JP5204512B2 - Thermoplastic elastomer composition - Google Patents

Description

  The present invention relates to a thermoplastic elastomer and its use, and more particularly to a thermoplastic elastomer suitable for welding and molding corner-shaped connection portions and shaped end portions such as automobile weather strips and door trims.

  Conventionally, the production of a weatherstrip having a connecting portion is generally performed by cutting an extrusion vulcanized molded article composed of a rubber compound of ethylene / propylene / non-conjugated diene terpolymer (EPDM), and one or both of them. The mold is then set in a mold, and a rubber molding material of the same type as this EPDM rubber compound is injected into a cavity to be formed, followed by vulcanization molding.

  On the other hand, instead of vulcanized rubber using ethylene / propylene / non-conjugated diene terpolymer (EPDM) as a molding material, the vulcanization process from the viewpoint of productivity, environmental friendliness and weight reduction Thermoplastic elastomers (compositions) that do not need to be used are beginning to be used.

  However, in general, vulcanized rubber and thermoplastic elastomer cannot be vulcanized and bonded, so they have been integrated using an adhesive, but this is not sufficient in terms of productivity or environmental friendliness. . Moreover, sufficient adhesiveness was not obtained also in the adhesion | attachment of thermoplastic elastomers.

  As a technique related to the composition of the thermoplastic elastomer, addition of a polar group-containing resin (see Patent Documents 1 to 3) can be mentioned. In the case of addition of a polar group-containing resin, release from a mold of a molded product during molding. The molding cycle becomes longer due to the deterioration of properties. In addition, α-olefin-based amorphous polymers are used or thermoplastic elastomers have been proposed (see Patent Documents 4 to 5), but the adhesiveness is insufficient, and the rubber elasticity deteriorates. End up.

  Furthermore, as a technique of the vulcanized rubber, there is a technique in which microcrystalline polypropylene is added in addition to the composition of the conventional vulcanized rubber (see Patent Document 6). However, when microcrystalline polypropylene such as atactic polypropylene is added, not only the rubber elasticity of the conventional vulcanized rubber is deteriorated, but also the stickiness of the molded product and the increase in the hardness of the molded product after time may occur. .

  In addition to the technology related to the composition of the thermoplastic elastomer and vulcanized rubber as described above, after cutting the vulcanized rubber, an attempt is made to obtain an anchor effect by adding irregularities on the cut surface (see Patent Document 7), There is a technique such as one in which polyolefin resin powder is applied to the cut surface of vulcanized rubber (see Patent Document 8), but all have a drawback that the improvement in adhesiveness is not observed although productivity is lowered.

Therefore, a thermoplastic elastomer capable of forming a molded product that produces sufficient adhesive strength with respect to vulcanized rubber or thermoplastic elastomer without using an adhesive layer and the elastomer were welded to vulcanized rubber or thermoplastic elastomer. A thermoplastic elastomer excellent in moldability and economy that can form a molded article, and a lightweight molded article having sufficient hardness and rubber elasticity as a thermoplastic elastomer, and the elastomer were fused to vulcanized rubber or thermoplastic elastomer. Appearance of a molded body is desired.
JP-A-2-115249 JP-A-8-244068 JP-A-10-324200 Japanese Patent No. 3693017 JP 2006-282827 A Japanese Patent Laid-Open No. 10-7849 JP-A-9-118133 JP-A-6-47816

  The present invention is intended to solve the problems associated with the prior art as described above, and has sufficient adhesive strength and rubber elasticity against vulcanized rubber or thermoplastic elastomer without using an adhesive layer. It is an object to provide a thermoplastic elastomer capable of forming a molded body.

The present invention includes the following matters.
[1] 10 to 60 parts by weight of non-crosslinkable crystalline polyolefin resin (A) and 1 to 20 parts by weight of propylene / 1-butene / ethylene random copolymer (B) are partially or completely crosslinked. A thermoplastic elastomer composition (E) containing 89 to 20 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene (Provided that the total of (A), (B) and (C) is 100 parts by weight), and the propylene / 1-butene / ethylene random copolymer (B) is
(1) 90 to 50 mol% of units derived from propylene, 5 to 25 mol% of units derived from 1-butene, and 5 to 25 mol% of units derived from ethylene, (2) gel permeation chromatography The molecular weight distribution (Mw / Mn; standard polystyrene conversion) determined by chromatography (GPC) is in the range of 1.0 to 3.5. (3) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0. The thermoplastic elastomer composition (E), which is 0.7 to 10 dl / g, and (4) is a triad tacticity (mm fraction) of 85% or more calculated by ¹³ C-NMR.
[2] In addition to the above (A), (B) and (C), it further contains a softening agent (D), and the softening agent (D) contains these components (A), (B) and (C). The thermoplastic elastomer composition (E) according to [1], which is contained in an amount of 0 to 200 parts by weight per 100 parts by weight in total.
[3] The triad tacticity (mm fraction) calculated by ¹³ C-NMR of the propylene / 1-butene / ethylene random copolymer (B) is 88% or more and 98% or less. 1] or the thermoplastic elastomer composition (E) according to [2].
[4] The intrinsic viscosity [η] measured in decalin at 135 ° C. of the propylene / 1-butene / ethylene random copolymer (B) is 1.0 to 5.0 dl / g. The thermoplastic elastomer composition (E) according to any one of [1] to [3].
[5] The thermoplastic elastomer composition (E) according to any one of [1] to [4], which is used for welding to a vulcanized rubber molded body or a thermoplastic elastomer molded body.

  The thermoplastic elastomer composition (E) of the present invention can be suitably used for welding a vulcanized rubber or a thermoplastic elastomer to a molded body, and is melt-bonded to the vulcanized rubber molded body or the thermoplastic elastomer molded body. The adhesive strength during the peel test is high and the elongation is excellent.

The molded article of the present invention is suitably used for automobile interior and exterior materials such as weather strip materials. Specifically, in a weather strip material in which a linear part and a joining corner member are joined, the linear part is formed of a molded body of vulcanized rubber or thermoplastic elastomer, and the corner member is the thermoplastic of the present invention. It is suitably used as a weather strip material comprising a molded body formed from the elastomer composition (E).

A molded body obtained by welding the thermoplastic elastomer according to the present invention to a molded body made of vulcanized rubber or thermoplastic elastomer can be obtained, for example, by insert molding.
The thermoplastic elastomer composition (E) of the present invention has sufficient adhesive strength to vulcanized rubber or thermoplastic elastomer (base material) without using an adhesive layer, and is excellent in elongation at the time of peeling. . Further, it is possible to form a molded article having sufficient hardness and rubber elasticity as a thermoplastic elastomer, lightweight and excellent in moldability and economy.

  Hereinafter, the thermoplastic elastomer composition (E) according to the present invention and the use of the thermoplastic elastomer composition (E) for a vulcanized rubber or a molded article of a thermoplastic elastomer will be specifically described.

[Non-crosslinkable crystalline polyolefin resin (A)]
The non-crosslinkable crystalline polyolefin resin (A) used in the present invention is a crystalline high molecular weight obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method. It is a solid product and has a crystallinity of 20% or more as measured by DSC or X-ray. Examples of such crystalline polyolefin resin (A) include isotactic and syndiotactic monoolefin polymer resins. These crystalline polyolefin resins (A) may be used alone or in combination of two or more. Further, examples of the crystalline polyolefin resin (A) include various propylene polymers, and propylene homopolymers are particularly preferable.

A typical resin of the crystalline polyolefin resin (A) can be obtained commercially.
Specific examples of suitable raw material olefins for the crystalline polyolefin resin (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl- Examples thereof include α-olefins having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms such as 1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. These α-olefins are used alone or in admixture of two or more.

The polymerization mode may be random type or block type, and any polymerization mode may be used as long as a crystalline resin is obtained.
The crystalline polyolefin resin (A) is preferably a propylene polymer, and specific examples include a propylene homopolymer, a propylene / ethylene block copolymer, and a propylene / ethylene random copolymer. Of these, propylene homopolymer is particularly preferred.

The crystalline polyolefin resin (A) used in the present invention has a role of improving the fluidity and heat resistance of the thermoplastic elastomer composition (E).
The crystalline polyolefin resin (A) has a melt flow rate (MFR: ASTM D 1238-65T, 230 ° C., 2.16 kg load) usually from 0.01 to 100 g / 10 minutes, preferably from 0.05 to 50 g / It is preferably in the range of 10 minutes, more preferably in the range of 0.5 to 30 g / 10 min.

The non-crosslinkable crystalline polyolefin resin (A) used in the present invention is a non-crosslinkable crystalline polyolefin (A), a propylene / 1-butene / ethylene random copolymer (B), partially or entirely crosslinked. 10 to 60 parts by weight relative to a total of 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) made of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene The amount is preferably 12.5 to 50 parts by weight, more preferably 15 to 40 parts by weight.

[Propylene / 1-butene / ethylene random copolymer (B)]
The propylene / 1-butene / ethylene random copolymer (B) used in the present invention preferably has a crystallinity of 20% or less, more preferably a crystallinity measured by DSC or X-ray. 10% or less. The propylene / 1-butene / ethylene random copolymer (B) used in the present invention contains 90 to 50 mol%, preferably 85 to 55 mol%, more preferably 80 to 60 mol% of units derived from propylene. The amount of units derived from 1-butene is 5 to 25 mol%, preferably 7.5 to 22.5 mol%, more preferably 10 to 20 mol%. It is contained in an amount of mol%, preferably 7.5 to 22.5 mol%, more preferably 10 to 20 mol%.

The molecular weight distribution (Mw / Mn) of the propylene / 1-butene / ethylene copolymer (B) is 1.0 to 3.5, preferably 1.5 to 3.0, and more preferably 1.7 to 2.8. Range.
The molecular weight distribution (Mw / Mn) is measured by gel permeation chromatography (GPC) at a column temperature of 140 ° C. In addition, Mw represents a weight average molecular weight, Mn represents a number average molecular weight, and all are calculated in standard polystyrene conversion.

  The intrinsic viscosity [η] of propylene / 1-butene / ethylene copolymer (B) measured in decalin at 135 ° C. is 0.7 to 10 dl / g, preferably 1.0 to 5.0 dl / g. More preferably, it is 1.2 to 4.5 dl / g.

The stereoregularity of the propylene / 1-butene / ethylene copolymer (B) can be evaluated by triad tacticity (mm fraction), and is 85% or more, preferably 88 to 98%, more preferably 90. ~ 95%. Here, the “mm fraction” is defined as a ratio in which the branching directions of the methyl groups are the same when the three head-to-tail bonded propylene unit chains existing in the polymer chain are represented by a surface zigzag structure, It is calculated | required from a ¹³ C-NMR spectrum as follows. The mm fraction for the propylene / 1-butene / ethylene copolymer (B) used in the present invention is described in International Publication No. 2004/087775, page 21, line 7 to page 26, line 6. It is required by the method.

  The production method of the propylene / 1-butene / ethylene copolymer (B) in the present invention is not particularly limited, but is a known catalyst capable of stereoregular polymerization of olefins in an isotactic or syndiotactic structure. For example, it can be produced in the presence of a catalyst mainly composed of a solid titanium component and an organometallic compound, or a metallocene catalyst using a metallocene compound as one component of the catalyst. Among these, it is preferable to produce by copolymerizing propylene, 1-butene and ethylene in the presence of a metallocene catalyst. As the metallocene catalyst, it is preferable to use, for example, the catalysts described in Examples e1 to e5 of International Publication No. 2004/087775 pamphlet.

  The propylene / 1-butene / ethylene random copolymer (B) used in the present invention is a non-crosslinkable crystalline polyolefin (A), propylene / 1-butene random copolymer (B), ethylene / carbon number 3 1 to 20 parts by weight, preferably 3 to 18 parts by weight, based on 100 parts by weight of the total ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) composed of 20 α-olefin and nonconjugated polyene. More preferably, it is used in a proportion of 5 to 15 parts by weight.

  The propylene / 1-butene / ethylene random copolymer (B) used in the present invention is not added at the time of dynamic cross-linking, but is added to the thermoplastic elastomer by dry blending before molding, or is converted into a thermoplastic elastomer by an extruder. You may melt-mix.

  The thermoplastic elastomer composition (E) of the present invention is obtained by adding the propylene / 1-butene / ethylene random copolymer (B) to form the thermoplastic elastomer composition (E) and vulcanized rubber during welding. Improves adhesion to the body, adhesion strength in peel tests after welding, and elongation to peel.

[Ethylene / α-olefin / non-conjugated polyene copolymer rubber (C)]
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention is a rubber composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11-methyldodecene-1,12- And ethyl tetradecene-1. Of these, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are preferable, and propylene is particularly preferable.

These α-olefins are used alone or in combination of two or more.
Further, as the non-conjugated polyene, specifically,
1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7- Chain unconjugated dienes such as methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene and 4-ethylidene-1,7-undecadiene;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic nonconjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene and norbornadiene;
Such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and 4-ethylidene-8-methyl-1,7-nonadiene A triene etc. are mentioned, You may use individually or in combination of 2 or more types. Of these, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferable.

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention is derived from (1) (a) a unit derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms. The units to be removed are contained in a molar ratio of 40/60 to 95/5, preferably 60/40 to 80/20, more preferably 65/35 to 75/25 [(a) / (b)]. .

  The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention is 1 to 50, preferably 5 to 40, and more preferably 10 to 30. The content of non-conjugated diene in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) is 2 to 20% by weight. The iodine value is one of indexes indicating the content of non-conjugated polyene in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C).

  The intrinsic viscosity of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention, measured in decalin at 135 ° C., is 1.0 to 10.0 dl / g, preferably 1.5 to 8. 0.0 dl / g.

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention may be a so-called oil-extended rubber in which a softening agent, preferably a mineral oil-based softening agent, is blended during its production. Good. Examples of the mineral oil-based softener include conventionally known mineral oil-based softeners such as paraffin-based process oil.

The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) is usually 10 to 250, preferably 30 to 150.
The ethylene / α-olefin / non-conjugated polyene copolymer rubber can be produced by a conventionally known method.

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) may be blended with an ethylene / α-olefin copolymer rubber (C) as necessary. Examples of the α-olefin constituting the ethylene / α-olefin copolymer rubber include those similar to the α-olefin constituting the ethylene / α-olefin / non-conjugated polyene copolymer rubber. The ethylene / α-olefin copolymer rubber contains 50 mol% or more of units derived from ethylene, preferably 50 to 90 mol%, more preferably 60 to 85 mol%, and an α of 3 to 20 carbon atoms. -The unit derived from an olefin is 50 mol% or less, preferably 50 to 10 mol%, more preferably 40 to 15 mol%.

  The ethylene / α-olefin / non-conjugated polyene copolymer (C) used in the present invention is a non-crosslinkable crystalline polyolefin (A), a propylene / 1-butene / ethylene random copolymer (B), ethylene / 89 to 20 parts by weight, preferably 84.90 parts by weight, based on 100 parts by weight of the total of the ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) comprising an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene. 5 to 25 parts by weight, more preferably 80 to 30 parts by weight is used.

[Thermoplastic elastomer composition (E)]
The thermoplastic elastomer composition (E) of the present invention dynamically heat-treats a blend comprising the above components (A), (B) and (C) in the presence or absence of a crosslinking agent. Can be prepared accordingly. Here, “dynamically heat-treating” means kneading in a molten state and crosslinking.

  Examples of the crosslinking agent used in the present invention include organic peroxides, sulfur, sulfur compounds, phenolic vulcanizing agents such as phenol resins, etc. Among them, organic peroxides are preferably used.

Specific examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, and 2,5-dimethyl-2. , 5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n -Butyl-4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperbenzoate, t-butylperoxyisopropyl Carbonate, diacetyl peroxide, lauroyl peroxide, t- Such as chill cumyl peroxide. Among them, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne is preferable in terms of odor and scorch stability. -3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (t- Butylperoxy) valerate is preferred, and 1,3-bis (t-butylperoxyisopropyl) benzene is particularly preferred.

  This organic peroxide is composed of a non-crosslinkable crystalline polyolefin resin (A), a propylene / 1-butene / ethylene random copolymer (B), ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated group. 0.01 to 0.15 parts by weight, preferably 0.03 to 0.12 parts by weight are used with respect to 100 parts by weight as a total of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) made of polyene. It is done. When the organic peroxide is used in an amount within the above range, a thermoplastic elastomer composition (E) obtained by crosslinking the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) is obtained, and heat resistance, tensile properties, A molded article having sufficient rubber properties such as elastic recovery and rebound resilience and strength can be obtained. Moreover, this composition is excellent also in a moldability.

  In the present invention, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenyl are used in the crosslinking treatment with the organic peroxide. Cross-linking aids such as guanidine and trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate , Polyfunctional methacrylate monomers such as allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be formulated. By blending such a compound, a uniform and mild crosslinking reaction can be expected. In particular, when divinylbenzene is used in the present invention, it is easy to handle, non-crosslinkable crystalline polyolefin (A) as a main component of the object to be treated, propylene / 1-butene / ethylene random copolymer (B), Good compatibility with ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) composed of ethylene, C3-C20 α-olefin and nonconjugated polyene, and has an organic peroxide solubilizing action. In addition, since it functions as a dispersion aid for organic peroxides, it is most preferable because a composition having a uniform crosslinking effect by heat treatment and a balance between fluidity and physical properties can be obtained.

  Moreover, you may add a softening agent as a fluidity | liquidity and hardness adjusting agent at the time of dynamic bridge | crosslinking. The softener is non-crosslinkable crystalline polyolefin (A), propylene / 1-butene / ethylene random copolymer (B), ethylene / α-olefin having 3 to 20 carbon atoms and non-conjugated polyene. -0 to 200 parts by weight, preferably 30 to 170 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total of the olefin / non-conjugated polyene copolymer rubber (C).

Specific examples of the softener include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt and petroleum jelly;
Coal tar softeners such as coal tar and coal tar pitch;
Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil;
Tall oil;
Sub, (Factis);
Waxes such as beeswax, carnauba wax and lanolin;
Fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate and zinc laurate;
Naphthenic acid;
Pine oil, rosin or derivatives thereof;
Synthetic polymer materials such as terpene resins, petroleum resins, coumarone indene resins and atactic polypropylene;
Ester softeners such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate;
Examples thereof include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal-modified polyisoprene, hydrogenated terminal-modified polyisoprene, liquid thiocol, and hydrocarbon-based synthetic lubricating oil. Of these, petroleum softeners, particularly process oils, are preferably used.

The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide.
The kneading temperature is usually 150 to 280 ° C, preferably 170 to 240 ° C. The kneading time is usually 1 to 20 minutes, preferably 3 to 10 minutes. Further, the shear force applied is, 10～100,000Sec ^-1 as the shear rate is preferably 100~50,000sec ^-1.

  Examples of the kneading apparatus include a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single or twin screw extruder, and a non-open type apparatus.

  In addition, the thermoplastic elastomer composition (E) of the present invention may contain additives such as a foaming agent, a slip agent, a nucleating agent, a filler, an antioxidant, a weathering stabilizer and a colorant, if necessary. It can mix | blend in the range which does not impair the objective of invention.

  Specific examples of the blowing agent include inorganic blowing agents such as sodium bicarbonate (sodium bicarbonate), sodium carbonate, ammonium bicarbonate, ammonium carbonate and ammonium nitrite; N, N′-dimethyl-N, N′-dinitroso Nitroso compounds such as terephthalamide and N, N′-dinitrosopentamethylenetetramine (DPT); azodicarbonamide (ADCA), azobisisobutyronitrile (AZBN), azobiscyclohexylnitrile, azodiaminobenzene and barium azodi Azo compounds such as carboxylates; benzenesulfonyl hydrazide (BSH), toluenesulfonyl hydrazide (TSH), p, p'-oxybis (benzenesulfonyl hydrazide) (OBSH) and diphenylsulfone-3,3'-disulfonyl hydrazide What sulfonyl hydrazide compounds; calcium azide, azide compounds such as 4,4-diphenyl disulfonyl azide and p- toluenesulfonyl azide and the like.

  The molded product or foamed molded product formed from the thermoplastic elastomer composition (E) of the present invention is a vulcanized rubber molded product that may be foamed and / or a thermoplastic elastomer molded product that may be foamed. It can be joined to an object to be joined. The foamed molded body can be formed by a conventionally known method used when a rubber or elastomer foam is produced using the foaming agent.

  The thermoplastic elastomer composition (E) of the present invention can prepare a non-foamed or foamed molded article by various molding methods such as extrusion molding, press molding, injection molding, and calendar molding.

Examples of the nucleating agent include non-melting type and melting type crystallization nucleating agents, and these can be used alone or in combination of two or more.
Non-melting type crystallization nucleating agents include inorganic substances such as talc, mica, silica, aluminum, brominated biphenyl ether, aluminum hydroxydi p-t-butylbenzoate (TBBA), hydroxy-di-p-t-butylbenzoate And aluminum phosphates, organophosphates, rosin crystallization nucleating agents, substituted triethylene glycol terephthalates and Terylene & Nylon fibers, among others, hydroxy-di-pt-butylbenzoate aluminum, methylene bis (2,4-di- t-Butylphenyl) sodium phosphate, 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, rosin crystallization nucleating agent and PDTS are preferred.

  Examples of the melting crystallization nucleating agent include sorbitol-based compounds such as dibenzylidene sorbitol (DBS), substituted DBS, and lower alkyl dibenzylidene sorbitol (PDTS).

Specific examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax, and paraffinic oil.
The filler can be used without particular limitation as long as it is a conventionally known filler, specifically, carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, glass fiber. Etc.

<Vulcanized rubber molding>
As the vulcanized rubber constituting the vulcanized rubber molded body, an ethylene / α-olefin / polyene copolymer rubber is preferable from the viewpoint of weldability with the thermoplastic elastomer composition (E) of the present invention. As such copolymer rubber, ethylene / α-olefin / non-conjugated polyene copolymer rubber and / or ethylene / α-olefin copolymer rubber is preferably used.

Here, the “vulcanized rubber” includes not only those crosslinked with sulfur but also those crosslinked with other crosslinking agents.
The thermoplastic elastomer composition (E) of the present invention is a vulcanized rubber molded article used as an interior / exterior material for vehicles, preferably a corner portion welded to a polyolefin vulcanized rubber molded article, for example, a corner of an automobile weather strip. It is suitably used as a part (corner material). Specifically, the thermoplastic elastomer composition (E) of the present invention described above in the molding of a corner portion that cuts an extruded product of polyolefin-based vulcanized rubber and connects the obtained cut extrudates from different directions. A weather strip can be obtained by injection molding at a temperature equal to or higher than the melting point and bringing it into contact with an extruded product of vulcanized rubber and welding it.

A weather strip having a corner molded body made of the thermoplastic elastomer composition (E) of the present invention will be described more specifically with reference to FIG.
FIG. 1 is a schematic perspective view for explaining a weather strip (glass run channel) of an automobile and a molding method thereof.

  As shown in FIG. 1A, the weatherstrip is formed by connecting vulcanized rubber cut extruded products 1 and 2 and the cut extruded products 1 and 2 connected from different directions. It is comprised with the member 3. FIG. The cut extrudates 1 and 2 are obtained by extruding a vulcanized rubber into a channel shape and then cutting it into a predetermined length. The cut extruded products 1 and 2 have a linear shape in the longitudinal direction. In addition, the “joining corner member” here refers to a portion made of a thermoplastic elastomer formed when the cut extruded products are connected from different directions.

Such a weather strip can be prepared as follows.
First, the injection mold 4 is heated in advance to a predetermined temperature. Next, as shown in FIG. 1B, the cut extruded products 1 and 2 made of vulcanized rubber are inserted into the mold 4.

  Next, although not shown, the thermoplastic elastomer composition (E) of the present invention melted at a temperature equal to or higher than the melting point in the heating chamber (in the screw) is formed in a space formed between the cavity of the mold 4 and the core. The thermoplastic elastomer composition (E) of the present invention, which is injected and melted at a temperature equal to or higher than the melting point, is welded to the end faces of the cut extrudates 1 and 2, and then the thermoplastic elastomer composition (E) is cooled. Then, a weather strip having the corner member 3 as shown in FIG.

  The vulcanized rubber used for the preparation of the above cut extruded products 1 and 2 is preferably composed mainly of ethylene / α-olefin / non-conjugated polyene copolymer rubber, and ethylene / α-olefin non-conjugated polyene. Examples of the α-olefin having 3 to 20 carbon atoms in the copolymer rubber include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-octene, Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1, 11- And methyldodecene-1, 12-ethyltetradecene-1. These α-olefins can be used alone or in combination of two or more. Of these α-olefins, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are preferable.

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber provides a rubber composition capable of providing a vulcanized rubber molded article excellent in heat aging resistance, strength characteristics, rubber elasticity, cold resistance and processability. , (A) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms in a molar ratio of 50/50 to 90/10 [(a) / (b)]. It is preferable to contain. This molar ratio is preferably 65/35 to 90/10, more preferably 65/35 to 85/15, and still more preferably 65/35 to 80/20.

  Further, as the non-conjugated polyene, the same non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) used in the present invention can be used without any particular limitation. However, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, and 4-ethylidene-8-methyl-1,7-nonadiene are preferable. These non-conjugated polyenes can be used alone or in combination of two or more.

  The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber provides a rubber composition having a high crosslinking efficiency and a rubber composition capable of providing a vulcanized rubber molded article having excellent compression set resistance. In terms of cost, it is preferably 1 to 40, and more preferably 1 to 30.

  The intrinsic viscosity [η] of ethylene / α-olefin / non-conjugated polyene copolymer rubber measured in decalin at 135 ° C. provides a vulcanized rubber molded product with excellent strength properties, compression set resistance and processability. It is preferable that it is 2.0-4.5 dl / g at the point that the rubber composition which can be obtained is obtained, and it is further more preferable that it is 2.2-4.0 dl / g. These ethylene / α-olefin / non-conjugated polyene copolymer rubbers may be used alone or in combination of two or more.

  In the vulcanized rubber, in order to obtain an extruded vulcanized rubber molded article having sufficient mechanical strength, 30 to 30 parts of carbon black is added to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber. It is preferable to use 300 parts by weight.

As the carbon black, carbon black such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT can be used. Carbon black preferably has a nitrogen adsorption specific surface area of 10 to 100 m ² / g in that a rubber composition capable of providing a vulcanized rubber molded article having good mechanical strength and product skin can be obtained.

In the vulcanized rubber, conventionally known compounding agents such as anti-aging agents, processing aids, foaming agents, foaming aids, colorants, dispersants, flame retardants and the like are appropriately blended depending on the use of the vulcanizate. The
In addition, in the vulcanized rubber, a reinforcing agent such as an inorganic filler can be appropriately used as a reinforcing agent as necessary. The amount of the inorganic filler is usually an ethylene / α-olefin / non-conjugated polyene copolymer. The maximum amount is 100 parts by weight with respect to 100 parts by weight of the polymer rubber.

Specific examples of the inorganic filler include silica, soft calcium carbonate, heavy calcium carbonate, talc, and clay.
As the softener blended in the vulcanized rubber, the same softener as the softener used in the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer (C) can be used. The blending amount of these softeners is appropriately selected depending on the use of the vulcanizate.

Examples of the vulcanizing agent used for vulcanizing the vulcanized rubber include sulfur and sulfur compounds.
Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.

  Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, and polymer polysulfide. Also usable are sulfur compounds that release and vulcanize active sulfur at the vulcanization temperature, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, selenium dimethyldithiocarbamate, and the like. .

Of these, sulfur is preferred. The sulfur or sulfur compound is usually used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the copolymer rubber.
Moreover, when using sulfur or a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator in combination. Specifically, as a vulcanization accelerator,
N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-oxydiethylene-2-benzothiazole sulfenamide (OBS), Nt-butyl-2-benzothiazole sulfenamide (BBS), N, Sulfenamide-based compounds such as N-diisopropyl-2-benzothiazole sulfenamide;
2-mercaptobenzothiazole (MBT), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (4-morpholinothio) benzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole , Thiazole compounds such as dibenzothiazyl disulfide;
Guanidine-based compounds such as diphenylguanidine (DPG), triphenylguanidine, diorthonitrile guanidine (DOTG), orthotolyl biguanide, diphenylguanidine phthalate;
Aldehyde amines or aldehyde-ammonia compounds such as acetaldehyde-aniline condensate, butyraldehyde-aniline condensate, hexamethylenetetramine (H), acetaldehyde ammonia;
Imidazoline compounds such as 2-mercaptoimidazoline;
Thiourea compounds such as thiocarbanilide, diethylthiourea (EUR), dibutylthiourea, trimethylthiourea, diorthotolylthiourea;
Thiuram such as tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide (TOT), dipentamethylenethiuram tetrasulfide (TRA) Compounds;
Dithiocarbamate such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate ;
Xanthates such as zinc dibutylxanthate;
Examples thereof include compounds such as zinc white (zinc oxide).

These vulcanization accelerators are usually used at a ratio of 0.1 to 20 parts by weight with respect to 100 parts by weight of the copolymer rubber.
Moreover, you may add anti-aging agents, such as an amine type, a hindered phenol type, or a sulfur type, in the range which does not impair the objective of this invention.

Examples of amine-based antioxidants include diphenylamines and phenylenediamines.
As the sulfur-based anti-aging agent, a sulfur-based anti-aging agent usually used for rubber is used.

  As the processing aid, a processing aid used for ordinary rubber processing can be used. Specifically, higher fatty acids such as linoleic acid, ricinoleic acid, stearic acid, palmitic acid and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate; esters of the higher fatty acids It is done.

  Such a processing aid is usually used in an amount of 10 parts by weight or less based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber, and is suitably optimized depending on the required physical property values. It is desirable to determine the amount.

As the foaming agent, those similar to the foaming agent that may be added to the thermoplastic elastomer composition (E) of the present invention depending on the application can be used without particular limitation.
The vulcanized rubber may be blended with other known rubbers or resins.

  Examples of such other rubbers include isoprene-based rubbers such as natural rubber (NR) and isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber. And conjugated diene rubbers such as (CR).

Examples of other resins include polyethylene, polypropylene, 1,2-polybutadiene, and polybutene.
In order to form a vulcanized rubber molded body, first, a rubber composition for extrusion molding is prepared. The rubber composition for extrusion is made of an ethylene / α-olefin / non-conjugated polyene copolymer rubber, carbon black, rubber using an internal mixer (closed mixer) such as a Banbury mixer, kneader, or intermix. Additives such as reinforcing agents, inorganic fillers and softeners are kneaded at a temperature of 80 to 170 ° C. for 2 to 20 minutes, and further sulfur is added and kneaded. If necessary, a vulcanization accelerator and a vulcanization aid are added. An agent, a foaming agent, and a foaming aid are additionally mixed, kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes using a roll such as an open roll or a kneader, and then dispensed.

The rubber composition for extrusion molding prepared as described above is molded into a target shape by an extruder, and simultaneously or after molding, the molded product is introduced into a vulcanizing tank, and the temperature is 140 to 300 ° C. 1 to
It can be vulcanized by heating for 20 minutes.

  The vulcanization process is usually carried out continuously. Use heating means such as hot air, glass bead fluidized bed, molten salt tank (LCM), PCM (Powder Curing Medium or Powder Curing Method), UHF (Ultra High Frequency Electromagnetic Wave), steam, etc. Can do.

  Here, although the weather strip has been described as an example, the thermoplastic elastomer composition (E) of the present invention is not only used for forming a fusion-molded body on a vulcanized rubber molded body but also for melting a skin portion such as a door trim. The present invention can also be applied to the case of forming with an outer skin layer.

<Thermoplastic elastomer molded body>
Examples of thermoplastic elastomer moldings include olefins, styrenes, vinyl chlorides, urethanes, esters, amides, etc., but contain olefin resins and partially or fully crosslinked olefin rubbers. It is preferable that the composition is an olefin-based composition.

The olefin resin, which is a component of the thermoplastic elastomer molded article, is a crystalline high molecular weight obtained by polymerizing one or more monoolefins by either the high pressure method or the low pressure method. It is a solid product.

  Specific examples of suitable raw material olefins for the olefin resins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3- Examples thereof include α-olefins having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms such as methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. These α-olefins are used alone or in combination of two or more.

The polymerization mode may be random type or block type, and any polymerization mode may be used as long as a resinous form is obtained.
Of these, propylene polymers are preferred as the olefin resins, and specifically, propylene homopolymers, propylene / ethylene block copolymers, propylene / ethylene, and propylene / ethylene / butene random copolymers are preferred. Of these, isotactic and syndiotactic propylene polymers are particularly mentioned. Olefin resins may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as said olefin resin, A polypropylene etc. can be illustrated and a polypropylene is especially preferable. These representative resins are commercially available.

The olefin resin has a melt flow rate (MFR: ASTM D 1238-65T, 230 ° C., 2.16 kg load) usually in the range of 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min. It is desirable.
The olefin resin has a role of improving the fluidity and heat resistance of the thermoplastic elastomer composition (E) of the present invention.

The olefin rubber used as a component of the olefin rubber thermoplastic elastomer molding is not particularly limited, but ethylene / α-olefin / non-conjugated polyene copolymer rubber and ethylene / α-olefin copolymer rubber, etc. Is mentioned.

  The ethylene content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber or ethylene / α-olefin copolymer rubber is usually 25 to 95 mol%, preferably 30 to 90 mol%, more preferably 35 to 85 mol. %.

Examples of the α-olefin include the α-olefins having 3 to 20 carbon atoms described above, and propylene is preferable.
As the non-conjugated polyene, the same non-conjugated polyene that constitutes the vulcanized rubber molded body described above can be used without particular limitation.

The iodine value of the ethylene / α-olefin (• non-conjugated polyene) copolymer rubber is 1 to 30 g / 100 g, preferably 3 to 25 g / 100 g. Moreover, it is preferable that Mooney viscosity (ML1 _{+ 4} , 100 degreeC) is 10-250.

Thermoplastic elastomer molded product The olefinic resin and olefinic rubber are used in a proportion of 10 to 80% by weight, preferably 15 to 60% by weight of olefinic resin, based on the total of olefinic resin and olefinic rubber. Is 90 to 20% by weight, preferably 85 to 40% by weight. When the proportions of the olefin resin and the olefin rubber are in the above ranges, the heat-resistant thermoplastic elastomer composition of the present invention that is excellent in flexibility and rubber elasticity and excellent in molding is obtained.
As softeners and inorganic fillers used as other components, softeners and inorganic fillers usually used for rubber can be used.

〔Example〕
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.

In addition, the melt flow rate (MFR) of the thermoplastic elastomer composition (E) used in the examples and comparative examples, the tensile peel strength of the molded body formed from the thermoplastic elastomer composition (E), the elongation until peeling, Measurement and evaluation of hardness, tensile strength and elongation were performed according to the following methods.
(1) Melt flow rate (MFR)
The measurement was performed at 230 ° C. and a load of 2.16 kg according to ASTM D 1238-65T.
(2) Hardness Shore A hardness was measured according to JIS K6253.
(Measurement conditions) A sheet was prepared by a press molding machine, and the scale was read immediately after contact with the pressing needle using an A-type measuring instrument.
(3) Tensile strength and elongation In accordance with JIS K6251, a tensile test was performed under the following conditions, and the tensile strength and elongation at break were measured.
(Test conditions) A sheet was prepared by a press molding machine, a JIS No. 3 test piece was punched out, and the test was performed under the condition of a tensile speed of 500 mm / min.
(4) Adhesive strength strength and elongation until peeling Vulcanized rubber press sheet (12 cm long × 14.7 cm wide × 2 mm thick flat plate) obtained in Production Examples 1 and 2 described later, thermoplastic elastomer molded body (12 cm long) A JIS No. 3 test piece having a width of 14.7 cm and a thickness of 2 mm is punched out to produce adherends of a vulcanized rubber molded body and a thermoplastic elastomer molded body. Each of these molded bodies is cut in half with a cutter and set in an injection mold. The thermoplastic elastomer composition to be welded to the cut surface of the vulcanized rubber molded product and the thermoplastic elastomer molded product at an injection temperature of 250 ° C. and a mold temperature of 50 ° C. in a 100 Ton injection molding machine is in the injection stage. Then, it is molded so as to be melt-bonded to the adherend.

  A peel test is performed on the molded product (JIS No. 3 test piece) thus melt-bonded at a tensile speed of 200 mm / min, and the tensile peel strength (adhesive strength) and the elongation until peeling are measured.

[Production Example 1] Preparation of vulcanized rubber press sheet Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (ethylene content = 68 mol%, 135 ° C., intrinsic viscosity measured in decalin [η ] = 2.8 dl / g, iodine value = 12) 100 parts by weight, 170 parts by weight of FEF grade carbon black (Asahi Carbon Co., Ltd., trade name: Asahi # 60G), softener (Idemitsu Kosan Co., Ltd.) Product name: Diana Process Oil ^TM PS-430) 95 parts by weight, stearic acid 1 part by weight, zinc white No. 1 5 parts by weight, activator (product of Lion Corporation, trade name: ARCARD 2HT-F) ) 1 part by weight was kneaded with a 1.7 liter Banbury mixer (manufactured by Kobe Steel, Ltd., BB-2 type mixer).

  In the kneading method, the raw rubber was first kneaded for 1 minute, and then carbon black, softener, stearic acid, zinc white No. 1, and activator were added and kneaded for 2 minutes. Thereafter, the ram was raised, cleaned, and kneaded for another 2 minutes to obtain 1390 parts by weight of rubber compound (I). This kneading was performed at a filling rate of 75%, and further, two batches were kneaded in the same procedure to obtain a total of 4170 parts by weight.

3670 parts by weight of the obtained rubber compound (I) was weighed, and a 14-inch roll (manufactured by Nippon Roll Co., Ltd.) (front roll surface temperature 60 ° C., rear roll surface temperature 60 ° C., front roll rotation speed 16 rpm) The rubber composition (I) was wound around 5 parts by weight of sulfur and 2-mercaptobenzothiazole (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sunseller M). , Dibenzothiazyl disulfide (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sunseller DM) 5 parts by weight, zinc dibutyldithiocarbamate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sunseller BZ) 20 parts by weight, dimethyl Zinc dithiocarbamate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sunseller PZ) 5 parts by weight, ethylenethiourea (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sunseller 22) ) 10 parts by weight, 5 parts by weight of dithiodimorpholine (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sanfell R) and 50 parts by weight of calcium oxide (manufactured by Inoue Lime Industry Co., Ltd., trade name: Vesta PP) The mixture was then kneaded for 7 minutes with a 14-inch open roll (manufactured by Nippon Roll Co., Ltd., roll temperature 60 ° C.) to obtain a rubber compound (II).
Hereinafter, using this rubber compound (II), a vulcanized rubber press sheet was produced using a 150 ton press.

[Production Example 2] Production of thermoplastic elastomer press sheet Oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (ethylene content: 78 mol%, propylene content: 22 mol%, iodine value: rubber component) 13, Mooney viscosity [ML _{1 + 4} (100 ° C.)] 74, oil extended amount: 62 parts by weight of paraffinic process oil (trade name: PW-380, manufactured by Idemitsu Kosan Co., Ltd.) with respect to 100 parts by weight of rubber; Hereinafter referred to as “EPT”) 60.6 parts by weight and polypropylene as propylene homopolymer (MFR (ASTM D 1238, 230 ° C., 2.16 kg load): 55 g / 10 minutes, melting point (Tm): 162 ° C .; 27 parts by weight of propylene homopolymer (MFR (ASTM D 1238, 230 ° C., 2.16 kg load): 1.5 g / 10 min, melting point (Tm): 160 ° C .; hereinafter referred to as “PP-1”. 2 ”), 12.4 parts by weight, 0.1 parts by weight of a phenolic antioxidant (Nippon Ciba Geigy Co., Ltd., trade name: Irganox 1010) as an antioxidant, and a diazo weathering stable as a weathering agent 0.1 parts by weight of an agent (manufactured by Nippon Ciba-Geigy Co., Ltd., trade name: Tinuvin 326) and 0.3 parts by weight of oleic acid amide (trade name: Armoslip CP, manufactured by Lion Corporation) as a slip material An organic peroxide (manufactured by NOF Corporation, trade name: Perhexa 25B) 0.64 parts by weight as an agent and 0.48 parts by weight of divinylbenzene as a crosslinking aid are sufficiently mixed in a Henschel mixer, and an extruder ( Part number TEM-50, manufactured by Toshiba Machine Co., Ltd., L / D = 40, cylinder temperature: C1-C2 120 ° C., C3-C4 140 ° C., C5-C6 180 ° C., C7-C8 200 ° C., C9-C12 220 ° C., die temperature: 210 ° C., screw rotation speed: 280 rpm, extrusion amount: 40 kg / h) 21 parts by weight of paraffinic process oil (manufactured by Idemitsu Kosan Co., Ltd., trade name: PW-100) Granulation was performed while pouring into a cylinder to obtain pellets of a thermoplastic elastomer composition.
Next, a 2 mmt sheet was produced by a press molding machine.

Synthesis Example 1 Preparation of Propylene / 1-Butene / Ethylene Random Copolymer (B) (PBER-1) As a catalyst / cocatalyst, diphenylmethylene (prepared by the method described in JP-A-2007-186664) Ethylene as a raw material using 3-t-butyl-5-ethylcyclopentadienyl) (2,7-t-fluorenyl) zirconium dichloride / methylaluminoxane (manufactured by Tosoh Finechem, 0.3 ml in terms of aluminum) , Propylene and 1-butene were polymerized in a hexane solution using a continuous polymerization facility to obtain propylene / 1-butene / ethylene random copolymer (PBER-1) (propylene 67 mol%, 1-butene 19 mol). %, Ethylene 14 mol%, Mw / Mn = 2.1, intrinsic viscosity [η] = 1.8 dl / g, mm fraction 92.1%) was obtained.

Synthesis Example 2 Preparation of Propylene / 1-Butene / Ethylene Random Copolymer (B) (PBER-2) As a catalyst / cocatalyst, diphenylmethylene prepared by the method described in JP-A-2007-186664 ( Ethylene as a raw material using 3-t-butyl-5-ethylcyclopentadienyl) (2,7-t-fluorenyl) zirconium dichloride / methylaluminoxane (manufactured by Tosoh Finechem, 0.3 ml in terms of aluminum) , Propylene and 1-butene were polymerized in a hexane solution using a continuous polymerization facility to produce propylene / 1-butene / ethylene random copolymer (PBER-2) (propylene 76 mol%, 1-butene 6 mol%) , Ethylene 18 mol%, Mw / Mn = 2.1, intrinsic viscosity [η] = 1.4 dl / g, mm fraction = 90. %) Was obtained.

[Example 1]
35 parts by weight of polypropylene (A) (MFR (ASTM D 1238, 230 ° C., 2.16 kg load): 8 g / 10 minutes, melting point (Tm): 140 ° C .; hereinafter referred to as “PP-1”) and ethylene as a rubber component Propylene / 5-ethylidene-2-norbornene copolymer rubber (C) (ethylene content: 57 wt%, diene content: 7.3 wt%, Mooney viscosity [ML _{1 + 4} (125 ° C.)]
74, hereinafter referred to as “EPT”. ) 54 parts by weight, 1 part by weight of silicone oil (manufactured by Toray Dow Corning Co., Ltd., trade name: SH200), 2.5 parts by weight of 40% carbon master match as a carbon master batch, and phenolic as an antioxidant 0.1 parts by weight of an antioxidant (manufactured by Ciba Geigy Japan Ltd., trade name: Irganox 1010), and a diazo weathering stabilizer (manufactured by Ciba Geigy Japan Ltd., trade name: Tinuvin 326) 0.5 as a weathering agent 1 part by weight of organic peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perhexa 25B) as a crosslinking agent and 0.11 part by weight of divinylbenzene as a crosslinking aid are sufficiently mixed with a Henschel mixer. Extruder (product number: TEM-50, manufactured by Toshiba Machine Co., Ltd., L / D = 40, cylinder temperature: C1-C2 120 ° C., C3-C4 140 ° C., C -C6 180 ° C, C7-C8 200 ° C, C9-C12 220 ° C, Die temperature: 210 ° C, Screw rotation speed: 280rpm, Extrusion amount: 40kg / h) Paraffinic process oil (D) (Idemitsu Kosan Co., Ltd.) ), Product name: PW-380) Granulation was carried out while injecting 39 parts by weight into a cylinder to obtain pellets of a thermoplastic elastomer composition.

92 parts by weight of the obtained thermoplastic elastomer pellets, 8 parts by weight of PBER-1 obtained in Synthesis Example 1 were sufficiently mixed with a Henschel mixer, and an extruder (product number: TEM-50, manufactured by Toshiba Machine Co., Ltd.) L / D = 40, cylinder temperature: C1-C2 120 ° C., C3-C4 140 ° C., C5-C6 180 ° C., C7-C8 200 ° C., C9-C12 220 ° C., die temperature: 210 ° C., screw rotation speed: 800 rpm , Extrusion rate: 40 kg / h), and pellets of a thermoplastic elastomer composition were obtained.

This pellet-shaped thermoplastic elastomer composition was injection molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

[Example 2]
In Example 1, 32 parts by weight of PP-1, 13 parts by weight of PBER-1, 49 parts by weight of EPT, and 87 parts by weight of the obtained thermoplastic elastomer pellets were used in the same manner as in Example 1. A pellet of a thermoplastic elastomer composition was obtained.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

Example 3
A pellet of a thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that 8 parts by weight of PBER-2 was used instead of PBER-1 in Example 1.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

Example 4
A pellet of a thermoplastic elastomer composition was obtained in the same manner as in Example 2, except that 13 parts by weight of PBER-2 was used instead of PBER-1 in Example 2.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

Example 5
In Example 1, the thermoplasticity was the same as in Example 1, except that PP-1 was 54 parts by weight, PBER-1 was 8 parts by weight, EPT was 36 parts by weight, and paraffinic process oil was 29 parts by weight. A pellet of the elastomer composition was obtained.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

Example 6
In the same manner as in Example 1 except that PP-1 is 18 parts by weight, PBER-1 is 12 parts by weight, EPT is 70 parts by weight, and paraffinic process oil is 47 parts by weight. A pellet of the composition was obtained.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

[Comparative Example 1]
Example 1 was the same as Example 1 except that PBER-1 (component (B)) was not used, 35 parts by weight of PP-1, 54 parts by weight of EPT , and 39 parts by weight of paraffinic process oil were used. Thus, pellets of the thermoplastic elastomer composition were produced.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

[Comparative Example 2]
In Example 1, pellets of a thermoplastic elastomer composition were produced in the same manner as in Example 1 except that non-crosslinked rubber was used instead of EPT (component (C)). Since non-crosslinked rubber was used, no crosslinking agent or crosslinking aid was used.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

[Comparative Example 3]
In Example 1, instead of PBER-1 (component (B)), propylene / 1-butene / ethylene copolymer (PBER-3) (manufactured by Mitsui Chemicals, Inc., trade name: RS2605, propylene 54 mol%) 1-butene 21 mol%, ethylene 25 mol%, Mw / Mn = 5.3, intrinsic viscosity [η] = 1.8 dl / g, mm fraction = 95%) Similarly, pellets of the thermoplastic elastomer composition were produced.

This pellet-shaped thermoplastic elastomer composition was injection molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

[Comparative Example 4]
In Example 1, instead of PBER-1, amorphous propylene-1-butene copolymer (Huntsman Polymers, trade name: REXtac2780A, propylene 71 mol%, 1-butene 29 mol%, Mw / Mn = 5. 1 and pellets of a thermoplastic elastomer composition were prepared in the same manner as in Example 1 except that the intrinsic viscosity [η] = 0.5 dl / g, mm fraction = 15%) was used.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the resulting molded product was evaluated according to the method described above.
The results are shown in Table 1.

FIG. 1 (A) is a schematic perspective view showing an example of a weather strip for an automobile in which a corner portion is formed from the thermoplastic elastomer composition (E) of the present invention. FIG. 1 (B) is a schematic perspective view of FIG. It is a model perspective view which shows the formation method of the corner part of the weather strip of ().

Explanation of symbols

1, 2... Extrusion product 3 .. Joining corner member 4... Mold for injection molding

Claims (5)

10-60 parts by weight of a non-crosslinkable crystalline polyolefin resin (A) and an ethylene / α-olefin / nonconjugated polyene copolymer rubber (C) comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene ) After blending a blend containing 89 to 20 parts by weight in the presence of a crosslinking agent in a melted state, this and further propylene / 1-butene / ethylene random copolymer (B) 1 to 20 parts by weight Kneaded in a molten state (provided that the total of (A), (B) and (C) is 100 parts by weight) , a part of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (C) or The propylene / 1-butene / ethylene random copolymer (B) is all crosslinked,
(1) 90 to 50 mol% of units derived from propylene, 5 to 25 mol% of units derived from 1-butene, 5 to 25 mol% of units derived from ethylene,
(2) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5,
(3) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.7 to 10 dl / g,
(4) The thermoplastic elastomer composition (E), wherein the triad tacticity (mm fraction) calculated by ¹³ C-NMR is 85% or more. In addition to the above (A), (B) and (C), it further contains a softening agent (D), and the softening agent (D) is a total of 100 of these components (A), (B) and (C). The thermoplastic elastomer composition (E) according to claim 1, wherein the thermoplastic elastomer composition (E) is contained in an amount of 200 parts by weight or less based on parts by weight . The triad tacticity (mm fraction) calculated by ¹³ C-NMR of the propylene / 1-butene / ethylene random copolymer (B) is 88% or more and 98% or less. Or the thermoplastic elastomer composition (E) of 2.   2. The intrinsic viscosity [η] measured in decalin at 135 ° C. of the propylene / 1-butene / ethylene random copolymer (B) is 1.0 to 5.0 dl / g. The thermoplastic elastomer composition (E) according to any one of?   The thermoplastic elastomer composition (E) according to any one of claims 1 to 4, wherein the thermoplastic elastomer composition (E) is used for welding to a vulcanized rubber molded article or a thermoplastic elastomer molded article.

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