MXPA06002863A - Polymeric composition, polymer-extruded article and weather strip for automotive vehicle - Google Patents

Abstract

A polymer-extruded article produced by extrusion and vulcanization of a polymeric composition includes ethylene-+--olefin-nonconjugated polyene copolymer in an amount of 100 phr+ADs- carbon black in an amount ranging from more than 50 to 120 phr, the carbon black having an arithmetic average particle diameter of not smaller than 60 nm+ADs- a softener in an amount of not more than 100 phr+ADs- and thermo-expansive capsules in an amount ranging from 1 to 10 phr. The polymer-extruded article includes a surface section havingan uneven surface derived from thermal expansion of the thermo-expansive capsules, and a rough surface derived from carbon particle of the carbon black and formed at the uneven surface derived form the thermal expansion of the thermo-expansive capsules.

Description

POLYMERIC COMPOSITION, EXTRUDED POLYMER ARRAY AND AUTOMOTIVE VEHICLE CLIMATE BACKGROUND BACKGROUND OF THE INVENTION This invention relates to a polymeric composition, an extruded polymer article and a climate strip for a motor vehicle, to be used, for example, for a door panel, glass and the like. An extruded vulcanized article (hereinafter referred to as an extruded polymer article) formed of a polymeric composition in which a polymer material such as a rubber material or the like is mixed is applied to a variety of uses. The research and development has been done in the extruded polymer article to meet the characteristics according to the uses. For example, as a technique to achieve a lightening of weight, for the extruded polymer article, applied to a strip for climate, the following technique is known: The polymeric composition in which thermally expandable microcapsules are mixed (referred to later in present as heat-expansive capsules). During the vulcanization of the polymer composition, the heat-expansive capsules are thermally expanded (slightly foamed). This is to lower the specific gravity of the aforementioned extruded polymer article while obtag a sufficient hardness, as disclosed in the publication.

Japanese Provisional No. 6-183305. Additionally, the aforementioned extruded polymer article is low in sliding characteristics and in adhesion strength to an object (hereinafter referred to as an object to be used, for example, to a door panel, a glass and the like) whereby the extruded polymer article is used. In order to improve the characteristics and adhesion strength, a surface treatment agent including an elastomeric polymer material is applied to a surface (at least surfaces of sections requiring various characteristics) of the extruded polymer article. Examples of the characteristics required for the aforementioned surface treatment agent are improvements in the sliding characteristics, for example, a feature to prevent the low degree of noise due to the slip-slip generation in case the extruded polymer article be used to be slidably movable to the object to be used) of the surface of the extruded polymer article against the object to be used, resistance to adhesion (for example, a characteristic to prevent the extruded polymer article from doing its functional degradation due to to the adhesion of the polymer material to the object to be used), repellency water '(for example a feature to prevent freezing of the extruded polymer article) and the like. For example, in the event that a weather strip constitutes a seal section (eg, a seal section formed of a foamed rubber), a surface treatment agent is coated over the seal section thus preventing the adhesion between the seal section and a door panel when a door is opened or closed to avoid difficulty in opening and closing the door. Even in a cold region, the seal section can be prevented from freezing. Additionally, in case of a use in which the surface of the above-mentioned extruded polymer article is in sliding contact with the glass, the door panel, or the like, the sliding characteristics of the extruded polymer article is improved with the agent of above-mentioned surface treatment thus preventing the generation of low-grade noise due to slip-slip. As the above-mentioned surface treatment agent is known, for example, one formed by adding diorganopolysiloxane or hardenable polyurethane. This surface treatment agent is coated on the extruded polymer article thereby improving the sliding characteristics, adhesion resistance, water repellency and the like. BRIEF DESCRIPTION OF THE INVENTION However, in case the surface treatment agent is coated on the extruded polymer article as discussed above, there are concerns of formation of the coating macula (e.g., coating macule). it is formed due to the non-uniform coating of the surface treatment agent) according to the coating conditions (for example, the temperature, viscosity and the like of the surface treatment agent during the coating and the temperature and the like of the article of polymer extruded as an object to be coated) for the surface treatment agent and for rendering insufficient the thickness of a layer (hereina referred to as a surface treatment layer) formed of the coated surface treatment agent. Therefore, there are concerns to decrease productivity (practicability, product performance and the like), and to make it impossible to obtain sufficient gliding characteristics, adhesion resistance, water repellency and the like making it impossible in this way to sufficiently exhibit the functions and the like of the extruded polymer article.

Therefore, it is an object of the present invention to provide an improved polymer composition, an extruded polymer article and a climate strip for a motor vehicle, capable of overcoming the disadvantages found in the conventional similar polymer composition, the extruded polymer article. and the strip for climate for motor vehicle. Another object of the present invention is to provide an improved polymer composition, an extruded polymer article and a climate strip for a motor vehicle capable of sufficiently exhibiting the proposed function of the extruded polymer article, improving its gliding characteristics, adhesion strength, repellency to water without degrading productivity even when the surface treatment agent is not coated on the extruded polymer article. An aspect of the present invention resides in a polymer composition used for an extruded polymer article produced by extrusion and vulcanization comprising: ethylene-to-olefin-polyane copolymer non-conjugated in an amount of 100 phr carbon black in a amount that varies from more than 50 to 120 phr, the carbon black having an arithmetic mean of particle diameter of not less than 60 nm; a soer in an amount of not more than 100 phr and thermoexpansive capsules in an amount that varies from 1 to 10 phr. Another aspect of the present invention resides in an article of extruded polymer produced by the extrusion and vulcanization of a polymeric composition that includes a copolymer of ethylene-α-olefin-polyane non-conjugated in an amount of 100 phr, carbon black in an amount which varies more than 50 to 120 phr, the carbon black having an arithmetic mean of particle diameter of not less than 60 nm; a soer in an amount of no more than 100 phr; and the heat-expansive capsules in an amount ranging from 1 to 10 phr. The extruded polymer article comprises a surface section having an uneven surface derived from the thermal expansion of the heat-expansive capsules, and a rough surface derived from the carbon black carbon particles and formed on the uneven surface derived from thermal expansion of the thermoexpansive capsules. According to the present invention, the polymer composition contains at least one non-conjugated ethylene-α-olefin-polyene copolymer in an amount of 100 phr, the carbon black in an amount ranging from more than 50 phr to 120 phr. , the carbon black having an arithmetic mean of particle diameter of not less than 60 nm, a smoother in an amount of not more than 100 phr y. thermally expandable microcapsules in an amount that varies from 1 phr to phr, in what is being mixed. Accordingly, a surface treatment agent or the like is not coated, and therefore it is unnecessary to take it into account of its coating conditions and the like. In the extruded polymer article produced by the extrusion and vulcanization of the aforementioned polymer composition, the aforementioned thermally expandable microcapsules are expanded during vulcanization and therefore an uneven surface is formed derived from the thermal expansion of the heat-expansive capsules, the uneven surface having a shape according to the amount of mixing and a degree of thermal expansion of the heat-expansive capsules. Additionally, since carbon black having an arithmetic mean of particle diameter not less than 60 nm is mixed in an amount ranging from more than 50 phr to 120 phr, a part containing a large amount of ethylene-copolymer. Non-conjugated olefin-polyene is locally formed in the aforementioned extruded polymer article. The shrinkage or the like occurs in part, and therefore the rough surface derived from the carbon black particles of carbon are formed on the aforementioned uneven surface derived from the thermal expansion of the thermoexpansive capsules, the rough surface having an surface roughness according to the diameter of particle, amount of mixing and the similar of carbon black. With this, the contact area between the aforementioned extruded polymer article and the object to be used becomes small. The respective mixing amounts of the aforementioned non-conjugated ethylene-to-olefin-polyene copolymer, carbon black, softener and thermally expandable microcapsules are preferably within ranges that can degrade the characteristics of the proposed polymer composition and the article, respectively. of extruded polymer. For example with the mixing amounts of the aforementioned non-conjugated ethylene-to-olefin-polyene copolymer, carbon black, softener and thermally expandable microcapsules respectively outside the ranges of the present invention, it may be possible to degrade the practicality of the polymer composition and the characteristics (gliding characteristics, adhesion strength, water repellency and the like) of the extruded polymer article. In case the aforementioned silicone compound is mixed excessively, it may be possible that it becomes difficult to weld or bond the aforementioned extruded polymer article to the object to be used (e.g., bond a thermoplastic elastomer, or join it during the injection molding together with a rubber member). In addition to the aforementioned various materials, a variety of additional materials treated in the technical field of the extruded polymer article produced by general extrusion and vulcanization can be mixed. It is preferable that the respective mixing amounts of the additional mixed materials are within the ranges that do not degrade the proposed characteristics of the polymer composition and the extruded polymer article. For example, in case of using a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerating aid, and the like, if the mixing amounts thereof are very small, the vulcanization progress becomes slow; Considering that if the amount of mixing is too much, it may be possible to highlight a flowering phenomenon. BRIEF DESCRIPTION OF THE DRAWINGS In the drawings, like reference numerals designate similar parts and elements throughout the figures: Figs. 1A to 1E are sectional explanatory views which respectively show structural models of the extruded polymer articles produced by the extrusion and vulcanization of polymer compositions; Fig. 2 is a fragmentary schematic perspective view of a specimen of the extruded polymer article used as in each of the Examples and Comparative Examples; Figs. 3A to 3C are perspective views in plan, side and explanatory operational, respectively, showing a measurement method for a bond strength of a test piece of each of the Examples and Comparative Examples; Fig. 4 is an explanatory side view showing a measurement method for a coefficient of friction of a test piece of each of the Examples and Comparative Examples; Fig. 5 is an explanatory side view showing a measurement method for a water contact angle of a test piece of each of the Examples and Comparative Examples; Fig. 6 is a graph showing a surface roughness in terms of a quantity of coal blended 80 nm in relation to specimens of the Examples and Comparative Examples; and Fig. 7 is a graph showing a surface roughness in terms of a mixing amount of heat-expansive capsules relative to specimens of the Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the discussion will be made in detail about a polymeric composition, an extruded polymer article and a climate strip for a motor vehicle, according to the embodiments of the present invention, with reference to the drawings or the like. According to the present invention, a polymeric composition used for an extruded polymer article produced by extrusion and vulcanization comprises, in the mixing, an unconjugated ethylene-ot-alpha-olefin polyene copolymer in an amount of 100 phr ( parts per hundred parts of rubber); carbon black in an amount ranging from more than 50 to 120 phr, carbon black having an arithmetic mean of particle diameter of not less than 60 nm; a softener in an amount in no more than 100 phr; and thermoexpansive capsules in an amount ranging from 1 to 10 prh. The extruded polymer article is obtained by mixing a polymer material such as a rubber material (for example, ethylene-to-olefin-non-conjugated polyene copolymer) and the like and by extruding and vulcanizing the polymer material. More specifically, at least the aforementioned polymer material, carbon black, a softener, and capsules Thermoexpansives are mixed respectively in specified quantities. As the aforementioned carbon black, the carbon black having a relatively large particle diameter is used in a small amount which is less than an amount (for example, not less than 140 phr) treated in the technical field of the Extruded polymer article by extrusion and general vulcanization, on the basis of using 100 phr of the rubber material. The polymer composition of the present invention contains the ethylene-α-olefin-non-conjugated polyene copolymer in a mixing amount of 100 phr. The amount of mixing means an amount of a component that is contained in the polymer composition under mixing. With respect to other components of the non-conjugated ethylene-α-olefin-polyene copolymer, the amount of mixing thereof is an amount contained in the polymer composition, based on 100 phr of the ethylene-α-olefin-polyene copolymer. conjugate. In extrusion and general vulcanization, after a polymer composition is discharged from a mold of an extruder, a discharged body (extruded material) is placed in a free condition (ie, a condition where a pressure is applied strongly to the body discharged, different from that in the molding using a mold) where a crosslinking reaction is made thereby obtaining a proposed extruded polymer article. Therefore, for example, in case the carbon black having an average particle diameter smaller than 60 nm is mixed with the non-conjugated ethylene-to-olefin-polyene copolymer to form a polymeric composition, or in case carbon black having an average particle diameter of not less than 60 nm is mixed in an amount of more than 120 phr to the copolymer (100 phr) to form a polymer composition, an article of extruded polymer produced as a polymer article General extrudate by extrusion and vulcanization of the above polymeric composition becomes one shown in the structural model figure of Fig. 1A in which the surface of the extruded polymer article (indicated by number 10 in Fig. 1) It is relatively flat. Additionally, in the case that carbon black having an average particle diameter of not less than 60 nm is mixed in an amount of not more than 120 phr to the non-conjugated ethylene-to-olefin-polyene copolymer to form a composition polymer which is extruded and vulcanized to obtain an extruded polymer article, a rough surface which has a small surface roughness and is derived from the carbon black particle of carbon is formed on the surface of the article of extruded polymer as shown in the structural model figures of Fig. IB and Fig. 1C (partially elongated view of Fig. IB). This seems to be caused by the fact that the mixing amount of the carbon black having a large particle diameter is relatively small, and therefore a part that contains a large amount of ethylene-to-olefin-polyene copolymer Non-conjugated is formed locally in the aforementioned extruded polymer article, shrie or the like tend to occur in the part. Here, in the case of an extruded polymer article which is obtained by the extrusion and vulcanization of a polymeric composition prepared by mixing the thermally expandable microcapsules described in the column of the Background of the Invention to the ethylene-α-olefin copolymer. previously mentioned non-conjugated polyene, an uneven surface 10b derived from the thermal expansion of the heat-expansive capsules are formed on the surface of the extruded polymer article as shown in the structural model figure of Fig. ID in which the uneven surface is form in a form which is obtained under the breaking and incineration of the wall of the outer wrapper (discussed later in detail) of an extruded polymer article of the heat-expansive capsules 10c. In the case of an extruded polymer article which is obtained by extruding and vulcanizing a polymeric composition prepared by mixing an organic foaming agent or the like in place of the aforementioned heat-expansive capsules, first a coating film is formed on the surface of the extruded polymer article so that the surface of the coating film becomes highly rough. However, it will be noted that the simply formed, highly rough surface can not achieve good sliding characteristics and good adhesion strength as objectives of the present invention. In case the carbon black having an average particle diameter of not less than 60 nm is mixed in an amount of not more than 120 phr to the aforementioned ethylene-α-olefin-polyane-polyene copolymer (100 phr) while thermoexpansive capsules are mixed in the copolymer (100 phr) in this way a polymeric composition is prepared which is to be extruded and vulcanized to form an extruded polymer article, an uneven surface 10b derived from the thermal expansion of the capsules Thermoexpansive is formed on the surface of the extruded polymer article as shown in the structural model Fig. 1E, while a rough surface derived from the carbon black carbon particle is formed from the uneven surface 10B. In the polymeric composition and the extruded polymer article made of the polymeric composition, according to the embodiment of the present invention, not only the ethylene-to-olefin-non-conjugated polyene copolymer, carbon black, softener and thermoexpansive capsules also various additives such as foaming agents, silicone compound, vulcanization agent, vulcanization accelerator, vulcanization acceleration aid, processing aid, inorganic filler and the like can be mixed appropriately according to the application purposes. [Non-conjugated ethylene-to-olefin-polyene copolymer] Examples of α-olefin of a non-conjugated ethylene-to-olefin-polyene copolymer are propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl -l-pentene, 1-octene and the like. Propylene is preferable. This is a routine thing that a plurality of ones can be selected from the aforementioned a-olefin group, in which, for example, propylene and 1-butane are used in combination. Examples of unconjugated polyene are non-conjugated cyclic polyenes such as 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, methyltetrahydroindene and the like; and unconjugated chain polyenes such as 1,4-hexadiene, 7-methyl-l, 6-octadiene, 4-ethylidene-8-methyl-l, 7-nonadiene, 4-ethylidene-l, 7-undecadiene, 4, 8-dimethyl-1,4,8-decatriene and the like. Of these unconjugated polyenes, an individual one may be used or two or more are used in combination, in which a ratio of unconjugated polyene content in the non-conjugated ethylene-to-olefin-polyene copolymer is, for example in the range from 1% by weight to 20% by weight, preferably in a range of 1% by weight to 15% by weight, more preferably in a range of 5% by weight to 11% by weight. It can be used such as the non-conjugated ethylene-to-olefin-polyene copolymer, for example, Keltan 7341A (tradename) produced by DSM'Elastomers. [Carbon black] The aforementioned carbon black is one - used, for example, in the technical field of the extruded polymer article and having an average particle diameter (arithmetic average of particle diameter) of not less than 60 nm , preferably within a range of 79 nm to 90 nm, with respect to a mixing amount of this carbon black, if this is not more than 50 phr, a kneading process becomes difficult. Therefore, the amount of carbon black mixing is within a range of more than 50 phr to no more than 120 phr, of preference within a range of not less than 60 phr to no more than 120 phr. As such carbon black, for example, a batch that has an arithmetic mean of particle diameter of not less than 60 nm is used is selected from the carbon black Asahi · Asahi # 50 (trade name) or carbon black Asahi "Asahi # 55 (trade name) produced by Asahi Coal CO., Ltd. [Thermoexpansive capsules] Example of the aforementioned thermoexpansive capsules are thermoplastic resin particles filled with liquid (thermally expandable thermoplastic resin particles each of which has a wall of the thermoplastic envelope (eg, a spherical shell wall) filled with a liquid (eg, hydrocarbon or chlorinated hydrocarbon having a low boiling point) which generates gas in the heating.The particle of thermoplastic resin filled with liquid has a real specific gravity of not more than 0.1, a particle diameter (mean diameter) that varies from 5 p.m. to 100 p.m., and it is expandable in the heating (e.g., heating to the vulcanization temperature) at a temperature of not less than an expansion initiation temperature (e.g., 100 ° C to 200 ° C) of the liquid, so that a thermally expanded having a diameter, for example, from 30 pm to 300 pm is formed in the extruded polymer article proposed. Examples of the component of the thermoplastic resin constituting the wall of the coating of the aforementioned heat-expansive capsule are preferably nitrile (meth) acrylic polymer, and a polymer which contains a lot of (meth) acrylic nitrile. Examples of monomer (monomer or opposite comonomer) for the above acrylic nitrile in the polymer are monomers such as vinyl halide, vinylidene halide, styrene-based monomer, (meth) acrylate base monomer, vinyl acetate, butadiene, vinyl pyridine, chloroprene and the like. The aforementioned coating wall is preferably formed of a thermoplastic resin which is not crosslinked or can be formed of a thermoplastic resin which is crosslinked with a crosslinking agent such as generally used divinylbenzene, ethylene glycol di (meth) acrylate, and the similar ones.

Additionally, examples of filled liquids within the wall of the coating of the heat-expansive capsules are hydrocarbons such as n-pentane, isopentane, niopentane, butane, isobutene, hexane, petroleum ether, and the like; and chlorinated hydrocarbons such as methyl chloride, dichloroethylene, trichloroethane, trichlorethylene and the like. Like the heat-expansive capsules, Daifoam H750D, H770D, H850D and M430 in the same series produced by Dainicheiseika Color & Chemicals Mfg, Co. , Ltd. are suitably used. Additionally, for example, Matsumoto icrosphere F85D and F100D produced by Matsumoto Yushi-Seiyaku Co., Ltd., and Expancel 091DU-80, 092DU-120 and the like produced by Expancel in Switzerland are used as the heat-expansive capsules. The mixing amount of the heat-expansive capsules is within a range of 1.0 phr to 10 phr preferably within a range of 2 phr to 6 phr. When such heat-expansive capsules are added to the polymer material such as a non-conjugated ethylene-olefin-polyol copolymer, the heat-expansive capsules can be pre-mixed with others using materials (eg, one or more of polymer elastomer, thermoplastic resin) , softener, inorganic filler and the like) and are added to the polymer material in order to prevent the spreading of an improved dispersion of the thermoexpansive capsules: in the case that the thermoexpansive capsules are mixed with other materials of use to be added to the polymer material, the mixing ratio of the foaming agent is adjusted to be within a range of 10% by weight to 99% by weight, preferably within a range of 10% by weight to 50% by weight, based on the Thermoexpansive capsules. Additionally, one of the Thermoexpansive capsules mentioned above can be used, or a plurality of the aforementioned heat expandable capsules can be used in combination. [Softener] Examples of the aforementioned softener are petroleum base softeners such as process oil, paraffin base oil, lubricating oil, liquid paraffin, petroleum asphalt, petroleum jelly and the like; softeners based on coal mineral, coal pitch and the like; and fat based softeners such as castor oil, linseed oil, naba seed oil, coconut oil and the like. Of these softeners, petroleum base softeners are preferable, and paraffin base oils are more preferable. The softeners mentioned above are used in such an amount of mixing as does not degrade the proposed characteristics of the polymer composition and the extruded polymer article, for example, in an amount of not more than 100 phr. [Foaming agent] Examples of the aforesaid foaming agent are 4,4-oxybisbenzenesulfonylhydrazide (OBSH), azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), azobisisobutyronitrile (AIBN), paratoluenesulfonylhydrazide (TSH), hydrazodicarbonamide (HDCA), bariomazocarboxylate and the like. The aforesaid foaming agent is used in such an amount as does not degrade the characteristics of the proposed polymer composition and the extracted polymer article (e.g., in an amount of 0 to 10 phr). Additionally, foaming assistance such as urea base derivatives, salicylic acid, phthalic acid, stearic acid and / or the like can be used in conjunction with the aforesaid foaming agent. [Silicone compound] Examples of the aforementioned silicone compound are the silicone gel base compound, silicone oil base compound, silicone powder base compound, silicone-based polymer base compound, base compound of silicone graft polymer, organic resin containing silicone and the like. The silicone compound is, for example, KE76BS, KF99 and KF96 produced by Shin-Etsu Chemical Co., Ltd .; and the E500, E600, BY27 series (preferably BY27-001, BY27-002, BY27-201, BY27-201C, BY27-202, SP-300 and SP-310) produced by Dow Corning Toray Silicone Co., Ltd. , and the like. Additionally, other silicone compounds available in general are also suitably used as the silicone compound of the present invention.

The aforementioned silicone compound is used in such an amount of mixing as does not degrade the characteristics of the composite polymer composition and the extruded polymer article (for example, in a mixing amount of 0 to 30 phr). Additionally, any one of the aforementioned silicone compounds can be used, or a plurality of the aforementioned silicone compounds can be used in combination. [Vulcanizing agent] Example of the aforementioned vulcanizing agent is sulfur which is used in such amount of mixing as does not degrade the characteristics of the proposed polymer composition and the extruded polymer article, preferably in an amount varying from 0.5 phr. at approximately 2 phr. [Vulcanization Accelerator] Examples of the aforementioned vulcanization accelerator are thiazole base auxiliary, thiuram base auxiliary, sulfenamide base auxiliary, uganidine base auxiliary, thiourea base auxiliary and dithiocarbamic acid base auxiliary. . The vulcanization accelerator is used in such amount of mixing as does not degrade the characteristics of the proposed polymer composition and the extruded polymer article, preferably in a mixing amount ranging from about 2 phr to 8 phr. [Vulcanization acceleration aid] Examples of the vulcanization acceleration aid are zinc oxide (white zinc), magnesium oxide, calcium hydroxide, zinc monoxide and the like, in which the zinc oxide and / or oxide of magnesium are preferable. The vulcanization accelerating aid is used in such mixing amount as does not degrade the characteristics of the polymer composition and the proposed extruded polymer article, preferably in a mixing amount of about 5 phr. [Processing assistant] Examples of the aforementioned processing helper are higher fatty acids such as stearic acid, ricinolic acid, palmitic acid, lauric acid, and the like; esters of higher fatty acids; and salts of the higher fatty acids such as stearic acid and the like. Other compounds treated as processing aids in the technical field of the extruded polymer article can be used as the processing aid of the present invention. The processing assistant is used in such amount of mixing as does not degrade the characteristics. of the polymer composition and extruded polymer article proposed, preferably in an amount of about 5 phr, more preferably in an amount of not more than 3 phr. [Inorganic filler] Examples of the aforementioned inorganic filler are calcium carbonate, clay, silica, magnesium silicate, magnesium hydroxide, aluminum oxide, kaolin, mica, zeolite and the like. Either one of these fillers can be used, or a plurality of these fillers can be used in combination. Additionally, the above inorganic filler (s) is used in such amount of mixing as does not degrade the characteristics of the polymer composition and the proposed extruded polymer article, for example, in a mixing amount ranging from about 0. at 100 phr. [Other additives] Examples of additives other than the various other additives mentioned above are dehydrating agent, antioxidant, aging resistance, heat stabilizer, light stabilizer, ultraviolet ray absorber, neutralizer, lubricant, defoaming agent, antiblocking agent, slip agent, dispersant, flame retardant, antistatic agent, conductive agent, tackifier, crosslinking agent, crosslinking aid, metal deactivator, molecular weight modifier, flame retardant agent fungi and mildew, fluorescence whitening agent, sliding capacity improver, coloring agent (titanium oxide and the like), metal powder (ferrite and the like), fiberglass, inorganic fiber, (metal fiber and the like), carbon fiber, organic fiber (aramid fiber and the like), composite fiber, glass, flake glass, graphite, carbon nanotubes, fullerene, various sulfate, resin, polyolefin wax filler (polymer beads and the like), cellulose powder, rubber powder, regenerated rubber and the like. Any of one of the above additives can be used, or a plurality of the above additives can be used in combination. The above additives are suitably used according to the polymer composition and the polymer article extruded by the opposite. [Method of production] ? In order to obtain the polymer composition proposed by kneading the aforementioned ethylene-α-olefin-polyane copolymer, carbon black, softener, thermally expandable capsule, various additives and the like, for example, several closed type kneaders such as as a tangential mixer, a splice type mixer, a mixer or the like; a biaxial extruder of kneading type; or an open roll; and the similar are used properly. Additionally in order to obtaining the proposed extruded polymer article by extruding and vulcanizing the aforementioned polymer composition, for example, a continuous hot air vulcanization vessel (HAV), an ultra high frequency vulcanization apparatus (ÜHF), a continuous vulcanization apparatus of Horizontal fluid bed or similar can be used properly. Preferably, the continuous hot air vulcanization vessel and the ultra high frequency vulcanization apparatus are used in combination. EXAMPLES The present invention will be more readily understood with reference to the following Examples in comparison with the Comparative Examples; however, these Examples are proposed to illustrate the invention and will not be considered to limit the scope of the invention. A variety of polymeric compositions (rubber compounds SI at S13 ("Examples") and rubber compounds Pl at Pll ("Comparative Example") were produced according to the embodiments of the present invention, in which a practicability of their compositions of polymer material, physical properties of the extruded polymer article, and the like were inspected using specimens or samples GS1 to GS13 ("Examples") and specimens GP1 to GP11 ("Comparative Example").

In order to produce each polymeric composition, first, ethylene-propylene-5-ethylidene-2-norbornene (Keltan 7341A (trade name) produced by DS 'Elastorneros) was used in an amount of 100 phr as the polymer material and chewed in a closed type mixer to thereby obtain a chewed polymer material. Subsequently, for the chewed polymer material, one or more kinds of carbon black having an arithmetic average of particle diameters of 80 nm, 60 nm and 45 nm (respectively referred to hereinbelow as "80nm carbon black", "carbon black of 60 nm and" carbon black of 45 nm ") in an amount within a range of 50 phr to 140 phr, a softener (process oil P-300 produced by Japan Energy Corporation (JOMO)) in an amount ranging from 80 phr to 20 phr and a silicone compound (BY27-002 produced by Dow Corning Toray Silicone Co. Ltd.) in an amount ranging from 0 to 40 phr were added, in which the kneading was done for a specific time to obtain in this manner a kneaded polymer material In the Examples and Comparative Examples, the carbon black 80 nm, carbon black 60 nm and the carbon black 45 nm previously mentioned were used in selecting the blacks of coal have the average arithmetic of respective particle diameters of 80 nm, 60 nm and 45 nm of the respective batches of carbon black material Asahi • Asahi # 50, carbon black Asahi «Asahi # 55, and black carbon Asahi« Asahi # 60 produced by Asahi Carbon Co. Ltd. Additionally, in addition to the various materials mentioned above , stearic acid and / or polyethylene glycol in a mixing amount of 1 phr as processing aid, calcium carbonate in an amount of 30 phr as an inorganic filler and inactive blank in a mixing amount of 3 phr as an acceleration aid vulcanization were added to the aforementioned kneaded polymer material, in which the kneading was done for a specific time to thereby obtain an additional kneaded polymer material. The aforementioned additional aforementioned kneaded polymer material formed by the closed type mixer was extracted. Then, for the material of the extracted kneaded polymer, the heat-expansive capsules (Daifoam H750K produced by Dinichiseika Color &Chemicals Mfg. Co., Ltd) in an amount ranging from 1 to 20 phr, the base foaming agent of 4, 4 Oxidobenzenesulfonylhydrazide in a mixing amount ranging from 0 to 35 phr were added in the kneaded polymer material which was rolled up on a roll while kneading by an open mill, and then mixing or blending was done by a specified period of time.

As a result, the rubber compounds SI were obtained at S13 and Pl at Pll having a variety of compositions shown in Table 1 described below, in which the rubber compounds were tape-shaped or sheet-shaped and were the compounds of unvulcanized rubber. Additionally, in the Examples and Comparative Examples, in addition to the various materials mentioned above, the sulfur in a mixing amount of 1 phr as the vulcanization agent, the vulcanization accelerators of thiuram base, of tlazole base, of base of Sulfenamide and dithiocarbamic acid base were added in a total mixing amount of 5 phr, and then the mixing was done for a specified time. Then, each of the aforementioned rubber compounds were extruded by using an extruder for the extruded polymer article, in which the extruder had a nozzle shape such as to obtain an extruded polymer article shown in Fig. 2 as is described later to make an extrusion in adjusting a screw rotational speed thereof thereby forming an extruded formed body. Hereinafter, the extruded formed body was vulcanized in the continuous air vulcanization vessel, in which the vulcanization was done at a temperature of 200 ° C for a time of 10 minutes, thereby producing a specimen GS1 to GS13 , GP1 to GP11 (indicated by the reference number 20 in Fig. 2) of an extruded polymer article (having a height of 20 mm) as shown in Fig. 2. The specimen had a base section of shape of generally flat plate 21 (which has a thickness of 2 mm and a width of 25 mm) provided with a section of tube (or a tube having a thickness of 2 mm) which was circular in the section of the cross-section. The aforementioned GP4 or GP5 specimen surface was coated with a surface treatment agent which had been prepared by mixing urethane polyol in an amount of 85 phr, polyisocyanate in an amount of 15 phr, diorganosiloxane in an amount of 40 phr. , a curable silicone oil in an amount of 40 phr, a catalyst in an amount of 4 phr, a deslizante agent in an amount of 15 phr and a solvent in an amount of 1500 phr, thus forming a treatment coating Of surface. TABLE 1 The practicability (kneading workability and extrusion forming ability) of each rubber compound known as discussed above, and a surface condition (surface roughness), an adhesion strength (adhesion strength), sliding characteristics (coefficient of friction) and a water repellency (water contact angle) of each specimen were measured under methods of test discussed below, in which the measurement results are shown in table 2 described below. The characters "A", "B" and "C" in the Total Evaluation column of Table 2 represent respectively in case they are capable to be applied to a strip for climate or the similar for a motor vehicle, in case that they are capable of being applied sufficiently to the strip for weather or the like, and in case it is difficult to apply it to the strip for weather or the like.

[Practicability of kneading] Each of the aforementioned rubber compounds was kneaded by an open roller apparatus including rollers each having a diameter of 35 cm (14 inches), the distance between the rollers being adjusted to 5 mm . In the kneading workability column of Fig. 2 described below, an "A" character indicates a case that the rubber compound easily penetrated between the rolls and would be on the rolls in such a way as to be in tight contact with the rollers; a "C" character indicates a case that the rubber compound might not come into contact with each roller to hang or cut it halfway to the rubber compound; and a "B" character indicates a case that the rubber compound was difficult to penetrate between the rolls if it was not rolled over the rolls with a lapse of time. [Extrusion forming capacity) Each of the aforementioned rubber compounds (or rubber compounds) whose temperature was set at 60 ± 5 ° C corresponding to the temperature in the extrusion was extruded for one minute using an extruder whose speed rotational was adjusted to 15 rpm, provided with an extrusion device having a diameter of 75 mm, thereby obtaining an extruded polymer article (indicated by reference number 20) in the manner shown in Fig. 2. This extrusion was repeated 100 times for each rubber compound, in which the mass (g) of the extruded formed body (unvulcanized formed body) discharged from the extruder in each extrusion was weighed as a discharge amount. The value, the minimum value and an average value of the discharge quantities were respectively referred to as the maximum discharge amount, the minimum discharge amount and an average discharge amount. Then, the dispersion of the discharge quantities was calculated for each rubber compound, according to an equation (1) shown below. The dispersion of the discharge quantities (%) = (([the maximum discharge quantity] - [the minimum discharge quantity]) / the average discharge quantity) x 100 (1) [Surface roughness] The aforementioned specimen (Extruded polymer article 20 was punched out to form a rectangular and flat plate-shaped test piece (having a dimension of 5 mm x 100 rare x 2 mm) After the surface contamination the test piece was cleaned with alcohol, a surface roughness (or an average roughness of ten points) of the test piece was measured according to a so-called 10-point method (or a method according to JIS B 0601) when using a surface roughness meter (Surfcorder SE30D produced by Kosaka Laboratory Ltd.) - As the contact needles of the aforementioned roughness meter, a contact needle having a tip end radius of 2 μm (for a rough surface derived from the particles carbon black carbon) and a contact needle that has a tip end radius of 250 μp? (for an uneven surface derived from the thermal expansion of the thermally expandable capsule) were used to respectively measure the surface roughness of the rough surface derived from carbon black carbon particles and the uneven surface derived from of the thermal expansion of the thermoexpansive capsules. [Adhesion resistance] As shown in Figs. 3A (plan view), 3B (side view) and 3C (operational perspective view), the aforementioned specimen 20 was drilled to form two rectangular flat plate shape test pieces 30 (having a dimension of 5 mm x 50 rare x 2 mm). After contamination of the surface of each test piece was cleaned with alcohol, the test pieces were fixed to a stainless steel plate shaped rectangular and flat plate 31 spacing of 60 mm from each other, with a coated lid of double adhesive, in which the fixation of the test piece was completed on a surface (which has a mm x 50 mm dimension of the test piece). Additionally, a coated plate 32 (a steel plate coated with a white melamine resin coating for a motor vehicle was placed on the test pieces 30 in such a manner as to cover both of the aforesaid test pieces 30, in which the coated plate was of rectangular and flat plate shape (having a shape similar to that of the 31 stainless steel plate and had a thickness of 1.0 mm to 1.5 mm), then the two weight members 33 were placed on the coated plate 32 and stood in a thermostatic oven (ie in an atmosphere of a temperature of 80 ° C), applying a load of 49N (24.5N x 2) on portions of the coated plate in portions corresponding to the positions of the test pieces 30. Then, the aforementioned weight members 33 were removed (immediately before the measurement), and the aforementioned coated plate 32 was removed at a ratio of 50 mm / minute in a horizontal direction (i.e., longitudinal direction) of each test piece 30 or in a direction indicated by an arrow, in which the maximum load (unit: N / 5 cm2) generated when the coated plate 32 and the test pieces 30 were completely detached from one another, measured as a force of addition. The previous unit N / 5 cm2 used here was a specific unit for the inventors for the purpose of representing numerically a detachment load relative to the total contact areas of the two test pieces 30. [Coefficient of friction] As shown in Fig. 4, the specimen above mentioned (article of extruded polymer 20 was drilled to form a rectangular and flat plate-shaped test piece 40 (having a dimension of 5 mx 100 mm x 2 mm) After contamination on the surface of the test piece 40 was cleaned with alcohol, the test piece 40 was placed on a support table (test table 41.) Then, a weight member 42 formed with a spherical glass surface having a radius of 50 mm in section was mounted on the test piece 40, in which the side of the spherical surface having the radius of 50 mm in contact section with the test piece 40. Then, the weight member 42 moved slidably in a horizontal direction (ie, in a longitudinal direction of the test piece 40, or in a direction indicated by an arrow) at a rate of 100 mm / minute such that the sliding movement of the weight member was made while the weight member was brought into contact with the test piece 40, thereby measuring a coefficient of static friction (μe) and a coefficient of dynamic friction (μ?) [Water contact angle] As shown in Fig. 5, the aforementioned specimen (extruded polymer article 20) was perforated to form a rectangular and flat plate-shaped test piece 50 (having a dimension of 5). rom x 100 mm x 2 mm). After contamination on the surface of the test piece 50 was cleaned with alcohol, the test piece 40 was placed on a horizontal support table 52. The water in an amount of 1.5 ml was dripped onto the surface of the workpiece. 50 test, and the dripped water was allowed to remain for 10 seconds. Then, a contact angle 0 between the dripped water drop and the test piece 50 was measured by a contact angle meter (Face · Contact-Angle Meter type CA-D produced by Kyowa Interface Co. , Ltd.). Table 2 [Comparative example that does not contain capsules thermoexpansives] First, as shown in Table 2, the rubber compounds Pl to P5 in which the 80 nm carbon, the softener and the foaming agent were mixed while mixing the non-heat expanding capsules were good in workability. However, of the specimens that use the previous respective rubber compounds, the specimens using respectively the rubber compounds Pl and P2 were observed to be low in adhesion characteristics, slip characteristics and water repellency although the addition amount of the 80 nm carbon and the softener was adjusted. Additionally, the GP3 specimen using the rubber compound P3 which was formed by mixing the silicone compound to the same composition as the rubber compound P2 could obtain sufficient water repellency.; however, it was noted that it is down in addition resistance and sliding characteristics. In addition, GP4 specimens (which have a surface treatment layer thickness of 2 μm) and GP5 (which has a surface treatment layer thickness of 5 μm) that uses the same composition as the rubber compound Pl could obtain sufficient water repellency under the effect of the surface treatment layer; however, they are observed to be low in adhesion strength and slip characteristics if the thickness of the aforementioned surface treatment layer was not sufficient as the GP5 specimen. [Comparative example containing heat-expansive capsules] The rubber compound P6 which was similar in composition to the rubber compound P3, contained the heat-expansive capsules and was in general in the amount of coal blending 80 nm was good in workability. The GP6 specimen using the P6 rubber compound could have a sufficient water repellency; however, it was observed to decrease in adhesion strength and slip characteristics. Additionally, the aforementioned rubber compound P7 which was similar in composition to the aforementioned rubber compound P6 and very low in the amount of coal blending 80 nm was the worst in practicability; however, the GP7 specimen using the rubber compound P7 was found to be good in adhesion strength and slip characteristics. [Comparative example with large amount of mixing of the heat-expansive capsules and softener] The rubber compound P8 which was similar in composition to the relatively small P6 rubber compound in amount of coal mixing 80 nm and relatively much in amount of softener mixing It was good in practicability. The GP8 specimen using the rubber compound P8 could obtain a good water repellency; however, it was observed to be low in adhesion strength and slip characteristics. Additionally, the rubber compound P9 which was similar in composition to the rubber compound P6, relatively small in amount of coal blending 80 nm and relatively much in the amount of mixing or the heat-expansive capsules. The GP9 specimen using the P9 rubber compound could have good adhesion strength and sliding characteristics; however, it was observed to be low in water repellency. [Comparative example adjusted in particle diameter of carbon black] The PIO and Pll rubber compounds which were similar in composition to the rubber compound P3 and respectively contained the mixed carbon 45 nm and the mixed carbon 60 nm were good in practicability . The specimens GP10 and GP 11 are used respectively the rubber compounds PIO and Pll could obtain a good repellency; however, it was observed to be low in adhesion strength and slip characteristics. [Example containing heat-expansive capsules and using carbon black having large particle diameter] The rubber compounds SI to S9 contained the carbon 80 nm or the carbon 60 nm in an amount ranging from 60 phr to 120 phr, the softener in an amount varying from 80 phr to 100 phr, the thermoexpansion capsules in an amount that it varies from 2 phr to 10 phr, the silicone compound from 2 phr to 20 phr, and the foaming agent. The respective rubber compounds SI to S9 were good in workability. Specimens GSl to GS9 using respectively the rubber compounds SI to S9 were observed to be good in water repellency, adhesion strength and sliding characteristics. Additionally, rubber compounds S10 to S12 which were respectively similar in composition to rubber compounds S3, S4 or S5 and did not contain the mixed silicone compound and the mixed organic foaming agent were good in workability. The specimens GS10 to GS12 which respectively use the rubber compounds S10 to S12 were observed to be good in adhesion strength and slip characteristics. In addition, specimens GS10 and GS11 that did not contain the silicone compound were observed to be inferior in water repellency as compared to the specimen GS 12. In addition, the rubber compound S13 which was similar in composition to the rubber compound S2 and contained the mixed silicone compound in an amount of 40 phr was low in practicability. However, the GS13 specimen using rubber compound S13 was observed to be good in water repellency, adhesion strength and sliding characteristics. Here, the results measured in the roughness of the surface of the specimens GP6, GP7 and GS1 to the GS3 using respectively the rubber compounds each of which is 80 phr and 2 phr respectively in the mixing quantities of the softener and the capsules Thermoexpansives are shown in Fig. 6 which is a graph of surface roughness characteristics in terms of the amount of coal blending 80 nm. From these graphs of characteristics shown in Fig. 6, it was revealed that the uneven surface derived from the thermal expansion of the heat-expansive capsules was formed on the surface of each of the aforementioned specimens GS1 to GS3, GP6 and GP7, and the rough surface formed on the uneven surface derived from the thermal expansion of the heat-expansive capsules; and there is a correlation between the amount of coal blending 80 nm and the rough surface roughness derived from the carbon black carbon particles. Additionally, the results measured in the surface roughness of specimens GP3, GP9, GS2, GS5 and GS6 using rubber compounds respectively each of which is 80 phr and 100 phr respectively in the mixing quantities of the softener and the 80 nm carbon are shown in Fig. 7 which is a plot of the surface roughness characteristics in terms of the quantity of mixing of the thermoexpansive capsules. From these characteristics the graph is shown in Fig. 7, a correlation has been revealed between the amount of mixing of the thermoexpansive capsules and the uneven surface derived from the thermal expansion of the thermoexpansive capsules. Similar to the aforementioned rubber compounds Si at S13, sufficient practicability could be obtained if a rubber compound contained at least the mixed elastomeric polymer, carbon black softener and thermally expandable capsule, in which the carbon black had a arithmetic average of particle diameter of not less than 60 nm (for example, carbon 60 nm and carbon 80 nm and a mixing amount ranging from more than 50 phr to 100 phr, the softener had a mixed amount of more than 100 phr, and the thermoexpansive capsules had a mixing amount ranging from 1 phr to 10 phr It was confirmed that a specimen using the rubber compound was good in water repellency, adhesion resistance and sliding characteristics. is discussed above, according to the present invention, the roughened surface derived from the carbon black carbon particles is obtained at the uneven surface derived from the thermal expansion of the heat-expansive capsules, and the contact area between the surface of the extruded polymer article and the object to be used becomes small. As a result for example, the coating of a surface treatment agent and the like becomes unnecessary, thus obtaining sufficient slip characteristics, adhesion strength, water repellency and the like without degrading productivity. Accordingly, by applying the extruded polymer article to a climate strip and the like for a motor vehicle, the weather strip can sufficiently exhibit the functions that are required by it. Although the present invention has been discussed in the described embodiments, it will be understood by those skilled in the art that it is possible to make a variety of modifications and corrections to the embodiments without departing from the spirit and scope of the invention. It is a common thing that such modifications and corrections are within the scope of the claims of the present invention. The full contents of Japanese Patent Application No. 2005-78313, filed March 18, 2005, are incorporated herein by reference.

Claims (6)

1. CLAIMS 1. A polymeric composition used for an article of extruded polymer produced by extrusion and vulcanization, characterized in that it comprises: a non-conjugated ethylene-α-olefin-polyene copolymer in an amount of 100 phr; carbon black in an amount ranging from more than 50 to 120 phr, the carbon black having an arithmetic mean of particle diameter no smaller than 60 nm; a softener in an amount of no more than 100 phr; and thermoexpansive capsules in an amount ranging from 1 to 10 phr.
2. 2. A polymer composition according to claim 1, characterized in that it also comprises a silicone compound in an amount of not more than 30 phr.
3. 3. An extruded polymer article produced by extrusion and vulcanization of a polymer composition including a non-conjugated ethylene-α-olefin-polyene copolymer in an amount of 100 phr; carbon black in an amount ranging from more than 50 to 120 phr, the carbon black having an arithmetic mean of particle diameter no smaller than 60 nm; a softener in an amount of no more than 100 phr; and thermoexpansive capsules in an amount ranging from 1 to 10 phr, characterized in that the extruded polymer article comprising a surface section having an uneven surface derived from the thermal expansion of the heat-expansive capsules, and a rough surface derived from the carbon particle of the carbon black and formed on the uneven surface derived from the thermal expansion of the thermoexpansive capsules.
4. 4. An extruded polymer article according to claim 3, characterized in that the polymer composition further includes a silicone compound in an amount of not more than 30 phr.
5. 5. A climate strip for a motor vehicle, characterized in that it is produced by extrusion and vulcanization of a polymeric composition that includes a copolymer of etiieno-olefin-polyane non-conjugated in an amount of 100 phr; carbon black in an amount ranging from more than 50 to 120 phr, the carbon black having an arithmetic mean of particle diameter no smaller than 60 nm; a softener in an amount of no more than 100 phr; and heat-expansive capsules in an amount ranging from 1 to 10 phr, the climate strip characterized in that it comprises a surface section having an uneven surface derived from the thermal expansion of the capsules thermoexpansive that are formed, and a rough surface derived from the carbon black carbon particle and formed on the uneven surface derived from the thermal expansion of the thermoexpansive capsules.
6. 6. A strip for climate according to claim 5, characterized in that the polymer composition also includes a silicone compound in an amount of not more than 30 phr.