液体和气体)也少，能够良好地密封，使用这些方法，能够制作特别是在压力和/或真空下处理液体和/或气体的系统。
为了低成本且物理强度大，汽车燃料箱主体多为聚乙烯，根据本发明，能够与聚乙烯牢固接合。因此，本发明的叠层体能够合适地用于燃料阀、燃料系统的固定件、燃料管道(刚性和挠性)、燃料测量部件、燃料喷射器、燃料泵和这些商品的组件等燃料箱周边部件，特别适于作为燃料阀。
实施例
接着，列举实施例对本发明进行更具体地说明，但是，本发明只要不超出其主旨，则不受这些实施例的任何制约。
此外，实施例和比较例中的物性用以下的测定方法进行。
(1)MFR(g/10分钟)
根据ASTM D 1238，以温度：190℃、2160g负荷进行测定。
(2)密度(kg/m3)
根据ASTM D 1505进行测定。
(3)80℃以下时的洗脱量(g)
用交叉分级色谱(CFC)进行测定。
80℃以下的邻二氯苯可溶成分的比例(重量％)以以下的条件进行CFC测定来求出。
装置：交叉分级色谱CFC2(Polymer ChAR)、
检测器(内置)：红外分光光度计IR4(Polymer ChAR)、
检测波长：3.42μm(2,920cm－1)；固定、
试样浓度：120mg/30mL、注入量：0.5mL、
降温时间：1.0℃/min、
洗脱分级：4.0℃间隔(－20℃～140℃)、
GPC柱：Shodex HT－806M×3根(昭和电工株式会社)、
GPC柱温度：140℃、GPC柱校正：单分散聚苯乙烯(东曹株式会社)、
分子量校正法：通用校正法(聚苯乙烯换算)、
流动相：邻二氯苯(BHT添加)、流量：1.0mL/min。
(4)全切口蠕变
全切口蠕变试验根据ISO16770进行测定。具体而言，从厚度6mm的压制成型片切出试验片，使试验片的长度为40mm。然后，使用规定的夹具，在试验片中央部整个圆周切入深度1mm的切口。气氛设为80℃的温水，对试验片施以5.0MPa的恒定负荷，测定直至破裂的时间。
(5)浸渍燃料后的聚酰胺粘接强度(N/10mm)
浸渍燃料后的粘接强度如下测定：从叠层体的侧面以10mm宽度切出样品，在65℃的Fuel－C(异辛烷/甲苯重量比＝50/50)中浸渍200小时后，在室温(23℃)的恒温槽内测定粘接层(A)与树脂层(B)之间的粘接强度。
实施例中，通过注塑成型机制作粘接力评价用样品。具体而言，将实施例和比较例的改性乙烯系聚合物在200℃注塑成型，得到宽度12mm、长度130mm、厚度3mm的长条状的树脂片。然后，将上述改性乙烯系聚合物制的长条片插入与上述使用的模具不同的模具中，在改性乙烯系聚合物上以280℃注射聚酰胺树脂(PA6)。这样操作就得到了宽度12mm、长度130mm、厚度6mm(改性乙烯系聚合物/聚酰胺＝3mm/3mm)的改性乙烯系聚合物/聚酰胺粘接力评价用试验片。
将上述粘接力评价用试验片以90°方向剥离改性乙烯系聚合物层，以50mm/min的拉伸速度评价了改性乙烯系聚合物/聚酰胺树脂间的粘接力(参照图1)。
(6)燃料透过系数
在具有20mL的容积的SUS制容器(开放部面积1.26×10-3m2)中加入作为模拟燃料的Fuel－C 18mL，将压制成型的2mm厚的片材状试验片置于容器开放部并密闭，由此制作了试验体。将该试验体放入恒温装置(65℃)，测定试验体的重量，在每单位时间的重量减少达到一定时，通过下述式子求出燃料透过系数。
Figure BDA0001296886110000101
[实施例1]
使用在茂金属系催化剂的存在下制得的密度＝951kg/m3、MFR＝0.27g/10分钟的高密度聚乙烯的一部分，用马来酸酐0.22g/100g在挤出机内进行熔融接枝改性，从而准备了改性乙烯系聚合物(MFR＝0.27g/10分钟；密度＝951kg/cm3)，通过上述的方法评价了上述(1)～(6)。
[实施例2]
使用在茂金属系催化剂的存在下制得的密度＝951kg/m3、MFR＝0.27g/10分钟的高密度聚乙烯，用马来酸酐0.15g/100g在挤出机内进行熔融接枝改性，从而准备了改性乙烯系聚合物(MFR＝0.26g/10分钟；密度＝951kg/cm3)，与实施例1同样地进行了评价。
[实施例3]
使用在茂金属系催化剂的存在下制得的密度＝951kg/m3、MFR＝0.27g/10分钟的高密度聚乙烯，用马来酸酐0.30g/100g在挤出机内进行熔融接枝改性，从而准备了改性乙烯系聚合物(MFR＝0.30g/10分钟；密度＝951kg/cm3)，与实施例1同样地进行了评价。
[比较例1]
使用在齐格勒系催化剂的存在下制得的密度＝951kg/m3、MFR＝0.11g/10分钟的高密度聚乙烯，用马来酸酐0.22g/100g在挤出机内进行熔融接枝改性，从而准备了改性乙烯系聚合物(MFR＝0.12g/10分钟；密度＝951kg/cm3)，与实施例1同样地进行了评价。
[比较例2]
使用在茂金属系催化剂的存在下制得的密度＝951kg/m3、MFR＝0.27g/10分的高密度聚乙烯的一部分，用马来酸酐0.11g/100g在挤出机内进行熔融接枝改性，从而准备了改性乙烯系聚合物(MFR＝0.25g/10分钟；密度＝951kg/cm3)，与实施例1同样地进行了评价。
[比较例3]
使用在茂金属系催化剂的存在下制得的密度＝951kg/m3、MFR＝0.27g/10分钟的高密度聚乙烯的一部分，用马来酸酐0.44g/100g在挤出机内进行熔融接枝改性，从而准备了改性乙烯系聚合物(MFR＝0.32g/10分钟；密度＝951kg/cm3)，与实施例1同样地进行了评价。
在表1中表示结果。
[表1]
Figure BDA0001296886110000121
符号说明
1 改性乙烯系聚合物
2 聚酰胺
3 辊

Claims (8)

1.一种改性乙烯系聚合物，其特征在于：
其为乙烯系聚合物的至少一部分被不饱和羧酸或其衍生物接枝改性得到的改性乙烯系聚合物，
所述改性乙烯系聚合物的接枝改性量在0.15重量％～0.30重量％的范围，并且，所述改性乙烯系聚合物的交叉分级色谱测得的80℃以下时的洗脱量为10重量％以下，
所述乙烯系聚合物的至少一部分是在茂金属催化剂的存在下进行聚合得到的。
2.如权利要求1所述的改性乙烯系聚合物，其特征在于：
所述改性乙烯系聚合物的洗脱量为80℃以下时的向邻二氯苯的洗脱量。
3.一种粘接性树脂组合物，其特征在于：
含有权利要求1或2所述的改性乙烯系聚合物。
4.一种叠层体，其特征在于：
包括由权利要求3所述的粘接性树脂组合物形成的粘接层、和设置于该粘接层的至少一个面的树脂层。
5.如权利要求4所述的叠层体，其特征在于：
所述树脂层包含选自聚酰胺和乙烯-乙烯醇共聚物中的至少1种。
6.如权利要求4或5所述的叠层体，其特征在于：
其为由共挤出成型法制得的。
7.如权利要求4或5所述的叠层体，其特征在于：
其为由注射成型法制得的。
8.一种塑料燃料箱用的燃料阀，其特征在于：
使用了权利要求4～7中任一项所述的叠层体。
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