CN86104975A - 对气体和有机液体具有低渗透性的韧性聚对苯二甲酸乙酯制品的加工方法 - Google Patents
对气体和有机液体具有低渗透性的韧性聚对苯二甲酸乙酯制品的加工方法 Download PDFInfo
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- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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Abstract
从PET和增韧聚合物的共混物熔制对有机液体和蒸气低渗透性的韧性制品。后者可为α-烯烃/α，β-不饱和羧酸共聚物，或由该共聚物用镁或锌离子中和所得的离子键聚合物，或E/X/Y型共聚物(E为乙烯，X为丙烯酸的、甲基丙烯酸的或乙基丙烯酸的低级烷酯，Y为甲基丙烯酸的或丙烯酸的缩水甘油酯)。控制条件能减小PET的结晶作用，如使与其接触的熔制设备表面保持100℃以下或在高温下让制品骤冷，以及在共混聚合物中避免成核剂存在。
Description
本发明涉及对有机液体和蒸气具有低渗透性的韧性聚对苯二甲酸乙酯制品及其加工方法。
聚对苯二甲酸乙酯（PET）不仅广泛用于制造包装薄膜和封皮，而且用以制造各种液体容器。它还可以和种种别的树脂掺和一起，采用象挤塑、注塑与热成型等技术来加工其它类型的制品。常用工业级PET树脂不具有良好的韧性，因此往往要采取加入增韧剂的办法，例如加入橡胶或软质聚烯烃来进行改性。这方面的实例可查阅美国专利4，172，859（属Epstein公司）和英国专利1，208，585（属帝国化学工业公司（I.C.I））。美国专利3，435，093（属Cope公司）公布了由乙烯与α、β不饱和羧酸及其盐类的共聚物和PET树脂组成的共混体系。
通常用注塑制成的PET制品或挤塑制品，如薄膜或纤维，或吹塑的容器，所有这些制品都要进行加工或改性以使PET获得最大的结晶度。至于吹塑容器，如充碳酸气的饮料瓶，常常先进行分子定向（例如用拉伸的办法），然后进行热变定和退火处理（见Wyeth申请的美国专利3，733，309）。在注塑或热成形工艺中，通过热油使模具保温（一般高于100℃）的办法，可以提高PET树脂的结晶度。常常在PET树脂混合物中加入各种成核剂，例如滑石来诱导生成结晶（见Furukawa申请的美国专利3，368，955）。成核剂与增塑剂二者必须同时
用，以获得具有良好的表面特性，经过充分结晶化的韧性产品，加工时，熔融的PET树脂在水冷却至100℃以下的标准模具中成形（见Deyrup美国专利4，352，904和4，486，564）。上面引述的专利强调需要让PET充分地结晶化，以改善由此制得的制品性能。
特别是注塑制品，很重要的一个问题是要对聚对苯二甲酸乙酯进行改性，以便获得各种满意的机械性能，如切口冲击强度，刚性和拉伸强度。因此由这种改性聚对苯二甲酸乙酯制成的注塑容器，一方面具有极良好的抗渗透性能，但同时对许多应用而言，价格也太昂贵。
人们希望用PET树脂为基科生产的制品，如容器、薄膜、管子等，既有韧性又对有机液体和蒸气有满意的抗渗透性能，同时做到价廉和加工较为简便，这样才能达到大量生产满足供应市场的需要。特别是人们要求生产PET的各种制品，如油漆罐及装各种市售产品，包括各种有机液体，特别是烃类溶剂或稀释剂在内的包装容器。
依照本发明，现在提出了一种制造方法，使制品既坚韧又对许多有机液体和蒸气具有低渗透性，它是将45-95%（重量）PET树脂与5-55%（重量）由碳原子数为2-5的α-烯烃和3-5个碳原子的α、β-不饱和羧酸的共聚物组成共混物，其中的共聚物也可以是部分中和或全部中和羧酸的锌盐或镁盐所形成的一种离子交联聚合物;也可以用PET树脂与乙烯/含缩水甘油基共聚物组成共混物，这些共混物在尽量减少结晶化的条件下经过熔融-成形加工成制品，成形设备可以是注塑、吹塑或挤塑设备;特别要注意避免在共混物中加入成核剂;要使设备与共混物接触表面的温度低于100℃，较好是低于90℃，更好是低于50℃;同时为获得最大的韧性，当设备在较高操作温度下加工制品时，要使之迅速急冷至这样的温度以下。
本发明在加工过程中所采用的PET树脂是来自几种渠道的商品，最好是它的比浓对数粘度（inherent viscosity）为0.4-4.0分升/克。
本说明书和权利要求中所使用的“共聚物”一词是指至少由两种单体进行共聚合后得到的聚合物;但它并不局限于仅仅由两种单体共聚合而成。
一种α烯烃和一种α，β-不饱和羧酸制成的共聚物，其中α-烯烃至少占70%（重量），而α，β-不饱和羧酸最多占30%（重量），羧酸基团是无规地分布在整个共聚物分子中。羧酸基团可以用锌离子或镁离子中和，中和程度范围为0-100%。用碱金属离子进行中和是不合适的，因为它会促进PET树脂的结晶化。较好的α-烯烃是乙烯;其它α-烯烃包括：例如丙烯，1-丁烯和1-戊烯。具有代表性的不饱和羧酸有：丙烯酸，甲基丙烯酸，顺丁烯二酸单乙酯和顺丁烯二酸单甲酯，及丁烯二酸单乙酯和反丁烯二酸单甲酯，反丁烯二酸单乙酯和反丁烯二酸单甲酯，亚甲基丁二烯单甲酯和亚甲基丁二酸单乙酯，乙基丙烯酸，顺丁烯二酸，反丁烯二酸以及亚甲基丁二酸等。
在那些共聚物中还可以引入第三种含乙烯基的不饱和单体，尤其是丙烯酸酯或乙烯酯，例如：丙烯酸丁酯，甲基丙烯酸甲酯或乙烯醋酸酯。当共聚物是由乙烯与α、β-不饱和羧酸以及第三种含乙烯基的不饱和单体组成的三元共聚物时，这些单体的重量百分比分别为：乙烯占40-90%，α，β-不饱和羧酸占0.5-20%，第三种含乙烯基的不饱和单体占10-40%。象二元共聚物的情况一样，羧酸基团可以不被中和，也可用锌离子或镁离子进行不同程度的中和。
所有这种共聚物都是共知的，其中一些共聚物有商品出售，而其它共聚物能用自由基共聚法制备，最好是在烃类溶剂的溶液中进行共聚，或者在液相中，或者在汽相中。当所需的羧酸含量很少时，聚合最好用连续法进行，调整单体的比例使之适合于各自的聚合活性，同时限制滞留时间，防止α-烯烃完全转化为聚合物。
乙烯含缩水甘油基团的共聚物是一种E/X/Y型的共聚物，其中单体E、X、Y分述如下：
E代表乙烯，在共聚物中占40-90%（重量）;
X代表羧酸酯，其化学式为
式中R1代表含有2-8个碳原子的烷基，4-6个碳原子较好，尤其是碳原子数为4更好;R2代表H，CH3或C2H5，H或CH3较好，特别是H更好;X在E/X/Y共聚物中占有的重量百分率为10-40%，以15-35%较好，尤其是20-35%更好;
Y选自甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯所含的基因，Y在E/X/Y共聚物中占有的重量百分率为0.5-20%，以2-10%范围较好，特别是3-8%更好。
此外还可存在少量多加的共聚单体，例如CO和丙烯酸甲酯，只要乙烯共聚物的基本性能，象熔体粘度和增韧能力，不发生明显变化。
上面的共聚物可以用直接共聚合的方法制备，例如将乙烯，甲基丙烯酸缩水甘油酯或丙烯酸缩水甘油酯与上述的羧酸酯X，在有游离基聚合用引发剂存在和提高温度与压力的条件下，进行共聚反应，较好的反应温度为100-270℃，最好是130-230℃反应压力最低应为70兆帕，最好是140-350兆帕。
除了上面所需的两种成分外，聚合物共混物也可以包含第三种聚合物，它在熔融加工条件下不会对其它两种聚合物有化学作用。典型的这种附加聚合物有：各种聚烯烃，比如聚乙烯，聚丙烯和乙烯/丙烯共聚物;聚苯乙烯;乙烯/乙烯醋酸酯共聚物，乙烯/丙烯酸烷基酯共聚物等同类物和它们的混合物。如存在第三种聚合物，则其含量最多可等于α-烯烃/α，β-不饱和羧酸共聚物或E/X/Y共聚物的重量，在共混物中全部聚合物的总量要使PET的比例保持在45-99%范围内。
含羧酸基团的共聚物中较好的是乙烯/甲基丙烯酸（E/MAA）共聚物，较佳含量约占共混物重量的20-40%。较好的E/MAA共聚物中含约80-97%（重量）的乙烯和3-20%（重量）的丙烯酸，其中丙烯酸可以是游离状态，也可转变为任何所需量的锌酸或镁盐。
较佳的E/X/Y共聚物应为：其中X为丙烯酸正-丁酯，Y为甲基丙烯酸缩水甘油酯或丙烯酸缩水甘油酯。各单体的较佳重量比为：乙烯40-90%;丙烯酸正-丁酯10-40%;甲基丙烯酸缩水甘油酯或丙烯酸缩水甘油酯0.5-20.0%。
通常不希望加入填料，因为填料的存在会增加对有机液体和蒸气的渗透性，除非对填料的表面粘着性加以严格控制。但是少量的无成核作用的填料，例如颜料，炭黑或碳酸钙容许占聚合物总量的10%以下。填料要磨细以尽量减小这些添加剂对共混物的隔离性能方面的有害影响。
将预混物置于熔体-加工设备如挤塑机、辊研机和密炼设备中进行完全熔融混合，它可以在加工成制品之前独立进行，也可与注塑或挤塑成薄膜或薄板的制造程序同时进行。加工应在抑制PET树脂发生强烈结晶的条件下进行。
因为实际上很难直接测量到与共混聚合物接触的加工设备表面的温度，只能测量到靠近共混聚合物的接触表面的加工设备如模具中所通入的冷却剂的温度，对于本公开说明书和权利要求来说，认为这两种温度彼此十分接近，因而可看作彼此相同。
在本发明中所采用的聚合物共混物，对许多种有机液体，包括象工业上常用的溶剂、稀释剂或分散剂等，都具有良好的隔离性能。例如这种典型的有机液体有：烷烃或芳烃，酮类、醇类，醚类和酯类等。本发明中所采用的聚合物的共混物对于这些有机液体的蒸气，也具有良好的隔离性能。
本发明的制造方法特别适合于熔体-加工的制品，例如：各种容器，容器部件和外套以及薄膜或板材;特别是各种油漆贮罐，挤注管的管咀和柱塞，牙膏管的管咀，容器的螺帽，谷物箱内衬，污水池盖以及工业爆炸品用包装薄膜等。
现提出一些较佳实施方案中有代表性的实例对本发明加以阐述，所有的组分、配比和百分率在未作特别说明时都以重量表示。
试验制品用的是薄膜或者用园筒，园筒高约9.5厘米，上顶直径7厘米，底直径为5厘米，壁厚约1.25毫米，它是在一个Cincinnati Milacron成型设备中，用150吨合模压力经注塑而成。模具用18-20℃的自来水冷却。
那些试验园筒筒壁的韧性是通过落锤冲击试验进行测量，用几组样品对试验结果做统计计算，原来用英制单位表示的试验结果都换算为国际单位。
为了便于比较，有些模塑制品采用在110℃的炉中加热24小时进行退炎的办法以诱导形成结晶。
模塑制品的结晶度通过差示扫描量热法（DSC）用Du Pont热分析仪1090型进行测量。加热速度为每分钟10℃，在加热循环中所得放热峰代表非结晶PET，PET在操作过程中进行结晶，而在冷却中循环冷凝放热反应代表结晶的PET总量。
未经退火的园筒的渗透性能用下列办法进行测量：每个园筒中装入约100克工业级二甲苯，用-金属盖密封，在60℃下贮存688小时后测量重量损失。取三次试验结果的平均值。
薄膜渗透性试验方法如下：
薄膜是用2.5厘米Killion挤塑机和2.5厘米园形吹塑模用吹塑方法制成的。薄膜用氮气进行骤冷，薄膜厚度约1-2密耳（0.025-0.05毫米）。在一个直径为5厘米的铝杯中装入约50毫升二甲苯，用薄膜作杯盖，用这种办法测定薄膜对二甲苯蒸气渗透性的隔离性能。渗透性是通过在环境温度和压力条件下，测定二甲苯的重量损失来确定的。
实例1-5
试验结果汇集在表1中。在所有实例中，树脂是由65%的PET分别与35%的下述各种共聚物共混而成：
实例1-E/MAA 96∶4（熔体指数＝0.8）;
实例2-E/MAA 90.7∶9.3（熔体指数＝2.6）;
实例3-E/MAA 90∶10 71%中和成锌盐;
实例4-E/丙烯酸异丁酯/MAA 80∶10∶10，73%中和成锌盐;
实例5-与实例4相同，但还含有0.3%的四硬脂酸季戊四醇酯（润滑剂）
未退火的园筒按上述方法进行渗透性试验。
实例1-7
用70%PET和30%E/MAA共聚物共混而成的树脂重复进行落锤冲击强度试验。试验结果示如表Ⅱ。
表Ⅱ
实例 羧酸的共聚物 冲击强度（焦耳）
模塑物 经退火处理
6 A（1）30.28 1.41
7 B（2）37.0 2.7
（1）乙烯/甲基丙烯酸（96∶4）共聚物，熔体指数0.8
（2）乙烯/甲基丙烯酸（90∶10）共聚物，71%被锌离子中和
此表更清楚地说明，冷模成形制品比退火的成形制品的韧性好得多。
实例8-9
制成薄膜并按上述方法进行二甲苯渗透性试验。在环境温度和压力下试验456.5小时，结果汇集在表Ⅲ。
表Ⅲ
成份
实例 PET 乙烯聚合物 乙烯聚合物 薄膜厚度 损失
A（1）B（2）（毫米） （克）
8 60 40 0.05 0.05
9 60 30 10 0.05 0.23
（1）乙烯/甲基丙烯酸（96∶4）共聚物
（2）乙烯/甲基丙烯酸（90∶10）共聚物，71%用锌离子中和
Claims (14)
1、用熔体-加工制品的方法，其特征在于可采用45-95%(重量)聚对苯二甲酸乙酯与5-55%(重量)的增韧聚合物的共混物，增韧聚合物可选自：
(a)由至少70%(重量)碳原子数为2-5的α-烯烃与最多30%(重量)α，β-不饱和羧酸组成的共聚物；
(b)由乙烯与α，β-不饱和羧酸和第三组分乙烯基的不饱和单体所组成的共聚物，它们在聚合物中的重量比分别为40-95%，0.5-20%，10-40%；
(c)(a)或(b)的共聚物用锌离子或镁离子进行部分或完全中和得到的离子交联聚合物；
(d)E/X/Y型共聚物，其中单体E、X、Y分别为：
E为乙烯，在乙烯共聚物中占40-90%(重量)；
X为羧酸酯，其化学式为
，式中R1为碳原子数2-8的烷基；R2为H，CH3或C2H5；X在E/X/Y型共聚物中占有10-40%(重量)；
Y选自由甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯组成的基团，Y在E/X/Y型共聚物中占有0.5-20%(重量)；
上述共混物中含有占聚合物总重量0-10%的研细的无成核作用的填料；
在减少聚对苯二甲酸乙酯产生结晶化的条件下对熔体-加工方法加以改善，最好是不要有成核剂，同时将与共混聚合物接触的熔体-加工设备的表面温度保持在100℃以下，特别是保持50℃以下，这样就能制得对各种类型有机液体如烷烃和芳烃，酮类，醇类，醚类及酯类等和各种气体具有低渗透性的韧性制品。
2、按照权利要求1的方法，其中的增韧聚合物是乙烯与不饱和羧酸的共聚物。
3、按照权利要求2的方法，其中的不饱和羧酸是甲基丙烯酸。
4、按照权利要求3的方法，其中甲基丙烯酸在共聚物中的含量为3-20%（重量）。
5、按照权利要求3的方法，其中乙烯与甲基丙烯酸的共聚物在含聚对苯二甲酸乙二醇酯的共混物中所占的重量百分比为20-40%。
6、按照权利要求5的方法，其中乙烯与甲基丙烯酸的共聚物，是经镁离子和锌离子中和反应的产物。
7、按照权利要求1的方法，其中增韧聚合物是乙烯与α，β-不饱和羧酸和丙烯酸酯或乙烯基酯的共聚物。
8、按照权利要求7的方法，其中所用的酯是丙烯酸异丁酯，而酸是甲基丙烯酸或丙烯酸。
9、按照权利要求1的方法，其中增韧聚合物是一种E/X/Y型共聚物，其中R2代表氢或甲基，X在E/X/Y共聚物中的含量为15-35%，最好是20-35%（重量），而Y在其中的含量为2-10%，最好是3-8%（重量）。
10、按照权利要求9的方法，其中R1代表4-6个碳原子组成的烷基。
11、按照权利要求10的方法，其中增韧聚合物是一种F/X/Y型三元共聚物，其中X为丙烯酸正-丁酯，Y为甲基丙烯酸缩水甘油酯，丙烯酸正-丁酯与甲基丙烯酸缩水甘油酯所占重量百分比最好分别为10-40%和0.5-20%。
12、按照权利要求1的方法，其中部分的增韧聚合物可用另一种聚合物来代替，它在熔体-加工条件下对其它两种聚合物呈化学惰性，其含量最多与权利要求1中所述那种类型的增韧聚合物的含量相等，所说另一种聚合物最好是选自聚烯烃，聚苯乙烯，乙烯/乙烯醋酸酯共聚物，乙烯/丙烯酸烷基酯共聚物以及由上述诸聚合物组成的混合物。
13、按照权利要求1的方法，其中熔体-加工的制品是快速冷却到100℃以下，最好到50℃以下。
14、按照权利要求1-13中任何一条方法，可加工成容器，油漆罐，薄膜或薄板，食品箱内衬，污水池盖，爆炸品的包装薄膜，注射管或牙膏管的管咀或柱塞，容器包皮或螺帽等制品。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76287385A | 1985-08-06 | 1985-08-06 | |
| US762,873 | 1985-08-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86104975A true CN86104975A (zh) | 1987-02-11 |
Family
ID=25066252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686104975A Pending CN86104975A (zh) | 1985-08-06 | 1986-08-06 | 对气体和有机液体具有低渗透性的韧性聚对苯二甲酸乙酯制品的加工方法 |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0211649B1 (zh) |
| JP (1) | JPS6248762A (zh) |
| KR (1) | KR900004797B1 (zh) |
| CN (1) | CN86104975A (zh) |
| AT (1) | ATE62855T1 (zh) |
| AU (1) | AU590782B2 (zh) |
| BR (1) | BR8603652A (zh) |
| DE (1) | DE3678877D1 (zh) |
| DK (1) | DK372886A (zh) |
| ES (1) | ES2001868A6 (zh) |
| FI (1) | FI863195A (zh) |
| HK (1) | HK66391A (zh) |
| IL (1) | IL79629A (zh) |
| IN (1) | IN166380B (zh) |
| NZ (1) | NZ217096A (zh) |
| SG (1) | SG66491G (zh) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62149745A (ja) * | 1985-12-25 | 1987-07-03 | Sumitomo Chem Co Ltd | ポリアリ−レンエステル樹脂組成物 |
| JPH0674377B2 (ja) * | 1985-12-26 | 1994-09-21 | 住友化学工業株式会社 | 樹脂組成物 |
| US4826897A (en) * | 1986-12-30 | 1989-05-02 | E. I. Dupont De Nemours And Company | Process for reclaiming polyethylene terephalate scrap contaminated with chlorine-containing polymer |
| JPH0717826B2 (ja) * | 1987-03-31 | 1995-03-01 | ユニチカ株式会社 | 耐衝撃性ポリエステル樹脂組成物 |
| JPH0726002B2 (ja) * | 1987-04-06 | 1995-03-22 | ユニチカ株式会社 | 耐衝撃性ポリエステル樹脂組成物 |
| FR2625215B1 (fr) * | 1987-12-23 | 1990-04-27 | Charbonnages Ste Chimique | Compositions thermoplastiques a base de polyester sature et articles moules les contenant |
| US5300573A (en) * | 1988-04-11 | 1994-04-05 | Advanced Elastomer Systems, L.P. | High temperature stable, low solvent swelling thermoplastic elastomer compositions |
| ES2055162T3 (es) * | 1988-04-11 | 1994-08-16 | Advanced Elastomer Systems | Composiciones de elastomeros termoplasticos que presentan baja hinchazon con disolventes, estables a altas temperaturas. |
| AU627176B2 (en) * | 1988-05-13 | 1992-08-20 | E.I. Du Pont De Nemours And Company | Thermoplastic elastomeric compositions |
| US5023137A (en) * | 1989-03-27 | 1991-06-11 | The Goodyear Tire & Rubber Company | Polyester composition which is particularly suitable for use in thermoforming dual-ovenable trays |
| CA2017213C (en) * | 1989-05-23 | 2000-10-31 | Tadayuki Ohmae | Method for producing thermoplastic elastomer composition |
| SE9002100L (sv) * | 1990-06-13 | 1991-12-14 | Tetra Pak Holdings Sa | Laminerat foerpackningsmaterial med goda arombarriaeregenskaper samt saett att framstaella materialet |
| US5128202A (en) * | 1991-04-12 | 1992-07-07 | E. I. Du Pont De Nemours And Company | Melt fabrication of foam articles |
| US5310787A (en) * | 1991-06-04 | 1994-05-10 | Du Pont-Mitsui Polychemicals Co., Ltd. | Polyester packaging material |
| US5256359A (en) * | 1992-05-06 | 1993-10-26 | E. I. Du Pont De Nemours And Company | Process for manufacturing cast amorphous film |
| WO1994006864A1 (en) * | 1992-09-11 | 1994-03-31 | Eastman Chemical Company | A process for preparing high impact strength polyethylene terephthalate/ionomer blends |
| IT1264976B1 (it) * | 1993-11-17 | 1996-10-17 | Leopoldo Michelotti | Manufatto a forma di lastra sagomata a base di polietilene tereftalato e procedimento per produrlo |
| GB2287673A (en) * | 1994-03-22 | 1995-09-27 | Draftex Ind Ltd | Composite thermoplastic material for blow moulding applications |
| GB9415557D0 (en) * | 1994-08-02 | 1994-09-21 | Chamberlain Vinyl Products Ltd | Shoe stiffener |
| CA2314592A1 (en) * | 1999-09-01 | 2001-03-01 | Owens-Illinois Closure Inc. | Multi-layer plastic closure with barrier properties |
| WO2002061013A1 (en) * | 2001-02-01 | 2002-08-08 | E.I. Dupont De Nemours And Company | Composition suitable for seals and seals made therefrom |
| WO2004039887A1 (ja) * | 2002-10-29 | 2004-05-13 | Kaneka Corporation | 熱可塑性ポリエステル樹脂用増粘剤およびそれを含む熱可塑性ポリエステル樹脂組成物、ならびにそれからなる成形体 |
| US7304107B2 (en) * | 2004-12-21 | 2007-12-04 | E.I. Du Pont De Nemours And Company | Toughened poly(ethylene terephthalate) compositions |
| JP4700453B2 (ja) * | 2005-09-20 | 2011-06-15 | 共同印刷株式会社 | 無延伸フィルム及び蓋材 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3435093A (en) * | 1965-12-17 | 1969-03-25 | Du Pont | Polymer blends of polyethylene terephthalate and alpha-olefin,alpha,beta-unsaturated carboxylic acid copolymers |
| DE1694170A1 (de) * | 1967-07-20 | 1971-06-09 | Hoechst Ag | Thermoplastische Polyesterformmassen |
| US3931114A (en) * | 1972-06-12 | 1976-01-06 | Celanese Corporation | Polybutylene terephthalate blow molded article |
| US4352904A (en) * | 1978-02-28 | 1982-10-05 | E. I. Du Pont De Nemours And Company | Molding resins |
| JPS5714643A (en) * | 1980-06-30 | 1982-01-25 | Toray Ind Inc | Polyethylene terephthalate composition for molding |
| EP0044616B1 (en) * | 1980-07-17 | 1985-01-09 | Imperial Chemical Industries Plc | Films from compositions of polyesters and olefine polymers |
| JPS5755955A (en) * | 1980-09-19 | 1982-04-03 | Mitsubishi Chem Ind Ltd | Thermoplastic polyester resin composition |
| BR8200008A (pt) * | 1981-01-06 | 1982-10-26 | Du Pont | Placa passivel de moldagem a quente e processo de fabricacao de objetos por moldagem a quente |
| JPS58157852A (ja) * | 1982-03-16 | 1983-09-20 | Teijin Ltd | ポリエステル中空成形体又はその前駆成形体の製造法 |
| US4378444A (en) * | 1982-05-12 | 1983-03-29 | E. I. Du Pont De Nemours And Company | Molding material |
| JPS61501270A (ja) * | 1984-02-24 | 1986-06-26 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | 強化熱可塑性ポリエステル組成物 |
-
1986
- 1986-08-01 IN IN589/CAL/86A patent/IN166380B/en unknown
- 1986-08-01 BR BR8603652A patent/BR8603652A/pt unknown
- 1986-08-04 JP JP61182070A patent/JPS6248762A/ja active Pending
- 1986-08-05 FI FI863195A patent/FI863195A/fi not_active Application Discontinuation
- 1986-08-05 AT AT86306027T patent/ATE62855T1/de not_active IP Right Cessation
- 1986-08-05 NZ NZ217096A patent/NZ217096A/xx unknown
- 1986-08-05 DE DE8686306027T patent/DE3678877D1/de not_active Expired - Lifetime
- 1986-08-05 KR KR1019860006463A patent/KR900004797B1/ko not_active IP Right Cessation
- 1986-08-05 ES ES8600876A patent/ES2001868A6/es not_active Expired
- 1986-08-05 DK DK372886A patent/DK372886A/da not_active Application Discontinuation
- 1986-08-05 EP EP86306027A patent/EP0211649B1/en not_active Expired - Lifetime
- 1986-08-05 IL IL79629A patent/IL79629A/xx unknown
- 1986-08-05 AU AU60877/86A patent/AU590782B2/en not_active Ceased
- 1986-08-06 CN CN198686104975A patent/CN86104975A/zh active Pending
-
1991
- 1991-08-16 SG SG66491A patent/SG66491G/en unknown
- 1991-08-22 HK HK663/91A patent/HK66391A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE62855T1 (de) | 1991-05-15 |
| DK372886A (da) | 1987-02-07 |
| AU6087786A (en) | 1987-02-12 |
| DE3678877D1 (de) | 1991-05-29 |
| KR870002188A (ko) | 1987-03-30 |
| NZ217096A (en) | 1988-09-29 |
| SG66491G (en) | 1991-09-13 |
| EP0211649A2 (en) | 1987-02-25 |
| IN166380B (zh) | 1990-04-21 |
| JPS6248762A (ja) | 1987-03-03 |
| FI863195A (fi) | 1987-02-07 |
| FI863195A0 (fi) | 1986-08-05 |
| DK372886D0 (da) | 1986-08-05 |
| EP0211649B1 (en) | 1991-04-24 |
| IL79629A0 (en) | 1986-11-30 |
| KR900004797B1 (ko) | 1990-07-05 |
| ES2001868A6 (es) | 1988-07-01 |
| HK66391A (en) | 1991-08-30 |
| AU590782B2 (en) | 1989-11-16 |
| IL79629A (en) | 1991-09-16 |
| BR8603652A (pt) | 1987-03-10 |
| EP0211649A3 (en) | 1987-08-19 |
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