CN101198653A - 基于mxd.10聚酰胺的不透性结构 - Google Patents
基于mxd.10聚酰胺的不透性结构 Download PDFInfo
- Publication number
- CN101198653A CN101198653A CN200680020956.1A CN200680020956A CN101198653A CN 101198653 A CN101198653 A CN 101198653A CN 200680020956 A CN200680020956 A CN 200680020956A CN 101198653 A CN101198653 A CN 101198653A
- Authority
- CN
- China
- Prior art keywords
- mxd
- repeating unit
- polycondensation
- film
- polyamide
- 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
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- 230000004888 barrier function Effects 0.000 title abstract 2
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- 239000000463 material Substances 0.000 claims abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 13
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- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
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- REEBJQTUIJTGAL-UHFFFAOYSA-N 3-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1 REEBJQTUIJTGAL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种包含至少一层由聚酰胺MXD.10/Z组成的结构,其中:MXD.10为包含70-100%的间苯二甲胺的苯二甲胺与癸二酸的混合物的缩合产物,Z为至少一种选自以下的重复单元:得自内酰胺单体的缩聚反应的重复单元、得自α-Ω氨基羧酸的缩聚反应的重复单元、重复单元X1.Y1,其中X1表示得自脂族、芳基脂族、脂环族或芳族二胺的缩聚反应的重复单元,Y1表示得自脂族羧酸、脂环族或芳族二酸的缩聚反应的重复单元,重量比Z/(MXD.10+Z)为0-15%。本发明的结构可由一层该聚酰胺组成,或者可包含含有聚酰胺MXD.10的层和至少一层其他材料的层。本发明还涉及使用以上结构制成的瓶子、罐、容器、管道、管子和许多类型的容纳装置。该结构还可制成薄膜形式以生产包装物。所有的这些物品具有良好的防透性能。本发明还涉及这些物品以及这些结构和物品的用途。
Description
发明领域
本发明涉及一种基于聚酰胺MXD.10的不透性结构。“MXD.10”代表包含70-100%重量的间苯二甲胺的苯二甲胺与癸二酸的共混物的缩合产物。
该结构可由一层包含该聚酰胺的层组成,或者由一层聚酰胺MXD.10和至少一层另一种材料组成。该结构用于制备瓶子、罐、管道、管子和许多类型的容纳装置。该结构还可制成薄膜形式,使用该薄膜可例如生产包装物。所有的这些物品显示良好的防透性能。本发明还涉及这些结构和物品的用途。
现有技术和技术问题
半芳族聚酰胺例如聚邻苯二酰胺(polyphtalamide)和MXD.6通常断裂伸长小于50%,且较刚性。为了改进其机械性能,需要将其与其他产品共混。
专利GB 1490453公开了(i)间苯二甲胺与具有6-12个碳原子的二酸的缩合产物与(ii)某些PA6.6的共混物。各实施例公开了某些MXD.6(间苯二甲胺与己二酸的缩合产物)与PA6.6(聚己二酰己二胺)的共混物。未提及任何有关防透性能。
专利GB 1472615公开了(i)间苯二甲胺与具有6-12个碳原子的二酸的缩合产物与(ii)某些纤维的共混物。所有的实施例包含某些己二酸。如上一篇专利,未提及任何有关防透性能。
专利EP 940444公开了(i)间苯二甲胺与包含大于70%的己二酸的二酸的缩合产物与(ii)选自脂肪酸的金属盐、二酰胺和二酯的产品的共混物。当存储于潮湿的环境时,该组合物轻微受影响变白。未提及任何有关防透性能。
专利申请US 2002-0142179公开了(i)间苯二甲胺与具有6-12个碳原子的二酸的缩合产物与(ii)乙烯和丙烯酸乙酯的马来酸酐接枝共聚物的共混物。所有的实施例包含MXD.6。该组合物的薄膜作为阻氧层。
专利EP 1308478公开了(i)间苯二甲胺与由大于70%的己二酸组成的二酸的缩合产物与(ii)绿土的共混物。该组合物的薄膜作为阻氧层。
专利EP 1350806公开了(i)间苯二甲胺与二酸的缩合产物与(ii)绿土的共混物,该二酸包含大于70%的具有4-20个碳原子的二酸。每个实施例基于MXD.6。该组合物的薄膜作为阻氧层。
专利申请US 2004-0076781描述了间苯二甲胺与(i)具有4-20个碳原子的二酸和(ii)间苯二甲酸的共混物的缩合产物。每个实施例基于MXD.6/MXD.I。该组合物的薄膜作为阻氧层。
我们发现聚酰胺MXD.10同时具有良好的防透性能以及良好的机械性能。在防透性能中,关注的是对水蒸汽、氧和香味的防透性能。现有技术(如下所示)已描述了未提及防透性能的MXD.10。除此以外,这些现有技术未描述也未提出由一层该聚酰胺组成或包含一层聚酰胺MXD.10和至少一层另一种材料的结构。
专利US 2766221公开了间苯二甲胺与具有6-10个碳原子的二酸的缩合产物。实施例3公开了将聚酰胺MXD.10制成纤维的方法。还提到了可用于制备透明薄膜。未提及任何有关防透性能。
专利US 2878235与上一篇专利类似。公开了MXD.10的断裂伸长为360%。未提及任何有关防透性能。
发明概述
本发明涉及一种包含至少一层由聚酰胺MXD.10/Z组成的结构,其中:
·MXD.10为包含70-100%的间苯二甲胺的苯二甲胺与癸二酸的共混物的缩合产物,
·Z为至少一种选自以下的重复单元:得自内酰胺单体的缩聚反应的重复单元、得自α-Ω氨基羧酸的缩聚反应的重复单元、重复单元X1.Y1,其中X1表示得自脂族、芳基脂族、脂环族或芳族二胺的缩聚反应的重复单元,Y1表示得自脂族羧酸、脂环族或芳族二酸的缩聚反应的重复单元,
重量比Z/(MXD.10+Z)为0-15%。
本发明描述的结构可仅由一层该聚酰胺组成,或可包含含有聚酰胺MXD.10的层和至少一层其他材料的层。其他材料可例如为任何其他聚酰胺(例如PA6、PA6.6)或共聚多酰胺、EVOH、聚烯烃(例如聚乙烯、聚丙烯)、聚酯。本发明的聚酰胺层可任选在一个方向取向或双轴拉伸。
在本发明的结构中,包含聚酰胺MXD.10/Z的层还可包含其他聚合物、填料例如纤维或纳米复合材料。这意味着包含聚酰胺MXD.10/Z的层由MXD.10/Z和其他聚合物及任选的填料的共混物组成。这些其他聚合物的实例可提及的有聚酰胺、EVOH、PPS、PPO、聚碳酸酯、ABS、增韧剂(EPR)、聚烯烃。
MXD.10/Z与其他聚合物、填料例如纤维或纳米复合材料的这些共混物本身为新产品。本发明还涉及这些产品。
本发明还涉及由以上结构制成的瓶子、罐、容器、管子、管道和许多类型的容纳装置。该结构还可为用于制备包装物的薄膜。所有的这些物品具有良好的防透性能。本发明还涉及这些物品以及这些结构和物品的用途。
发明详述
最好Z的比例选择为0-10%重量(包括端点),优选为0-5%。基于内酰胺的单体可选自己内酰胺和十二烷基内酰胺单体。α-Ω氨基羧酸可为氨基十一烷酸。X1的碳原子数可为6-22。Y1的碳原子数可为6-14。Z可为MXD.Y1,例如为MXD 6。这意味着本发明的聚酰胺可为MXD.10/MXD.6。
根据用于制备聚酰胺的公知的技术如缩聚来制备聚酰胺MXD.10/Z。
在本发明的结构中,包含聚酰胺MXD.10/Z的层还可包含其他聚合物、某些填料例如纤维或纳米复合材料以及通常的添加剂例如抗氧化剂、UV稳定剂、阻燃剂、抗静电剂例如炭黑、碳纳米管和导电纤维。
用于本发明结构的半芳族聚酰胺具有在典型的脂族聚酰胺预期的通常值内的热机械性能。熔点(小于或等于190℃)和模量(弯曲模量小于或等于1800MPa,拉伸模量小于或等于1500MPa),使得:
·可使用用于脂族聚酰胺的工业设备,
·易在约210℃下加工,使得能与许多其他聚合物(聚酰胺-PA-、PE、官能化的聚烯烃、EVOH)混配和共加工,和
·使用通常的模具注射/模塑(不加热)。
其断裂伸长大于或等于200%,比典型的半芳族PA优异。
除了这些热机械性能以外,MXD.10/Z具有良好的对氧、水蒸汽和汽油的防透性能。MXD.10的密度小于MXD.6的密度。
同时具有热机械性能和防透性能使得这些产品可用于许多应用,例如:
·挤出产品:用其本身挤出或与其他材料混配挤出成一层或多层,用于运输应用(液体和油箱输送线)、空调(软管)等,其中需要良好的汽油防透特性。
·包装物:用其本身挤出或与其他材料混配制成一层或多层薄膜和用于包装的注塑部件(其中需要阻氧层)。
实施例
实施例1:合成MXD.10
将以下单体引入配备搅拌器的反应器中:14.1kg(103.5mol)间苯二甲胺、20.9kg(103.5mol)癸二酸和500g H2O。将这样形成的混合物放置在惰性气氛下,随后加热,直至温度达到240℃,同时保持最大压力为30巴。在这些条件下保持1小时后,将压力缓慢释放2小时,直至达到大气压。将反应器置于氮气流下,缩聚反应于275℃下持续约2小时,直至达到聚合物所需的粘度。终产物的特性粘度为1.18dl/g。
表1.MXD.10和MXD.6的热机械性能
Tg(DSC) | Tm:熔点 | 加工温度 | ΔH | 弯曲模量(DMA,牵引) | 拉伸强度 | 断裂伸长 | 断裂拉伸强度 | |
本发明的MXD.10 | 60℃ | 190℃ | 210℃ | 45J/g | 1800MPa(>1500) | 91MPa | 200% | 48MPa |
MXD 6(参考文献实施例) | 90℃ | 241℃ | 250-270℃ | 52J/g | 2400MPa(>2000) | 95MPa | 5% | 60MPa |
使用方法ISO 307(1994),于20℃下,在间甲酚中测定特性粘度。根据方法ISO 111357-3(1999),通过DSC测定玻璃化转变温度、熔点和熔化焓。
使用方法ISO 527(1/2),以25mm/分钟的速度,用注塑试样测定拉伸和弯曲热机械性能。将各试样事先在Tg+50℃下调适。
在Randcastel挤出机上,在将产品挤出为薄膜的过程中观察加工温度,由DSM注塑条件证实。
实施例2:使用吹膜技术薄膜挤出MXD10
将在实施例1中制得的组合物通过30mm单螺杆挤出机的环形模头挤出。将聚合物以7.9kg/h的排出量通过直径50mm的环形模头挤出。熔融状态的膜泡以9.8m/分钟的速度垂伸,吹胀比(定义为冷却后的膜泡直径与模头直径之比)等于2.5。模头间隙等于0.8mm,冷却装置为简单的吹20℃空气的风环(flux air ring),使得冷固线距离为150mm。这些牵伸条件得到宽度为393mm的30μm的MXD 10薄膜。该薄膜称作实施例2.1的薄膜。薄膜的性能见述于表2。
表2
吹膜MXD.10的机械性能(实施例2.1) | ||
纵向 | 横向 | |
拉伸模量(MPa) | 1377 | 1323 |
屈服形变(%) | 2.9 | 2.8 |
屈服应力(MPa) | 24.8 | 24.7 |
断裂形变(%) | 241 | 293 |
断裂应力(MPa) | 50.8 | 56.8 |
实施例2.1的光学性能 | ||
雾度 | 1.96 | |
实施例2.1的渗透性能 | ||
在0%相对湿度下的氧渗透性(cc.25μm/m224h) | 56 | |
在50%相对湿度下的氧渗透性(cc.25μm/m224h) | 47 | |
在90%相对湿度下的氧渗透性(cc.25μm/m224h) | 36 |
使用ASTM D 882方法,于23℃下测定拉伸模量和牵引性能(Traction Property)。将各试样事先在23℃和50%相对湿度下调适,直至湿含量稳定。
使用ASTM D 1003方法测定雾度性能。
使用ASTM D 3985方法,用OTRAN仪器于23℃下测定渗透性能。
为了比较MXD10薄膜(实施例2.1)的固有性能与聚酰胺6的性能,在用于制造实施例2.1薄膜的相同的仪器上制备聚酰胺6的薄膜。Ultramid B35(得自BASF company)以9.9kg/h的排出量通过直径50mm的环形模头挤出。熔融状态的膜泡以10.1m/分钟的速度垂伸,吹胀比(定义为冷却后的膜泡直径与模头直径的比)等于2.5。模头间隙等于0.8mm,冷却装置为简单的吹20℃空气的风环,使得冷固线距离为150mm。这些牵伸条件得到宽度为约400mm的30μm的Ultramid B35薄膜。该薄膜的性能见述于表3。PA 6的薄膜称作实施例2.2的薄膜。
表3比较了MXD10薄膜、Ultramid B35薄膜(PA6)和MXD6薄膜的固有性能,MXD10具有独特的平衡的性能,在高相对湿度下,断裂形变非常高、拉伸模量柔软、透明性非常好且氧渗透性非常好。
表3
实施例2.1(MXD10) | 实施例2.2(聚酰胺6) | MXD6 | |
拉伸模量(MPa)MD/TD | 1377/1323 | 754/767 | 3125/3103 |
断裂形变(%)MD/TD | 241/293 | 323/315 | 3/2 |
雾度 | 1.96 | 10.51 | 2.11 |
在50%相对湿度下的氧渗透性(cc.25μm/m224h) | 47 | 36 | 3 |
在70%相对湿度下的氧渗透性(cc.25μm/m224h) | 35 | 54 | 9 |
在90%相对湿度下的氧渗透性(cc.25μm/m224h) | 36 | 125 | 6 |
使用ASTM D 882方法,于23℃下测定拉伸模量和牵引性能。将各试样事先在23℃和50%相对湿度下调适,直至湿含量稳定。
使用ASTM D 1003方法测定雾度性能。
使用ASTM D 3985方法,用OTRAN仪器于23℃下测定渗透性能。
实施例3:使用流延薄膜技术薄膜挤出MXD10
将在实施例1中制得的组合物通过30mm单螺杆挤出机的扁平模头挤出。挤出机以80rpm的速度运行,与250mm的扁平模头相连。熔融状态的MXD10以19.9m/分钟的速度垂伸,牵引比(定义为线速度与挤出速度的比)等于11.2。模头间隙等于0.3mm,冷却辊的温度设定为60℃。这些牵引条件得到25μm的MXD10薄膜。该薄膜的性能见述于表4,具有使用流延薄膜技术时类似的平衡的性能。
表4
机械性能 | ||
纵向 | 横向 | |
拉伸模量(MPa) | 1233 | 1129 |
断裂形变(%) | 334 | 329 |
渗透性能 | ||
在50%相对湿度下的氧渗透性(cc.25μm/m224h) | 40 | |
在90%相对湿度下的氧渗透性(cc.25μm/m224h) | 50 |
使用ASTM D 882方法,于23℃下测定拉伸模量和牵引性能。将各试样事先在23℃和50%相对湿度下调适,直至湿含量稳定。
使用ASTM D 1003方法测定雾度性能。
使用ASTM D 3985方法,用OTRAN仪器于23℃下测定渗透性能。
实施例4:使用吹膜技术薄膜共挤出MXD10和EVOH
将在实施例1中制得的组合物与Soarnol 3803 ET(EVOH,乙烯基含量38%)通过环形模头共挤出。使用表5中规定的以下挤出机挤出各层。
表5:对用于进行共挤出的挤出机的描述
螺杆直径(mm) | L/D | 排出量(kg/h) | |
MXD10-层1 | 25 | 30 | 2.5 |
EVOH-中间层 | 30 | 30 | 2.9 |
MXD10-层2 | 30 | 30 | 2.5 |
使用“薄饼”技术,将聚合物通过直径50mm的环形模头挤出。熔融状态的膜泡以10.1m/分钟的速度垂伸,吹胀比(定义为冷却后的膜泡直径与模头直径的比)等于2.5。模头间隙等于0.8mm,冷却装置为简单的吹20℃空气的风环,使得冷固线距离为150mm。这些牵引条件得到宽度为约400mm的具有以下结构的三层薄膜:[MXD10(10μm)/EVOH(10μm)/MXD(10μm)]。该薄膜具有非常好的可加工性,包括共挤出性和膜泡稳定性。该薄膜的性能见述于表6。共挤出薄膜称作实施例4.1的薄膜。将该薄膜的性能与在相同的设备上共挤出并使用常规的聚酰胺6(Ultramid B 35,得自BASF公司)代替MXD10的三层薄膜比较。比较用薄膜称为实施例4.2的薄膜,具有如下结构:[Ultramid B35(10μm)/Soarnol 3803 ET(10μm)/UltramidB35(10μm)],其性能如下所示。
表6
实施例4.1 | 实施例4.2 | |
(cc.25μm/m224h) | (cc.25μm/m224h) | |
在50%相对湿度下的氧渗透性 | 1 | 1 |
在70%相对湿度下的氧渗透性 | 3 | 3.5 |
在90%相对湿度下的氧渗透性 | 22 | 29 |
使用ASTM D 3985方法,用OTRAN仪器于23℃下测定渗透性能。将各试样事先在23℃和50%相对湿度下调适,直至湿含量稳定。
Claims (9)
1.一种包含至少一层由聚酰胺MXD.10/Z组成的结构,其中:
MXD.10为包含70-100%的间苯二甲胺的苯二甲胺与癸二酸的混合物的缩合产物,
Z为至少一种选自以下的重复单元:得自内酰胺单体的缩聚反应的重复单元、得自α-Ω氨基羧酸的缩聚反应的重复单元、重复单元X1.Y1,其中X1表示得自脂族、芳基脂族、脂环族或芳族二胺的缩聚反应的重复单元,Y1表示得自脂族羧酸、脂环族或芳族二酸的缩聚反应的重复单元,
重量比Z/(MXD.10+Z)为0-15%。
2.权利要求1的结构,其中在所述聚酰胺MXD.10/Z中Z的比例为0-10%。
3.权利要求2的结构,其中所述比例为0-5%。
4.上述权利要求中任一项的结构,其中Z中的内酰胺选自己内酰胺和十二烷基内酰胺。
5.上述权利要求中任一项的结构,其中Z中的X1的碳原子数为6-22。
6.上述权利要求中任一项的结构,其中在Z中的Y1的碳原子数为6-14。
7.由上述权利要求中任一项的结构制成的瓶子、罐、容器、管子和任何类型的容纳装置。
8.使用上述权利要求中任一项的结构制造的薄膜制成的包装物。
9.MXD.10/Z与至少一种选自其他聚合物、填料例如纤维或纳米复合材料的产品的共混物。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0503712A FR2884518B1 (fr) | 2005-04-14 | 2005-04-14 | Structure barriere a base de polyamide mxd.10 |
FR05.03712 | 2005-04-14 | ||
US60/719,838 | 2005-09-23 |
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CN101198653A true CN101198653A (zh) | 2008-06-11 |
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CN200680020956.1A Pending CN101198653A (zh) | 2005-04-14 | 2006-04-12 | 基于mxd.10聚酰胺的不透性结构 |
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US (1) | US20080193691A1 (zh) |
EP (1) | EP1869124A1 (zh) |
JP (1) | JP2008535984A (zh) |
CN (1) | CN101198653A (zh) |
CA (1) | CA2604553A1 (zh) |
FR (1) | FR2884518B1 (zh) |
WO (1) | WO2006108721A1 (zh) |
Cited By (6)
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CN102282199A (zh) * | 2008-11-21 | 2011-12-14 | 阿克马法国公司 | 具有改善的机械性能的聚酰胺与生物资源增强材料的组合物 |
CN102471574A (zh) * | 2009-07-23 | 2012-05-23 | 阿克马法国公司 | 聚酰胺组合物、由这样的组合物制造的物品、及其用途 |
CN103154088A (zh) * | 2011-09-12 | 2013-06-12 | 三菱瓦斯化学株式会社 | 薄壁成型品 |
CN103261327A (zh) * | 2010-12-27 | 2013-08-21 | 三菱瓦斯化学株式会社 | 聚酰胺组合物 |
CN103987782A (zh) * | 2011-12-16 | 2014-08-13 | 三菱瓦斯化学株式会社 | 成型品 |
CN105283511A (zh) * | 2013-06-14 | 2016-01-27 | 阿科玛法国公司 | 由聚酰胺mxd.10制成的组合物 |
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FR2909433B1 (fr) | 2006-11-30 | 2014-01-10 | Arkema France | Utilisation d'une structure multicouche pour la fabrication de conduites de gaz, notamment de methane. |
FR2934803B1 (fr) * | 2008-08-08 | 2013-03-22 | Arkema France | Procede de fabrication d'un materiau barriere a base de polyamide |
JP5471009B2 (ja) * | 2009-04-24 | 2014-04-16 | 三菱瓦斯化学株式会社 | 多層容器 |
US8487039B2 (en) * | 2009-12-11 | 2013-07-16 | E I Du Pont De Nemours And Company | Salt resistant polyamide compositions |
US20110144256A1 (en) * | 2009-12-11 | 2011-06-16 | E. I. Du Pont De Nemours And Company | Salt resistant polyamides |
CN102762636B (zh) * | 2009-12-28 | 2014-02-19 | 三菱瓦斯化学株式会社 | 聚酰胺化合物 |
EP2528973A2 (en) * | 2010-01-29 | 2012-12-05 | E.I. Du Pont De Nemours And Company | Polyamide compositions with improved salt resistance and heat stability |
ES2620755T3 (es) | 2010-07-27 | 2017-06-29 | Mitsubishi Gas Chemical Company, Inc. | Resina de poliamida |
JP2014213595A (ja) * | 2013-04-30 | 2014-11-17 | クリロン化成株式会社 | 低カール性多層フィルム |
BR112016002466B8 (pt) * | 2013-08-16 | 2022-09-20 | Mitsubishi Gas Chemical Co | Estrutura multicamada |
FR3053694B1 (fr) * | 2016-07-11 | 2018-07-06 | Arkema France | Structure barriere a base de copolyamide bact/xt de haute tg |
JP7011898B2 (ja) * | 2017-04-05 | 2022-01-27 | 三菱エンジニアリングプラスチックス株式会社 | 金属接合用ポリアミド樹脂組成物、金属樹脂複合体および金属樹脂複合体の製造方法 |
JP2019524471A (ja) * | 2017-07-10 | 2019-09-05 | 東莞市森特塑膠製品有限公司 | プラスチックフィルム |
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US2766221A (en) * | 1953-06-04 | 1956-10-09 | California Research Corp | Synthetic fiber-forming polymers from meta-xylylene diamine and adipic acid |
US2878235A (en) * | 1956-10-08 | 1959-03-17 | California Research Corp | Polyamide of meta-xylylene diamine and 8 to 10 carbon atom aliphatic dicarboxylic acids |
JPS5061449A (zh) * | 1973-10-02 | 1975-05-27 | ||
JPS5432458B2 (zh) * | 1974-11-26 | 1979-10-15 | ||
JPS61152411A (ja) * | 1984-12-26 | 1986-07-11 | Mitsubishi Gas Chem Co Inc | 多層パリソン及びその製造方法 |
CN1075730A (zh) * | 1992-02-23 | 1993-09-01 | 雷廷扬 | 电镀用绝缘涂料的配制 |
DE4426753A1 (de) * | 1994-07-28 | 1996-02-01 | Bayer Ag | Mittel zur Bekämpfung von Pflanzenschädlingen |
JPH10195211A (ja) * | 1996-12-27 | 1998-07-28 | Kureha Chem Ind Co Ltd | 包装用フィルムまたはシート |
JPH11254615A (ja) * | 1998-03-09 | 1999-09-21 | Toyobo Co Ltd | ポリアミド系積層フィルム |
JP4961632B2 (ja) * | 2001-02-01 | 2012-06-27 | 三菱瓦斯化学株式会社 | ポリアミド延伸フィルム |
-
2005
- 2005-04-14 FR FR0503712A patent/FR2884518B1/fr not_active Expired - Fee Related
-
2006
- 2006-04-12 EP EP06724763A patent/EP1869124A1/en not_active Withdrawn
- 2006-04-12 CN CN200680020956.1A patent/CN101198653A/zh active Pending
- 2006-04-12 WO PCT/EP2006/004317 patent/WO2006108721A1/en active Application Filing
- 2006-04-12 JP JP2008505847A patent/JP2008535984A/ja not_active Abandoned
- 2006-04-12 CA CA002604553A patent/CA2604553A1/en not_active Abandoned
- 2006-04-12 US US11/911,215 patent/US20080193691A1/en not_active Abandoned
Cited By (12)
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CN102282199A (zh) * | 2008-11-21 | 2011-12-14 | 阿克马法国公司 | 具有改善的机械性能的聚酰胺与生物资源增强材料的组合物 |
CN102471574A (zh) * | 2009-07-23 | 2012-05-23 | 阿克马法国公司 | 聚酰胺组合物、由这样的组合物制造的物品、及其用途 |
CN102471574B (zh) * | 2009-07-23 | 2014-08-27 | 阿克马法国公司 | 聚酰胺组合物、由这样的组合物制造的物品、及其用途 |
TWI481666B (zh) * | 2009-07-23 | 2015-04-21 | Arkema France | 以聚醯胺為底的組成物、由彼所得的物件及彼之用途 |
CN103261327A (zh) * | 2010-12-27 | 2013-08-21 | 三菱瓦斯化学株式会社 | 聚酰胺组合物 |
CN103261327B (zh) * | 2010-12-27 | 2015-09-09 | 三菱瓦斯化学株式会社 | 聚酰胺组合物 |
CN103154088A (zh) * | 2011-09-12 | 2013-06-12 | 三菱瓦斯化学株式会社 | 薄壁成型品 |
CN103154088B (zh) * | 2011-09-12 | 2014-06-25 | 三菱瓦斯化学株式会社 | 薄壁成型品 |
US9096714B2 (en) | 2011-09-12 | 2015-08-04 | Mitsubishi Gas Chemical Company, Inc. | Thin-wall article |
CN103987782A (zh) * | 2011-12-16 | 2014-08-13 | 三菱瓦斯化学株式会社 | 成型品 |
CN103987782B (zh) * | 2011-12-16 | 2018-02-06 | 三菱瓦斯化学株式会社 | 成型品 |
CN105283511A (zh) * | 2013-06-14 | 2016-01-27 | 阿科玛法国公司 | 由聚酰胺mxd.10制成的组合物 |
Also Published As
Publication number | Publication date |
---|---|
US20080193691A1 (en) | 2008-08-14 |
EP1869124A1 (en) | 2007-12-26 |
CA2604553A1 (en) | 2006-10-19 |
WO2006108721A1 (en) | 2006-10-19 |
FR2884518B1 (fr) | 2007-09-21 |
FR2884518A1 (fr) | 2006-10-20 |
JP2008535984A (ja) | 2008-09-04 |
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