CN103068911A - 交联的弹性体组合物和包括这样的组合物的产品 - Google Patents
交联的弹性体组合物和包括这样的组合物的产品 Download PDFInfo
- Publication number
- CN103068911A CN103068911A CN2011800301427A CN201180030142A CN103068911A CN 103068911 A CN103068911 A CN 103068911A CN 2011800301427 A CN2011800301427 A CN 2011800301427A CN 201180030142 A CN201180030142 A CN 201180030142A CN 103068911 A CN103068911 A CN 103068911A
- Authority
- CN
- China
- Prior art keywords
- composition
- alpha
- segmented copolymer
- olefin
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/026—Crosslinking before of after foaming
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
-
- 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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
本发明涉及交联的弹性体组合物,所述交联的弹性体组合物包含乙烯/α-烯烃多嵌段共聚物、弹性体和可交联聚合物,所述多嵌段共聚物包含聚合的乙烯和α-烯烃单元,所述弹性体包含具有至少两个相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物,所述可交联聚合物如二烯弹性体。本发明也涉及包括该组合物的产品,以及这样的产品作为密封物的应用。
Description
本发明涉及弹性体组合物,特别是基于热塑性弹性体的组合物。这些组合物特别用于建筑行业中的密封剂领域、用于机动车辆用途或用于需要高压缩强度的大规模生产的产品的制造。
意欲用于机动车辆用途或在建筑行业中的用途中的密封物必须具有稳定的尺寸,提供低的压缩永久变形(DRC)并具有在范围可高至100℃的宽温度范围限定的密封特性。此外,这些密封物必须能够防噪音、防风和防水,同时能够长期抵抗紫外(UV)辐射。同时,该组合物必须保持它的对于该应用领域而言所需的挠性和弹性性质。
在历史上,从基于聚氯乙烯(PVC)的混合物制备密封物。然而,这些混合物含有并在燃烧的情况下释放卤化分子,这需要能够替代这些卤化组合物的其它组合物的研究。此外,为了拓宽应用范围,也必须改善这些组合物的物理性质。
被提议的备选物主要是:橡胶,且特别是基于三元乙丙橡胶(EPDM)的那些,热塑性弹性体硫化橡胶(TPE-V)以及苯乙烯热塑性弹性体(TPE-S)。然而这些备选物对于目前的应用领域具有一种以上的缺点,特别是差的着色能力、差的表面外观、气味问题等。
本发明意在补救这些缺点。
根据第一方面,本发明的目的在于,提出一种经济的组合物,优选不含卤化化合物,这使得可以获得在低压缩永久变形、无光泽的或缎光(satin)的外观以及对紫外曝光的稳定性之间的改善的折衷。
该组合物包括:
-例如在5至50重量%之间,优选在9至25重量%之间的乙烯和α-烯烃的多嵌段共聚物,所述乙烯和α-烯烃的多嵌段共聚物包含乙烯的聚合单元和α-烯烃的聚合单元,
-例如在3至50重量%之间的弹性体,所述弹性体包含具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物,和
-例如在3至50重量%之间,优选在4至30重量%之间的可交联聚合物,例如二烯弹性体。
术语“弹性体嵌段”意在表示其玻璃化转变温度Tg低于环境温度且优选低于0℃的嵌段。玻璃化转变温度是例如通过差示扫描量热法根据标准ISO 11357-2测量的。
特别地,在专利申请WO 2006/101966和WO 2006/101930中定义了乙烯和α-烯烃的多嵌段共聚物。该共聚物是特别能够抵抗紫外线的聚合物,并且具有低压缩永久变形(DRC)。这特别使得可以限制组合物由于紫外辐射而老化,而无需添加降低产品某些性能的黑色颜料或其它添加剂。
术语“可交联聚合物”意在表示其大分子可以通过在例如聚合、缩聚或加聚过程中发生的化学反应而相互连接的聚合物。例如,可交联的聚合物使得可以,特别是通过向组合物中引入交联点,赋予组合物无光泽的或缎光的外观,并且使得可以降低压缩永久变形。与非交联的组合物相比,它也使得在长时间对紫外辐射曝光期间,任选地包含部分不饱和的弹性体的组合物有更好的抗性。可交联聚合物可以与所述具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物是相同的或不同的。
最后,所述具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物允许在组合物中形成芳族嵌段的结节,而弹性体嵌段将与可交联聚合物和/或乙烯和α-烯烃的多嵌段共聚物缔合。在环境温度,具有高于环境温度的玻璃化转变温度的结节则处于玻璃态并且因此可以被比作交联节点,从而形成除了通过可交联聚合物提供的化学交联之外的物理伪交联。应当注意,物理交联和化学交联可以是由于同一聚合物导致的,例如当使用SBS时。于是,与未交联的组合物相比,借助受控化学交联,获得了具有低压缩永久变形但也具有更好的抗紫外辐射性、同时特别保持了可挤出性的组合物。当嵌段共聚物是SEBS时,该组合物可以包含在3至50重量%之间的SEBS,优选在4至30%之间,且甚至更优选在10至20重量%之间。当嵌段共聚物是SBS时,该组合物可以包含在3至50重量%之间的SBS,优选在4至30%之间。
优先地,可交联聚合物是聚丁二烯或苯乙烯-丁二烯-苯乙烯(SBS)三嵌段共聚物。当可交联聚合物是SBS时,该组合物可以包含在3至50重量%之间的SBS,优选在4至30%之间。当可交联聚合物是聚丁二烯时,该组合物可以包含在3至50重量%之间的聚丁二烯,优选在4至30%之间,且甚至更优选在4%至6重量%之间。
根据一个实施方案,可交联聚合物是间同立构1,2-聚丁二烯。
苯乙烯-丁二烯-苯乙烯(SBS)三嵌段共聚物是其末端为苯乙烯嵌段且中央弹性体嵌段是丁二烯共聚物的三嵌段共聚物。SBS使得可以获得更显著的无光泽外观,而在具有SBS的混合物中,聚丁二烯特别是间同立构1,2-聚丁二烯使得可以获得更低的压缩永久变形、更好的抗紫外辐射性以及无光泽的或缎光的外观。
所述具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物的弹性体嵌段优先至少包含乙烯单元和丁烯或丙烯单元。选择弹性体嵌段,使其显示出与组合物的其它聚合物的相容性。然而,该共聚物的弹性体嵌段不限于这两个实例。弹性体嵌段因此可以选自C2-C8烯烃均聚物或共聚物,或备选地选自乙烯/丁烯/苯乙烯或者乙烯/丙烯/苯乙烯嵌段。
所述具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物的芳族嵌段优先包含至少一个苯乙烯单元。选择芳族嵌段,首先使其与弹性体嵌段不非常相容,并且其次使其具有高于环境温度的玻璃化转变温度。芳族嵌段将随后形成组合物中的结节。这些结节在环境温度是玻璃态的,并且形成物理伪交联,其赋予最终产品其弹性和抗性的机械性质。
优选地,所述具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物的苯乙烯单元的摩尔质量占所述嵌段共聚物的总摩尔质量的10至50%之间,优选在10%至30%之间。选择苯乙烯单元的百分数,使得芳族嵌段与弹性体嵌段不非常相容。芳族嵌段也可以包含非芳族单元。然而,芳族嵌段将有利地包含至少80摩尔%的芳族单元。芳族嵌段可以包含,例如,至少一个苯乙烯单元且优选至少50摩尔%的一个或多个苯乙烯单元、要不然包括一个或多个其它的α-甲基苯乙烯或乙烯基-萘单元。
优先地,所述具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物是苯乙烯-乙烯/丁烯-苯乙烯(SEBS)三嵌段共聚物或苯乙烯-丁二烯-苯乙烯(SBS)三嵌段共聚物。
SBS是这样一种共聚物,其具有低压缩永久变形,并且也使得可以向组合物中引入一定量的油,因此使得可以降低组合物的总体成本。SEBS是其末端为苯乙烯嵌段且中央弹性体嵌段为乙烯/丁烯无规共聚物的三嵌段共聚物。选择SEBS更具体地是为了其更高的抗紫外辐射性。
乙烯和α-烯烃的多嵌段共聚物具有0.1至0.3的平均嵌段指数且大于1.3,优选在1.7至3.5之间的分子量分布指数(或多分散性指数)Mw/Mn。平均嵌段指数及测定该指数的方法具体定义于专利申请WO 2006/101966中。
乙烯和α-烯烃的多嵌段共聚物具有小于0.91g/cm3,例如在0.89至0.91g/cm3之间的密度。该多嵌段共聚物也可以具有0.1至0.3g/10min,或甚至1.2至2g/10min的熔体流动指数。
α-烯烃选自丙烯、1-丁烯、1-己烯、1-辛烯、4-甲基-1-戊烯、降冰片烯、1-癸烯、1,5-己二烯,或这些化合物的组合。
乙烯和α-烯烃的多嵌段共聚物具有至少一个以摄氏度计的熔点Tm和以克每立方厘米计的密度d,它们的数值满足关系式:
Tm>-2002.9+4538.5(d)-2422.2(d)2,
优选: Tm>-6288.1+13141(d)-6720.3(d)2,
且甚至更佳: Tm>858.91-1825.3(d)+1112.8(d)2
多嵌段共聚物可以包含一个以上含有至少98重量%的乙烯的硬链段,以及一个以上含有少于95重量%、优选少于50重量%的乙烯的软链段。优先地,硬链段以5至85重量%的量存在。在嵌段共聚物中的乙烯含量可以大于50摩尔%。
该组合物可以含有补强填充剂或惰性填充剂如:碳酸钙、粘土、二氧化硅、滑石、炭黑、二氧化钛、热塑性橡胶的增塑剂和油、加工助剂、抗氧化剂、抗紫外线剂、蜡和其它稳定剂、颜料、滑动剂、润滑剂、抗静电剂、抗划剂、物理或化学发泡剂以及其它剂型辅助剂。也可以向该组合物添加以下发泡剂:偶氮二甲酰胺、磺酰肼、碳酸氢盐或脲族,或者含有压缩气体或挥发性液体的微孔发泡剂。
根据第一方面的组合物因此在宽的温度范围具有挠性和弹性性质,具有无光泽的或缎光的外观以及优良的着色能力,并且不产生任何由于气味的问题。此外,如果该组合物包含聚丁二烯,它显示出改善的抗紫外辐射性。这些性能因此使得根据第一方面的组合物特别适宜于应用范围的广泛选择。
根据第二方面,提出了包含根据第一方面的组合物的产品。特别地,该产品可以通过将根据第一方面的组合挤出或注塑来制备。
该产品可以是注塑或挤出产品,用于机动车辆的用途或用于重叠注塑(overmolding)的用途,例如把手(grip)、厨房器具、体育用品等。
该产品可以包含含有如前文所述的物理或化学发泡剂的组合物并且可以是发泡的(expanded)产品。
根据本发明的第三方面,提出了使用根据第二方面的产品作为防漏密封物。
防漏密封物可用于建筑行业(建筑物)、用于机动车辆或用于工业应用(家用电器如冰箱、洗衣机)。
作为产品、特别是防漏密封物的一个优选实施方案,目前考虑的是组合物C1,其包含:
-21.8重量%的乙烯和α-烯烃的多嵌段共聚物(Infuse D9000,得自Dow),
-5.9重量%的聚丙烯均聚物,
-2.9重量%的中等密度聚乙烯,
-10.6重量%的SBS(高分子量,含有30%的苯乙烯的未充油的星形SBS),
-26重量%的石蜡油(高度精制的白石蜡油),
-32.3重量%的5μm白垩(Durcal 5(Omya)或Craie DRB 20(ImerysMinéraux)),
-0.35重量%的保护体系(得自Ciba Spécialités Chimiques SA(Additifs)的Irganox 1076FD或Chimassorb 944FDL或Tinuvin 327,或得自BASF的Irgafos 16),
-0.09重量%的过氧化物(α,α′-双(叔丁基过氧)-二异丙基苯),和
-0.06重量%的活性助剂氰尿酸三烯丙酯(TAC):TAC DL70,得自Lehvoss)。
组合物C1因此含有21.8重量%的乙烯和α-烯烃的多嵌段共聚物以及10.6重量%的具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的可交联聚合物。SBS因此同时起到作为交联剂(借助双键)和作为能够借助苯乙烯嵌段形成结节的特别弹性体的作用。
组合物可以以粒料形式制备,要不然在注塑或挤出产品如防漏密封物的生产过程中直接制备。因此,当它以粒料形式制备时,组合物C1可以通过在环境温度,将它的各种固体成分干燥混合并随后挤出而制备。
组合物C1具有以下性质:
-60肖氏A(Shore A)的硬度(根据标准ISO 868测量);
-41%的压缩永久变形(根据标准ISO 815测量,即用时22小时,在70℃测量),以及
-无光泽的外观。
组合物C1因此使得可以获得具有持久力和抗性的性质,适用于建筑行业或机动车辆工业的产品。特别是,特别借助所使用的SBS,该组合物具有无光泽的外观。
考虑产品的第二实施方案,所述产品特别是防漏密封物,其中组合物C2包含:
-13.6重量%的乙烯和α-烯烃的多嵌段共聚物(Infuse D9000,得自Dow),
-11.3重量%的聚丙烯均聚物(100-GB006(Ineos)或PP 571P(Sabic)或PPH3060(Total)),
-4.2重量%的中等密度聚乙烯(Lupolen 3721C,得自LydonDellBasell),
-13.6重量%的SEBS(Kraton G6151ES,得自Kraton Polymer),
-4.7重量%的1,2-聚丁二烯(RB830,得自JSR Corporation),
-37重量%的石蜡油(Primol 352,得自Esso),
-14.8重量%的5μm白垩(Durcal 5(Omya)或Craie DRB 20(ImerysMinéraux)),
-0.72重量%的保护体系(得自Ciba Spécialités Chimiques SA(Additifs)的Irganox 1076FD或Chimassorb 944FDL或Tinuvin 327,或得自BASF的Irgafos 16),
-0.05重量%的过氧化物(Luperox F40,得自Safic Alcan),和
-0.03重量%的试剂TAC(活性助剂氰尿酸三烯丙酯(TAC):TAC FL70,得自Lehvoss)。
组合物C2因此含有13.6重量%的乙烯和α-烯烃的多嵌段共聚物、13.6重量%的具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物,以及4.7重量%的起着交联剂作用的聚丁二烯。
组合物可以以粒料形式制备,要不然在注塑或挤出产品如防漏密封物的生产过程中直接制备。因此,当它以粒料形式制备时,组合物C2可以通过在环境温度,将它的各种固体成分干燥混合并随后挤出而制备。
组合物C2具有以下性质:
-60肖氏A的硬度(根据标准ISO 868测量),
-36%的压缩永久变形(根据标准ISO 815测量,即用时22小时,在70℃测量),
-缎光的外观,以及
-更长的抗紫外老化性。
组合物C2因此使得可以获得具有持久力和抗性的性质,适用于建筑行业或机动车辆工业的产品。此外,组合物不具有光泽的外观,而是缎光的外观,原因在于SEBS与可交联聚合物RB830的共混,这导致更不明显的无光泽的外观,但有更高的抗紫外辐射性。此外,为了获得有色的最终产品,也可以对组合物着色。特别是,高的抗紫外辐射性使得可以用浅色对产品着色,尽管后者通常会加速产品的老化。
考虑产品的第三实施方案,所述产品特别是防漏密封物,其中组合物C3包含:
-14重量%的乙烯和α-烯烃的多嵌段共聚物(Infuse D9000,得自Dow),
-13重量%的聚丙烯均聚物(100-GB006(Ineos)或PP 571P(Sabic)或PPH3060(Total)),
-3重量%的中等密度聚乙烯(Lupolen 3721C,得自LydonDellBasell),
-5.9重量%的1,2-聚丁二烯(RB830,得自JSR Corporation),
-12.5重量%的SEBS(Kraton G6151ES,得自Kraton Polymer),
-36重量%的石蜡油(Primol 352,得自Esso),
-14.8重量%的5μm白垩(Durcal 5(Omya)或Craie DRB 20(ImerysMinéraux)),
-0.62重量%的保护体系(得自Ciba Spécialités Chimiques SA(Additifs)的Irganox 1076FD或Chimassorb 944FDL或Tinuvin 327,或得自BASF的Irgafos 16),
-0.12重量%的过氧化物(Luperox F40,得自Safic Alcan),和
-0.06重量%的试剂TAC(活性助剂氰尿酸三烯丙酯(TAC):TAC DL70,得自Lehvoss)。
组合物C3因此含有14重量%的乙烯和α-烯烃的多嵌段共聚物、12.5重量%具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的可交联聚合物,以及5.9重量%的起着交联剂作用的聚丁二烯。
组合物可以以粒料形式制备,要不然在注塑或挤出产品如防漏密封物的生产过程中直接制备。因此,当它以粒料形式制备时,组合物C3可以通过在环境温度,将它的各种固体成分干燥混合并随后挤出而制备。
组合物C3具有以下性质:
-65肖氏A的硬度(根据标准ISO 868测量),
-36%的压缩永久变形(根据标准ISO 815测量,即用时22小时,在70℃测量),以及
-更长的抗紫外老化性。
组合物C3因此可以使得获得具有持久力和抗性的性质,适用于建筑行业或机动车辆工业的产品。此外,组合物不具有光泽的外观,而是缎光的外观,原因在于SEBS与可交联聚合物RB830的共混,这导致更不明显无光泽的外观,但有更高的抗紫外辐射性。
考虑产品的第四实施方案,所述产品特别是防漏密封物,其中组合物C4包含:
-13重量%的乙烯和α-烯烃的多嵌段共聚物(Infuse D9000,得自Dow),
-14.6重量%的聚丙烯均聚物(100-GB006(Ineos)或PP 571P(Sabic)或PPH3060(Total)),
-4重量%的中等密度聚乙烯(Lupolen 3721C,得自LydonDellBasell),
-4.7重量%的1,2-聚丁二烯(RB830,得自JSR Corporation),
-13重量%的SEBS(Kraton G6151ES,得自Kraton Polymer),
-35重量%的石蜡油(Primol 352,得自Esso),
-14.3重量%的5μm白垩(Durcal 5(Omya)或Craie DRB 20(ImerysMinéraux)),
-1.22重量%的保护体系(得自Ciba Spécialités Chimiques SA(Additifs)的Irganox 1076FD或Chimassorb 944FDL或Tinuvin 327,或得自BASF的Irgafos 16),
-0.12重量%的过氧化物(Luperox F40,得自Safic Alcan),
-0.06重量%的试剂TAC(活性助剂氰尿酸三烯丙酯(TAC):TAC FL70,得自Lehvoss)。
组合物C4因此含有13重量%的乙烯和α-烯烃的多嵌段共聚物、13重量%的具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的可交联聚合物,以及4.7重量%的起着交联剂作用的聚丁二烯。
组合物可以以粒料形式制备,要不然在注塑或挤出产品如防漏密封物的生产过程中直接制备。因此,当它以粒料形式被制备时,组合物C4可以通过在环境温度,将它的各种固体成分干燥混合并随后挤出而制备。
组合物C4具有以下性质:
-70肖氏A硬度(根据标准ISO 868测量),
-40%的压缩永久变形(根据标准ISO 815测量,即用时22小时,在70℃测量),以及
-缎光的外观,
-更长的抗紫外老化性。
组合物C4因此使得可以获得具有持久力和抗性的性质,适用于建筑行业或机动车辆工业的产品。此外,组合物不具有光泽的外观,而是缎光的外观,原因在于SEBS与可交联聚合物RB830的共混,这导致更不明显无光泽的外观,但有更高的抗紫外辐射性。
Claims (11)
1.一种交联的弹性体组合物,所述交联的弹性体组合物包括:
-乙烯和α-烯烃的多嵌段共聚物,所述多嵌段共聚物包含乙烯的聚合单元和α-烯烃的聚合单元,
-弹性体,所述弹性体包含具有至少两个可以相同或不同的、被至少一个弹性体嵌段分隔开的芳族嵌段的嵌段共聚物,和
-可交联聚合物。
2.根据权利要求1所述的组合物,其中所述可交联聚合物是聚丁二烯,例如间同立构1,2-聚丁二烯,或是苯乙烯-丁二烯-苯乙烯(SBS)三嵌段共聚物。
3.根据在前权利要求中任一项所述的组合物,其中所述嵌段共聚物是苯乙烯-乙烯/丁烯-苯乙烯(SEBS)三嵌段共聚物或苯乙烯-丁二烯-苯乙烯(SBS)三嵌段共聚物。
4.根据在前权利要求之一所述的组合物,其中所述乙烯和α-烯烃的多嵌段共聚物具有0.1至0.3的平均嵌段指数和大于1.3的分子量分布指数Mw/Mn。
5.根据在前权利要求之一所述的组合物,其中所述乙烯和α-烯烃的多嵌段共聚物具有小于0.91g/cm3的密度。
6.根据在前权利要求之一所述的组合物,其中所述α-烯烃表示丙烯、1-丁烯、1-己烯、1-辛烯、4-甲基-1-戊烯、降冰片烯、1-癸烯、1,5-己二烯,或这些化合物的组合。
7.根据在前权利要求之一所述的组合物,其中所述乙烯和α-烯烃的多嵌段共聚物具有至少一个以摄氏度计的熔点Tm和以克/cm3计的密度d,其中这些变量的数值满足关系式:
Tm>-2002.9+4538.5(d)-2422.2(d)2,
优选: Tm>-6288.1+13141(d)-6720.3(d)2,
且甚至更佳:Tm>858.91-1825.3(d)+1112.8(d)2。
8.根据在前权利要求之一所述的组合物,所述组合物包含一种以上物理或化学发泡剂,特别是下列发泡剂:偶氮二甲酰胺、磺酰肼、碳酸氢盐或脲族,或者含有压缩气体或挥发性液体的微孔发泡剂。
9.一种产品,特别是注塑或挤出产品,所述产品包含根据权利要求1至8之一所述的组合物。
10.根据前一权利要求所述的产品,所述产品包括根据权利要求8所述的组合物,并且其中所述产品是发泡的。
11.根据权利要求9或10所述的产品作为防漏密封物的应用。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1054860A FR2961517B1 (fr) | 2010-06-18 | 2010-06-18 | Composition elastomerique reticulee, et produit comprenant une telle composition |
FR1054860 | 2010-06-18 | ||
PCT/EP2011/060250 WO2011157852A1 (fr) | 2010-06-18 | 2011-06-20 | Composition élastomérique réticulée, et produit comprenant une telle composition |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103068911A true CN103068911A (zh) | 2013-04-24 |
Family
ID=43301824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2011800301427A Pending CN103068911A (zh) | 2010-06-18 | 2011-06-20 | 交联的弹性体组合物和包括这样的组合物的产品 |
Country Status (12)
Country | Link |
---|---|
US (1) | US20130210945A1 (zh) |
EP (1) | EP2582753B1 (zh) |
JP (2) | JP2013534552A (zh) |
KR (1) | KR20130041908A (zh) |
CN (1) | CN103068911A (zh) |
BR (1) | BR112012032253A2 (zh) |
ES (1) | ES2624281T3 (zh) |
FR (1) | FR2961517B1 (zh) |
MX (1) | MX337680B (zh) |
RU (1) | RU2590555C2 (zh) |
SG (1) | SG186736A1 (zh) |
WO (1) | WO2011157852A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2922839C (en) | 2013-09-13 | 2021-10-26 | Dow Global Technologies Llc | Peroxide-crosslinkable compositions and processes for their manufacture |
CN106147107B (zh) * | 2015-04-01 | 2020-09-04 | 李永腾 | 多层热塑性弹性体发泡材料及其制造方法 |
TWI659833B (zh) * | 2015-04-01 | 2019-05-21 | 李永騰 | 多層熱塑性彈性體發泡材料及其製造方法 |
JP6728646B2 (ja) * | 2015-11-18 | 2020-07-22 | 三菱ケミカルインフラテック株式会社 | パラフィン系組成物及び蓄熱材 |
DE102019110210A1 (de) * | 2019-04-17 | 2020-10-22 | Kraiburg Tpe Gmbh & Co. Kg | Thermoplastische Elastomerzusammensetzung als Verklebesystem für Gummi auf Basis vernetzter Kautschuke |
TWI792752B (zh) * | 2020-12-11 | 2023-02-11 | 南韓商Lg化學股份有限公司 | 包含由用於浸漬成型的乳膠組成物衍生的層之浸漬成型物件 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101277987A (zh) * | 2005-03-17 | 2008-10-01 | 陶氏环球技术公司 | 由乙烯/α-烯烃共聚体制备的聚合物掺合物以及由其制备的挠性模制品 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1230133B (it) * | 1989-04-28 | 1991-10-14 | Himont Inc | Composizioni polipropileniche plasto-elastiche |
US6048942A (en) * | 1996-09-30 | 2000-04-11 | Montell North America Inc. | Thermoplastic olefin articles having high surface gloss and mar resistance |
AR048104A1 (es) * | 2004-03-17 | 2006-03-29 | Dow Global Technologies Inc | Composicion catalizadora que comprende un agente de enlace para la formacion de copolimeros superiores de olefina en bloques multiples |
US7582716B2 (en) * | 2004-03-17 | 2009-09-01 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack |
US7671106B2 (en) * | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Cap liners, closures and gaskets from multi-block polymers |
US7714071B2 (en) * | 2004-03-17 | 2010-05-11 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom |
JP5221334B2 (ja) | 2005-03-17 | 2013-06-26 | ダウ グローバル テクノロジーズ エルエルシー | フィルムに適するエチレン/α−オレフィンマルチブロック共重合体の組成物 |
ES2320383T3 (es) | 2005-03-17 | 2009-05-21 | Dow Global Technologies Inc. | Interpolimeros de bloques de etileno/alfa-olefinas. |
US7737215B2 (en) * | 2005-03-17 | 2010-06-15 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
TW200635961A (en) * | 2005-03-17 | 2006-10-16 | Dow Global Technologies Inc | Cap liners, closures and gaskets from multi-block polymers |
MX2010009533A (es) * | 2008-03-13 | 2010-09-24 | Basf Se | Espuma de particulas elastica fabricada a partir de mezclas de polimeros de poliolefina/estireno. |
EP2401324B1 (en) * | 2009-02-25 | 2013-08-21 | Dow Global Technologies LLC | Phylon processes of making foam articles comprising ethylene/ -olefins block interpolymers |
-
2010
- 2010-06-18 FR FR1054860A patent/FR2961517B1/fr active Active
-
2011
- 2011-06-20 CN CN2011800301427A patent/CN103068911A/zh active Pending
- 2011-06-20 MX MX2012014566A patent/MX337680B/es active IP Right Grant
- 2011-06-20 EP EP11727431.6A patent/EP2582753B1/fr active Active
- 2011-06-20 JP JP2013514741A patent/JP2013534552A/ja active Pending
- 2011-06-20 BR BR112012032253A patent/BR112012032253A2/pt not_active IP Right Cessation
- 2011-06-20 RU RU2013102291/05A patent/RU2590555C2/ru active
- 2011-06-20 ES ES11727431.6T patent/ES2624281T3/es active Active
- 2011-06-20 US US13/805,330 patent/US20130210945A1/en not_active Abandoned
- 2011-06-20 WO PCT/EP2011/060250 patent/WO2011157852A1/fr active Application Filing
- 2011-06-20 KR KR1020137001354A patent/KR20130041908A/ko not_active Application Discontinuation
- 2011-06-20 SG SG2012092615A patent/SG186736A1/en unknown
-
2015
- 2015-10-09 JP JP2015200779A patent/JP6092977B2/ja active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101277987A (zh) * | 2005-03-17 | 2008-10-01 | 陶氏环球技术公司 | 由乙烯/α-烯烃共聚体制备的聚合物掺合物以及由其制备的挠性模制品 |
Also Published As
Publication number | Publication date |
---|---|
WO2011157852A1 (fr) | 2011-12-22 |
ES2624281T3 (es) | 2017-07-13 |
JP6092977B2 (ja) | 2017-03-08 |
FR2961517B1 (fr) | 2014-04-11 |
KR20130041908A (ko) | 2013-04-25 |
MX2012014566A (es) | 2013-05-28 |
EP2582753B1 (fr) | 2017-03-22 |
RU2013102291A (ru) | 2014-07-27 |
MX337680B (es) | 2016-03-15 |
JP2013534552A (ja) | 2013-09-05 |
RU2590555C2 (ru) | 2016-07-10 |
JP2016029179A (ja) | 2016-03-03 |
US20130210945A1 (en) | 2013-08-15 |
BR112012032253A2 (pt) | 2019-09-24 |
SG186736A1 (en) | 2013-02-28 |
EP2582753A1 (fr) | 2013-04-24 |
FR2961517A1 (fr) | 2011-12-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
RU2374278C2 (ru) | Термопластичная эластомерная композиция, имеющая высокую прочность расплава, для изготовления формовых эластичных изделий, способ ее получения, премикс, используемый в качестве гомогенной добавки для деформационного упрочнения расплава, для получения композиции, способ получения премикса, формованное гибкое термопластичное эластомерное изделие и способ его получения | |
CN103068911A (zh) | 交联的弹性体组合物和包括这样的组合物的产品 | |
JP6014594B2 (ja) | 架橋組成物、架橋組成物の製造方法、及び成形体 | |
US20060063850A1 (en) | Molded article of thermoplastic elastomer composition and process for producing the same | |
CN101688049A (zh) | 用于热塑性弹性体的功能添加剂 | |
WO2003048252A1 (en) | Thermoplastic elastomer with improved properties | |
Naskar et al. | Thermoplastic elastomers by dynamic vulcanization | |
CN101426828B (zh) | 改良的热塑性弹性体组合物 | |
WO2003066732A1 (en) | Polymer compositions | |
WO2012067609A1 (en) | Thermaoplastic elastomer composition with improved compression set values | |
JP6153788B2 (ja) | 発泡熱可塑性エラストマー組成物、及び複合成形体 | |
JP4184206B2 (ja) | 熱可塑性エラストマー組成物 | |
JP5498207B2 (ja) | 架橋組成物、架橋組成物の製造方法、成形体 | |
JP2003003038A (ja) | 熱可塑性エラストマー組成物およびその製造方法 | |
JP2003012887A (ja) | 熱可塑性エラストマー樹脂組成物 | |
WO2002072690A1 (fr) | Composition elastomere olefinique thermoplastique | |
JP2021161128A (ja) | 熱可塑性エラストマー組成物、成形体及びインストルメントパネル用表皮 | |
JP2003003039A (ja) | 熱可塑性エラストマー組成物の製造方法 | |
WO2021024347A1 (ja) | 熱可塑性エラストマー組成物 | |
JP2004238570A (ja) | 摩擦係数の大きい熱可塑性エラストマー組成物及びそれからなる滑り止め部材 | |
JP2003313394A (ja) | 熱可塑性エラストマー製シート | |
JPS59164351A (ja) | 耐熱性エラストマ−組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C53 | Correction of patent of invention or patent application | ||
CB02 | Change of applicant information |
Address after: France was Furi Applicant after: MCPP France Address before: France was Furi Applicant before: Thermoplastiques Cousin Tessier |
|
COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: THERMOPLASTIQUES COUSIN TESSIER TO: MCPP FRANCE COMPANY |
|
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130424 |