CN1090077C - 在橡胶上再模压热塑性材料的方法 - Google Patents
在橡胶上再模压热塑性材料的方法 Download PDFInfo
- Publication number
- CN1090077C CN1090077C CN96108085A CN96108085A CN1090077C CN 1090077 C CN1090077 C CN 1090077C CN 96108085 A CN96108085 A CN 96108085A CN 96108085 A CN96108085 A CN 96108085A CN 1090077 C CN1090077 C CN 1090077C
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- China
- Prior art keywords
- polyamide
- rubber
- polymer
- thermoplastic material
- block
- 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.)
- Expired - Fee Related
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- 239000005060 rubber Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 17
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- 239000004416 thermosoftening plastic Substances 0.000 title abstract description 4
- 229920002647 polyamide Polymers 0.000 claims abstract description 46
- 239000012815 thermoplastic material Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 239000004952 Polyamide Substances 0.000 claims description 45
- 229920000570 polyether Polymers 0.000 claims description 23
- 238000003825 pressing Methods 0.000 claims description 23
- 230000026030 halogenation Effects 0.000 claims description 14
- 238000005658 halogenation reaction Methods 0.000 claims description 14
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/20—Making multilayered or multicoloured articles
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- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/126—Halogenation
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- B29K2711/00—Use of natural products or their composites, not provided for in groups B29K2601/00 - B29K2709/00, for preformed parts, e.g. for inserts
- B29K2711/12—Paper, e.g. cardboard
- B29K2711/123—Coated
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- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
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Abstract
本发明涉及一种(1)选自于聚氨酯和以聚酰胺为主要组分的聚合物的热塑材料在(2)橡胶上重复模压的方法,其中要使所述的橡胶表面卤化,然后采用压制法或注塑法重复模压热塑材料。这种方法用于生产运动鞋的鞋底。
Description
本发明涉及在橡胶上再(重复)(模压(surmoulage)热塑材料的方法,所述的热塑材料选自于聚氨酯和以聚酰胺为主要成分的聚合物。
本发明的目的是得到一种含有所谓与橡胶结合的热塑材料的材料。这种材料,或这种结构例如对制造具有弹性聚酰胺鞋底的运动鞋是有用的,在该鞋底上固定了橡胶钉或橡胶鞋根或橡胶件,以便防止鞋磨损。
事实上,对运动鞋所要求的机械性质是这样的:全橡胶鞋底是不适合的,此外,鞋底很重。然而,橡胶不太贵,还很耐磨。
根据本发明,橡胶部分受到表面卤化作用处理,然后采用压制方法对热塑材料件进行再模压。还可以对热塑材料注塑,已卤化的橡胶则预先放在模底中。
橡胶部分只是因橡胶断裂才可能与热塑材料部分分离。
现有技术已经描述过这类材料。EP 550 346描述过在具有聚酰胺段和聚醚段的热塑性聚合物上进行的橡胶再模压。例如,把所述的热塑性聚合物膜或片放到模底,然后在关闭模之后,连同硫化剂和填料一起注入X-NBR橡胶(带羧酸官能的丙烯腈和丁二烯的共聚物)。加热进行橡胶的硫化作用。
得到橡胶/热塑性聚合物集合体,这种集合体是不可能分离的;只是可能发生橡胶断裂。这种方法用起作用的橡胶才是可使用的,这种方法恰当地说适于具有单一形式热塑性聚合物部分的材料。
DE 1942 462描述了采用溴和氯进行卤化的苯乙烯-丁二烯橡胶,然后用聚氨酯粘合剂将它们粘在PVC上。根据本发明,不是必需使用粘合剂。
JPO 5043724(公开)描述了采用盐酸进行表面处理的硫化苯乙烯/丁二烯橡胶。
将这样卤化的橡胶件浸在甲醇中的尼龙共聚物溶液里,然后干燥。这种操作重复两次,从而达到层厚40微米。也可以用尼龙覆盖橡胶刺。这种方法适合覆盖橡胶件,并不能将橡胶件与聚酰胺或聚氨酯件集合起来。此外,必不可少的是溶剂,干燥和干燥时的溶剂回收。另外,任何聚酰胺和聚氨酯在甲醇中都是不可溶的。
本发明涉及热塑材料(1)在橡胶(2)上再模压的方法,所述的热塑材料选自于聚氨酯和以聚酰胺为主要成分的聚合物,所述橡胶在表面被卤化,然后采用压制或注塑方法再模压热塑材料。
本发明中的橡胶应理解为一般含意的橡胶,即橡胶一旦被硫化,其产品压制时的暂留变形(DRC)在100℃低于50%,一般地是50-40%,优选地是低于30%。
作为可卤化橡胶的实例,可以列举以苯乙烯/丁二烯共聚物(SBR)、丁二烯(BR)、天然的异戊二烯(NR)、异戊二烯(IR)、乙烯/丙烯/二烯共聚物(EPDM)、丙烯腈/丁二烯(NBR)共聚物、(甲基)丙烯酸烷酯(ACM)为主要成分的橡胶。
在这些基体聚合物或共聚物中,加入硫化系统、增塑剂、填料,如碳黑、二氧化硅、高岭土、粘土、滑石、白垩等。这些填料可以用硅烷、聚乙二醇或任何其它的连接产品进行表面处理。所有这些产品本身,以及硫化技术都是已知的。
尽管能够使用任何卤素,但由于成本,以及经常是使用方便的原因,限制为氯和溴是有利的。实际上使用氯,因为氯的反应性强,这样就降低了卤化反应时间。
卤化可按多种方式进行:在有机介质中,在三氯异氰酸存在下,但优选地是在含水介质中,在盐酸和次氯酸钠存在下进行卤化。硫化同时受到酸的化学侵蚀、氧化作用和卤化作用,这些作用在于使橡胶表面极化。
在AQUEOUS CHLORINATION OF NATURAL RUBBER(American Chemical Society(Rubber Division)第129次会议,NEW YORK,1986年4月)中对天然橡胶描述了这种技术。
申请人发现能够在上面列举的橡胶上进行硫化。
如果橡胶含有酸性官能团或羧酸酐的话,没有超出本发明的范围。
作为热塑材料使用的聚氨酯可以是聚酯氨酯或聚醚氨酯,它们也具有弹性体的特性。
聚酯氨酯含有来自于聚异氰酸酯与聚丁烯-1,4-己二酸酯类型的聚酯二醇和乙二醇或1,4-丁二醇或链伸长剂二醇反应得到的结构单元。聚醚氨酯含有来自于聚异氰酸酯与聚四亚甲基二醇类型的聚醚二醇和乙二醇或1,4-丁二醇或粘伸长剂二醇反应得到的结构单元。
以聚酰胺为主要成分的聚合物可以是聚酰胺、聚酰胺和聚烯烃的混合物、具有聚酰胺段和聚醚段的聚合物或这些聚合物中两种或多种的混合物。
聚酰胺可以理解为下述缩合反应的产物:
-一种或多种氨基酸,如一种或多种内酰胺的氨基己酸、7-氨基庚酸、11-氨基十一酸、12-氨基十二酸,所述的内酰胺如六碳内酰胺、七碳内酰胺十二碳内酰胺;
-一种或多种盐或二胺与二酸的混合物,二胺如六甲二胺,十二甲二胺、间苯二甲基二胺、双-p-氨基环己基甲烷和三甲基六甲二胺,二酸如异酞酸、对苯二甲酸、二己酸、壬二酸、辛二酸、癸二酸和十二烷二酸;
或所有这些单体的混合物,这可得到共聚酰胺。
可以使用聚酰胺混合物。有利地使用PA-12和PA-11。
关于聚酰胺和聚烯烃混合物,它们含有上述的聚酰胺。这些混合物呈带聚烯烃结的聚酰胺基体状。
关于聚烯烃,可以理解为它是含有烯烃结构单元的聚合物,例如乙烯、丙烯、1-丁烯等结构单元。
作为实例,可以列举:
-聚乙烯、聚丙烯、乙烯与α烯烃的共聚物。这些产品可以用诸如马来酸酐之类的不饱和羧酸酐,或如甲基丙烯酸环氧丙酯之类的环氧化物接枝。
-乙烯与至少一种选自如下产品的共聚物:(1)不饱和羧酸,它们的盐,它们的酯,(2)饱和羧酸乙烯酯,(3)不饱和二羧酸,它们的盐、酯、半酯、酸酐,(4)不饱和环氧化物。
这些乙烯共聚物可以用不饱和二羧酸酐或不饱和环氧化物接枝
-可能马来酸化的苯乙烯/乙烯-丁烯/苯乙烯(SEBS)嵌段共聚物。
可以使用这些聚烯烃中两种或多种聚烯烃的混合物。
有利地是使用:
-聚乙烯,
-乙烯与α烯烃的共聚物,
-乙烯/(甲基)丙烯酸烷酯共聚物,
-乙烯/(甲基)丙烯酸烷酯/马来酸酐的共聚物,马来酸酐被接枝或被共聚合,
-乙烯/(甲基)丙烯酸烷酯/甲基丙烯酸环氧丙酯的共聚物,甲基丙烯酸环氧丙酯被接枝或被共聚合,
-聚丙烯。
为了有利于生成聚酰胺基体,并且如果聚烯烃具有不多或没有能有利于相容性的官能的话,建议加入相容剂。
相容剂是使聚酰胺和聚烯烃相容的本身为已知的产品。
例如可以列举:
-聚乙烯、聚丙烯、乙烯-丙烯共聚物、乙烯-丁烯共聚物,所有这些产品用马来酸酐或甲基丙烯酸环氧丙酯接枝,
-乙烯/甲基丙烯酸烷酯/马来酸酐的共聚物,马来酸酐被接枝或被共聚合,
-乙烯/乙酸乙烯酯/马来酸酐共聚物,马来酸酐被接枝或被共聚合,
-其中马来酸酐被甲基丙烯酸环氧丙酯取代的上述二种共聚物聚,
-乙烯/(甲基)丙烯酸,或许它们的盐的共聚物,
-聚乙烯、聚丙烯或乙烯丙烯共聚物,这些聚合物可用具有与胺进行反应的反应点的产品接以枝;然后,这些接枝共聚物与聚酰胺或具有只一个胺端的聚酰胺低聚物缩合。
这些产品在FR 2 291 225和EP 342 066专利中描述过,在本申请中加入了有关这些产品的内容。
生成基体的聚酰胺的量可以是每5-45份聚烯烃为55-95份。
相容剂的量是足以使聚烯烃在聚酰胺基体中以结的形式分散的量。其量最高达到20%(重量)聚烯烃。根据常用的熔融态混合技术(双螺杆,Buss,单螺杆)将聚酰胺、聚烯烃或许和相容剂混合生产这些聚合物。
有利地,基体是聚酰胺6(PA-6)或(66PA-6,6)分散在其中的有低密度聚乙烯和乙烯与(甲基)丙烯酸烷酯和马来酸酐或甲基丙烯酸环氧丙酯共聚物的混合物结,或聚丙烯结。
这些产品在US 5 070 145和EP 564 338专利中描述过。
在聚丙烯的情况下,加入一种相容剂,这种相容剂有利地是在数量上主要为丙烯结构单元的乙烯/丙烯共聚物,这种共聚物用马来酸酐接枝,然后与己内酰胺单胺化低聚物缩合。
内层为聚酰胺与聚烯烃的这些混合物可以被塑化,这些混合物或许含有如碳黑等填料。
在US 5 342 886专利中描述过这些聚酰胺和聚烯烃混合物。
具有聚酰胺段和聚醚段的聚合物是由在反应端聚酰顺序(嵌段链区)与在反应端聚醚嵌段序(顺序)彼此共缩聚生成的,如:
(1)二胺链末端的聚酰胺顺序与二羧酸链末端的聚亚氧烷基顺序,
(2)二羧酸链末端的聚酰胺顺序与二胺链末端的聚亚氧烷基顺序,二胺链末端的聚亚氧烷基顺序是由称之聚醚二醇的α-ω脂族二羟基化的聚亚氧烷基顺序氰乙基化和氢化得到的。
(3)二羧酸链末端的聚酰胺顺序与聚醚二醇,所得到的产品在这种特殊的情况下是聚醚酯酰胺。
二羧酸链末端的聚酰胺顺序,例如在链限制剂二羧酸存在下,由内酰胺α-ω氨基羧酸或二羧酸和二胺缩合得到。
聚酰胺顺序在数量上摩尔质量Mn是300-15000,优选地是600-5000。聚醚顺序质量Mn是100-6000,优选地是200-3000。
聚醚嵌段聚合物例如可以由聚乙二醇、聚氧丙二醇或聚亚氧四甲基乙二醇衍生得到。或者使用原样聚醚嵌段化合物,与具有羧酸端的聚酰胺嵌段聚合物共缩聚,或者聚醚嵌段化合物被胺化,以便转化成二胺聚醚,并与具有羧酸端的聚酰胺嵌段聚合物缩合。它们还可以与聚酰胺前身和链限制剂混合,以便使它们生成具有聚酰胺段和聚醚段的聚合物,这种聚合物具有统计分布的那些结构单元。为了简化起见,把聚醚嵌段聚合物看作″聚亚氧烷基乙二醇嵌段或结构单元……”。
具有聚酰胺段和聚醚段的聚合物也可以含有随机分布的结构单元。这些聚合物可以采用聚醚与聚酰胺嵌段聚合物的前身同时反应进行制备。
例如,可以在少量水的存在下,让聚醚二醇、内酰胺(或α-ω氨基酸)和链限制剂二酸进行反应。得到主要具有聚醚段、长度变化很大的聚酰胺段,但还具有随机进行反应的不同反应物的聚合物,它们以统计方式沿聚合物链分布。
由预先或一步反应制备的聚酰胺和聚醚顺序(嵌段)共缩聚所得到的具有聚酰胺嵌段和聚醚嵌段聚合物,具有例如肖氏硬度D可以是20-75,有利地是30-70,起始浓度为0.8克/100毫升,在250℃于间甲酚中测定的固有硬度是0.8-2.5。
这些具有聚酰胺嵌段和聚醚嵌段聚合物在US 4331 786、US4 115 475、US 4 195 015、US 4 839 441、US 4 864014、US 4 230 838和US 4 332 920中作过描述。
有利地是,具有聚酰胺嵌段和聚醚嵌段的聚合物是这样的:聚酰胺在重量上是主要组分,即呈嵌段形式,或许在链中以统计方式分布的聚酰胺的量,以具有聚酰胺段和聚醚段聚合物的重量计是50%以上。有利地,聚酰胺的量与聚醚的量的比例(聚酰胺/聚醚)是1/1至3/1。
热塑性材料部分可能已经是成型的件,这时采用压制将它再模压在已卤化的橡胶上。也可以采用注塑进行再模压,将已卤化的橡胶部分放到模中,然后在关闭模之后注入热塑材料。
本发明的材料是由不用粘合剂,彼此连接在一起的,一部分为橡胶一部分为热塑材料构成的;即橡胶卤化和热塑材料的性质足以避免使用粘合剂。
所述的材料在橡胶中是内聚断裂。
当将这两部分分开,断裂没有发生在它们的界面时,可以说断裂是所谓的内聚断裂。相反地,断裂发生在这个界面时,断裂是所谓的粘合断裂。
实施例:
在内混合器中用填料、石蜡油配制SBR、NBR和EPDM橡胶。然往圆柱中加硫化系统。在板状模子中对这些配方进行硫化。
将这些板浸在次氯酸钠和盐酸溶液中。从浴中出来后,这些板或许要碱化,再用水冲洗,并干燥。使用这些板研究不同热塑材料的粘合性,并在下面的实施例中作了描述。
每种类型的热塑材料都采用注塑技术和压制技术进行了再模压试验。
表1 实施例中列出的热塑材料的基本特征标号 类 型 生产者 熔化点 肖氏
硬度Pebax 1 聚酰胺嵌段醚 Elf Atochem 200℃ 55Pebax 2 聚醚胺嵌段醚 Elf Atochem 160℃ 55Elastollan C 85 聚酯聚氨酯 BASF 87Elastollan C 90 聚酯聚氨酯 BASF 92Elastollan C 1185 聚酯聚氨酯 BASF 87Elastollan C 1190 聚酯聚氨酯 BASF 92根据NFT 46008标准在试验24小时测定剥开力(La force depelage)。在热塑材料再模压之前,在橡胶上放置铝粘合带,在卤化橡胶与热塑材料之间提供无粘合区域,进行剥开试验。
在这个表中,PEBAX 1表示具有质量 1300聚酰胺6嵌段和量650聚亚丁基乙二醇嵌段聚合物。
在25℃与间甲酚中以0.5克/100克测定的PEBAX固有粘度是1.55
PEBAX 2表示具有质量2000聚酰胺12嵌段和质量1000聚亚丁基乙二醇嵌段聚合物。
在25℃于间甲酚中以0.5克/100克测定的PEBAX 2固有粘度是1.65。A-表面氯化的SBR
实施例1:
根据下述的方法,在表面已硫化和已氯化的SBR上采用压制方法对表1列出的热塑材料进行再模压:
1.准备橡胶半成品:用冲头将半成品切割成大小为100×40毫米
2.准备热塑材料半成品:采用模压压制得到厚度约1毫米的薄膜并用冲头将半成品切割成大小为100×40毫米。
3.在压制模中,将热塑材料在5分钟升温到180℃,或者在已硫化和已氯化的橡胶表面上在没有压力的条件下,在3分钟升温到220℃。然后施加很小的压力达2分钟,为的是保证半成品成型。再用循环水冷却复合材料。试验后24小时测量剥开力。
表2:在氯化SBR上用压制法再模压热塑材料标号 操作条件 剥开力DaN/cm 断裂观察结果Pebax 1 180℃,5分钟 9 Pebax伸长Pebax 2 180℃,5分钟 12 RPebax 1 220℃,3分钟 6.8 Pebax伸长Elastollan C90 180℃,5分钟 4.5 RCElastollan C90 220℃,3分钟 7.5 R/RCElsatollan 1190 180℃,5分钟 9.3 R在表2和下表中:
R代表在橡胶中的断裂,
RC代表热塑材料/橡胶界面的断裂,
伸长表示在集合体脱胶之前达到热塑材料断裂的伸长。
实施例2:
给注塑热塑材料的压力机配置一个大小为100×100×3毫米的模。
将SBR半成品切割成大小为模块100×100毫米,并放在嵌件中。然后将热塑材料在其塑化温度下注塑,以便再模压在SBR上。在试验后24小时测定剥开力。
表3:在氯化SBR上注塑再模压热塑材料标号 注塑温度 剥开力DaN/cm 断裂观察结果Pebax 1 250-270℃ 9.3 RPebax 2 240-260℃ 10.5 RElastollan C85A 9 Elastollan伸长Elastollan 1185 190-210℃ 7.5 RCB-在表面上氯化的NBR
实施例3:
在与实施例1相同的条件下,在表面硫化和氯化的NBR上压制重复模压不同的热塑材料。
表4:在氯化NBR上用压制法再模压热塑材料标号 操作条件 剥开力DaN/cm 断裂观察结果Pebax 2 180℃,5分钟 7 RCPebax 2 220℃,3分钟 8 Pebax伸长Pebax 1 180℃,5分钟 6.5 RCPebax 1 220℃,3分钟 8 Pebax伸长Elastollan C90 180℃,5分钟 4.5 RCElastollan 1190 180℃,5分钟 6.4 RC
实施例4
在与实施例2相同的条件下,在硫化和氯化的NBR上注塑再模压不同的热塑材料。
表5:在氯化NBR上注塑再模压热塑材料标号 注塑温度 剥开力DaN/cm 断裂观察结果Pebax 5513 220℃-270℃ 7.8 RPebax 553 240-260℃ 5.8 RCElastollan C85A 6.5 Elastollan伸长Elastollan 1185 190-210℃ 7 RCC-表面氯化的EPDM
实施例5
在与实施例1相同的条件下,在表面硫化和氯化的EPDM上用压制法重复模压不同的热塑材料。热塑材料标号 操作条件 剥开力DaN/cm 断裂观察结果Pebax 1 220℃,2分30秒 8.5 Pebax伸长Pebax 2 200℃,2分30秒 8.5 Pebax伸长
Claims (4)
1.选自于以聚酰胺为主要成分的聚合物的热塑材料(1)在橡胶(2)上重复(再)模压的方法,其中使所述的橡胶表面卤化,然后采用压制法或注塑重复模压热塑材料,所述卤化是在有机介质中在三氯异氰酸存在下或者在含水介质中在盐酸和次氯酸钠的存在下进行。
2.根据权利要求1所述的方法,其中以聚酰胺为主要成分的聚合物是具有聚酰胺嵌段和聚醚嵌段的聚合物。
3.根据权利要求1所述的方法,其中具有聚酰胺嵌段和聚醚嵌段的聚合物是聚醚酯酰胺。
4.由上述权利要求中任何一个权利要求所述的方法所得到的,含有一部分是橡胶和一部分是热塑材料的材料,热塑材料选自于以聚酰胺为主要成分的聚合物。
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FR9504913 | 1995-04-25 | ||
FR9504913 | 1995-04-25 |
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CN1090077C true CN1090077C (zh) | 2002-09-04 |
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EP (1) | EP0739931A1 (zh) |
JP (1) | JP2863132B2 (zh) |
KR (1) | KR100191477B1 (zh) |
CN (1) | CN1090077C (zh) |
CA (1) | CA2174895C (zh) |
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EP1184150A4 (en) * | 2000-03-09 | 2007-07-18 | Toyo Tire & Rubber Co | PROCESS FOR PRODUCING RUBBER RESIN COMPOSITE |
EP1424189B1 (en) | 2001-08-10 | 2006-01-11 | NOK Corporation | Process for production of vulcanized rubber-resin composites |
JP5705427B2 (ja) * | 2008-12-11 | 2015-04-22 | 美津濃株式会社 | 靴底および靴底の製造方法 |
EP2684478B1 (en) | 2011-03-11 | 2017-05-31 | Daicel-Evonik Ltd. | Sheet for shoe sole and shoe sole using sheet |
CN102672882A (zh) * | 2012-05-23 | 2012-09-19 | 新疆泰安鞋业有限公司 | 橡胶外鞋底与聚氨酯中鞋底形成组合鞋底的制作工艺 |
WO2020204892A1 (en) * | 2019-03-29 | 2020-10-08 | Compagnie Generale Des Etablissements Michelin | Bonding rubber and plastic surfaces during injection molding |
CN111040420A (zh) * | 2019-09-04 | 2020-04-21 | 晋江兴迅新材料科技有限公司 | 一种pebax制备tpv泡沫材料的方法及tpv泡沫材料 |
FR3131329A1 (fr) * | 2021-12-23 | 2023-06-30 | Arkema France | Composition comprenant un copolymère à blocs polyamides et polyéthers et une poudre de caoutchouc réticulé |
FR3131326B1 (fr) * | 2021-12-23 | 2023-12-22 | Arkema France | Composition comprenant un élastomère thermoplastique et une poudre de caoutchouc réticulé |
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JPS55152040A (en) * | 1979-05-16 | 1980-11-27 | Bridgestone Corp | Adhesion of vulcanized rubber to polyamide resin |
EP0071587A1 (en) * | 1981-07-31 | 1983-02-09 | INTERMARP (ITALIA) S.p.A. | Chemical bath process for the treatment of sealing rings provided with a lip |
EP0137114A2 (en) * | 1983-09-12 | 1985-04-17 | The Firestone Tire & Rubber Company | Adhering cured polymers or prepolymers to cured elastomer utilizing hypochlorous acid treating agent |
EP0550346A1 (fr) * | 1991-12-31 | 1993-07-07 | Elf Atochem S.A. | Procédé de préparation de matériau composite formé d'un élastomère vulcanisé associe à un élastomère thermoplastique à séquences polyamides; et matériau composite ainsi constitué |
JP3024177B2 (ja) * | 1990-07-10 | 2000-03-21 | 株式会社デンソー | 内燃機関用燃料噴射ポンプ |
AU8941501A (en) * | 1998-02-13 | 2002-01-03 | A & E Products Group Lp | Secure pinch-grip hanger |
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JPH0755510B2 (ja) * | 1988-06-27 | 1995-06-14 | 株式会社ブリヂストン | 加硫ゴム―合成樹脂複合体の製造方法 |
JPH0543724A (ja) * | 1991-08-09 | 1993-02-23 | Polytec Design:Kk | ゴム製ブーツ |
-
1996
- 1996-04-16 EP EP96400806A patent/EP0739931A1/fr not_active Withdrawn
- 1996-04-24 CA CA002174895A patent/CA2174895C/fr not_active Expired - Fee Related
- 1996-04-25 CN CN96108085A patent/CN1090077C/zh not_active Expired - Fee Related
- 1996-04-25 KR KR1019960012965A patent/KR100191477B1/ko not_active IP Right Cessation
- 1996-04-25 JP JP8128939A patent/JP2863132B2/ja not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55152040A (en) * | 1979-05-16 | 1980-11-27 | Bridgestone Corp | Adhesion of vulcanized rubber to polyamide resin |
EP0071587A1 (en) * | 1981-07-31 | 1983-02-09 | INTERMARP (ITALIA) S.p.A. | Chemical bath process for the treatment of sealing rings provided with a lip |
EP0137114A2 (en) * | 1983-09-12 | 1985-04-17 | The Firestone Tire & Rubber Company | Adhering cured polymers or prepolymers to cured elastomer utilizing hypochlorous acid treating agent |
JP3024177B2 (ja) * | 1990-07-10 | 2000-03-21 | 株式会社デンソー | 内燃機関用燃料噴射ポンプ |
EP0550346A1 (fr) * | 1991-12-31 | 1993-07-07 | Elf Atochem S.A. | Procédé de préparation de matériau composite formé d'un élastomère vulcanisé associe à un élastomère thermoplastique à séquences polyamides; et matériau composite ainsi constitué |
AU8941501A (en) * | 1998-02-13 | 2002-01-03 | A & E Products Group Lp | Secure pinch-grip hanger |
Also Published As
Publication number | Publication date |
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KR100191477B1 (ko) | 1999-06-15 |
KR960037731A (ko) | 1996-11-19 |
EP0739931A1 (fr) | 1996-10-30 |
JPH08294933A (ja) | 1996-11-12 |
CN1140652A (zh) | 1997-01-22 |
CA2174895C (fr) | 2002-06-04 |
CA2174895A1 (fr) | 1996-10-26 |
JP2863132B2 (ja) | 1999-03-03 |
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