JP2006328306A - Olefin polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymer composition excellent in continuous productivity and mechanical strengths. <P>SOLUTION: The olefin polymer composition comprises a crosslinkable rubbery polymer (A) and an olefin polymer (B), where the component (B) comprises a non-crystalline olefin polymer (B-1) as an essential ingredient and optionally a crystalline polymer (B-2). The crosslinked olefin polymer composition comprising the components (A) and (B) is also provided. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to an olefin polymer composition. More specifically, the present invention relates to an olefin polymer composition having excellent mechanical strength and excellent continuous productivity.

In the presence of a radical initiator, a rubbery polymer such as a thermoplastic olefin elastomer and a thermoplastic elastomer or radical crosslinkable elastomer comprising a thermoplastic resin such as polypropylene (PP) and a resin having no radical crosslinkability such as PP, A thermoplastic elastomer composition by so-called dynamic crosslinking, which is crosslinked while melt-kneaded in an extruder, is already a known technique and is widely used for applications such as automobile parts.
As such a thermoplastic elastomer composition, a dynamic crosslinking technique using an olefin-based elastomer (for example, see Patent Documents 1 and 2) produced by ethylene-propylene-diene rubber (EPDM) is known. Productivity and mechanical strength are not sufficient and not always satisfied in the market.

On the other hand, as a conventional technique for improving flexibility and mechanical strength, the use of an amorphous polypropylene resin has been proposed. For example, a polypropylene resin composition comprising a crystalline polypropylene resin and an amorphous polypropylene resin ( For example, see Patent Document 3.), a thermoplastic elastomer composition obtained by dynamically crosslinking a crystalline olefin polymer and an amorphous olefin rubber with an organic peroxide and phenyl bismaleimide (for example, see Patent Document 4). However, due to insufficient mechanical strength, there is a need in the industry for thermoplastic elastomer compositions that can withstand practical use.
JP-A-8-120127 Japanese Patent Laid-Open No. 9-137001 Japanese Patent Laid-Open No. 9-309982 JP-A-9-132678

  In view of such a current situation, an object of the present invention is to provide an olefin polymer composition that does not have the above-described problems, that is, has excellent continuous productivity and mechanical strength.

As a result of intensive investigation of an olefin polymer composition excellent in continuous productivity and mechanical strength, the present inventors have surprisingly achieved continuous productivity and mechanical strength by combining specific polymers. The present invention has been completed.
That is, the present invention comprises a crosslinkable rubber-like polymer (A) and an olefin polymer (B), and the component (B) comprises the amorphous olefin polymer (B-1) as an essential component and is necessary. And an olefin polymer composition characterized by containing a crystalline olefin polymer (B-2), and a crosslinked olefin system comprising (A) and (B) components A polymer composition is provided.

  The olefin polymer composition of the present invention has excellent mechanical strength and enables quality stabilization due to excellent continuous productivity.

The present invention will be specifically described below.
The composition of the present invention comprises a crosslinkable rubbery polymer (A) and an amorphous olefin polymer (B-1) as essential components, and if necessary (crystalline olefin polymer (B-2)). It consists of an olefin resin (B) containing
Here, it is important that the component (A) and the component (B) are crosslinked while maintaining thermoplasticity. Crosslinking of the above components improves excellent mechanical properties, particularly rubber properties and durability.
And when (B) component was amorphous, it discovered that the balance characteristic of continuous productivity and mechanical strength improved remarkably, and completed this invention.

Hereinafter, each component of the present invention will be described in detail.
(A) Component In the present invention, (A) the crosslinkable rubber-like polymer is obtained by hydrogenating a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and the diene rubber. Saturated polymer rubber (hydrogenated copolymer rubber), isoprene rubber, chloroprene rubber, acrylic rubber such as polybutyl acrylate, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-propylene-diene monomer Examples thereof include a crosslinked rubber or non-crosslinked rubber such as an ethylene / α-olefin copolymer such as a terpolymer (EPDM), and a thermoplastic elastomer containing the rubber component.

Further, (A) preferably has a glass transition temperature (Tg) of −10 ° C. or lower.
And (A) Mooney viscosity (ML) (ISO 289-1985 (E) conformity) measured at 100 degreeC has preferable 20-150, More preferably, it is 50-120.
In this invention, it is preferable in (A) crosslinkable rubber-like polymer. One of the polymers is an ethylene / α-olefin copolymer, more preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, and dodecene-1. Etc. Among them, hexene-1, 4-methylpentene-1, and octene-1 are preferable, and an α-olefin having 3 to 12 carbon atoms is particularly preferable, and propylene, butene-1, and octene-1 are most preferable.

Further, (A) the crosslinkable rubber-like polymer can contain a monomer having an unsaturated bond, if necessary, such as conjugated diolefins such as butadiene and isoprene, 1,4-hexadiene and the like. Non-conjugated diolefins, cyclic diene compounds such as dicyclopentadiene and norbornene derivatives, and acetylenes are exemplified. In particular, ethylidene norbornene (ENB) and dicyclopentadiene (DCP) are most preferable.
In the present invention, an ethylene / α-olefin copolymer (hereinafter referred to as “(A) ethylene / α-olefin copolymer)”, which is one of the preferred copolymers of (A), is a known metallocene catalyst. It is preferable to manufacture using.

In general, a metallocene catalyst comprises a cyclopentadienyl derivative of a group IV metal such as titanium or zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst but also a polymer obtained in comparison with a Ziegler catalyst. The molecular weight distribution is narrow and the distribution of the α-olefin having 3 to 20 carbon atoms, which is a comonomer in the copolymer, is uniform.
The ethylene / α-olefin copolymer (A) used in the present invention preferably has a copolymerization ratio of α-olefin of 1 to 60% by weight, more preferably 10 to 50% by weight, most preferably. 20 to 45% by weight. The copolymerization ratio of α-olefin is preferably 60% by weight or less from the viewpoints of the hardness and tensile strength of the composition, and is preferably 1% by weight or more from the viewpoints of flexibility and mechanical strength.

The density of the ethylene / α-olefin copolymer (A) is preferably in the range of 0.8 to 0.9 g / cm ³ . By using an ethylene / α-olefin copolymer having a density in this range, the thermoplastic elastomer composition of the present invention having excellent flexibility and low hardness can be obtained.
The ethylene / α-olefin copolymer (A) used in the present invention preferably has long chain branching. Due to the presence of long chain branching, it is possible to make the density smaller compared to the proportion (% by weight) of the α-olefin copolymerized without reducing the mechanical strength. An ethylene / α-olefin copolymer having high hardness and high strength can be obtained. The ethylene / α-olefin copolymer having a long chain branch is described in US Pat. No. 5,278,272.

The ethylene / α-olefin copolymer of (A) desirably has a melting point peak of a thermobalance (DSC) above room temperature. When it has a melting point peak, the form is stable in the temperature range below the melting point, it is easy to handle and has little stickiness.
The melt index of the ethylene / α-olefin copolymer (A) used in the present invention is in the range of 0.01 to 100 g / 10 min (190 ° C., 2.16 kg load (0.212 Pa)). Those are preferably used, and more preferably 0.2 to 10 g / 10 min. From the viewpoint of crosslinkability of the thermoplastic crosslinked rubber composition of the present invention, 100 g / 10 min or less is preferable, and from the viewpoint of fluidity and processability, 0.01 g / 10 min or more is preferable.

In the present invention, the hydrogenated copolymer which is another preferred copolymer of (A) is a homopolymer rubber of at least one conjugated diene monomer, or a conjugated diene monomer and an aromatic A copolymer rubber comprising a vinyl monomer, preferably a hydrogenated copolymer rubber in which the hydrogenation rate of the full double bond of the random copolymer is 50% or more, particularly in the main chain and the side chain. A hydrogenated copolymer rubber in which 50% or more of the total olefinic double bonds of the unsaturated polymer rubber comprising a polymer and / or copolymer having a double bond is hydrogenated is preferable.
In the hydrogenated copolymer rubber, if necessary, for example, olefinic, methacrylic ester, acrylic ester, unsaturated nitrile, vinyl chloride monomer and other conjugated dienes can be copolymerized. A monomer (hereinafter referred to as a copolymerizable monomer) can be copolymerized.

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3- Hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like can be mentioned, and 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, Most preferred are 3-butadiene and isoprene.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, and vinylpyridine. Styrene and α-methylstyrene are preferable. The aromatic monomers can be used alone or in combination of two or more. The aromatic vinyl monomer content is preferably 0 to 80% by weight, more preferably 0 to 50% by weight, and most preferably 0 to 30% by weight.

  In the hydrogenated copolymer as (A), the vinyl bond in the conjugated diene monomer portion before hydrogenation may be present uniformly in the molecule, or may increase or decrease or decrease along the molecular chain. In addition, a plurality of blocks having different vinyl bond contents may be included. When the aromatic vinyl monomer and / or copolymerizable monomer is included, the conjugated diene monomer and the aromatic vinyl monomer and / or copolymerizable monomer are randomly bonded. However, it may contain a block-like aromatic vinyl monomer and / or a block-like copolymerizable monomer. The content of the block-like aromatic vinyl polymer is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total aromatic vinyl monomer.

The total olefinic double bonds in the hydrogenated copolymer rubber are 50% or more, preferably 90% or more, more preferably 95% or more, and the remaining double bonds in the main chain are 5% or less. The residual double bond in the side chain is 5% or less. Specific examples of such hydrogenated copolymer rubbers include partially or completely hydrogenated diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), polyisoprene, polychloroprene. Examples thereof include rubber-like polymers, and hydrogenated butadiene-based or hydrogenated isoprene-based rubber is particularly preferable.
Such a hydrogenated copolymer rubber can be obtained by partially hydrogenating the above-described diene rubber by a known hydrogenation method. For example, F.A. L. Ramp, etal, J. et al. Ameri. Vhem. Soc. , 83, 4672 (1961), a method of hydrogenation using a triisobutylborane catalyst, Hung Yu Chen, J. et al. Polym. Sci. Polym. Letter Ed. , 15, 271 (1977), or hydrogenation using a toluenesulfonyl hydrazide, or an organic cobalt-organic aluminum catalyst or an organic nickel-organic aluminum catalyst described in Japanese Patent Publication No. 42-8704 And the like.

Here, particularly preferred hydrogenation methods are disclosed in JP-A-59-133203 and JP-A-60-220147 using inert catalysts that can be hydrogenated under mild conditions of low temperature and low pressure, or inert organic compounds. Contacting with hydrogen in a solvent in the presence of a catalyst comprising a bis (cyclopentadienyl) titanium compound and a hydrocarbon compound having a sodium atom, a potassium atom, a rubidium atom or a cesium atom This is the method shown in the gazette.
The hydrogenated copolymer rubber preferably has a 5 wt% styrene solution viscosity (5% SV) at 25 ° C. in the range of 20 to 300 centipoise (cps). A particularly preferred range is 25 to 150 cps.
The hydrogenated copolymer rubber preferably has crystallinity, and the endothermic peak calorific value, which is an index of crystallinity, is controlled by adding a polar compound such as tetrahydrofuran or controlling the polymerization temperature. The reduction of the endothermic peak heat amount is achieved by increasing the amount of polar compound during the production of the rubbery polymer or increasing the 1,2-vinyl bond by decreasing the polymerization temperature.

The (A) crosslinkable rubbery polymer used in the present invention may be used by mixing a plurality of types. In such a case, the workability can be further improved.
In the present invention, the proportion of the polymer having a polystyrene-reduced molecular weight of 150,000 or less in the crosslinkable rubber-like polymer (A) is preferably 30% by weight or less, more preferably 25% or less, and still more preferably. 20% or less, most preferably 15% or less, and most preferably 10% or less. When the ratio is 30% or less, the crosslinkability is remarkably increased, and the mechanical strength, appearance, feel, wear resistance and oil resistance are improved.
In the present invention, as a method for controlling the proportion of the polymer having a polystyrene-reduced molecular weight of 150,000 or less in the crosslinkable rubber-like polymer (A) in the present invention, the entire molecular weight of 150,000 or less is 30% or less. And a method of removing a part having a molecular weight of 150,000 or less by an operation such as extraction, or a polymerization method in which a molecular weight of 150,000 or less is not selectively generated by a polymerization catalyst or the like.

(B) Component The (B) olefin polymer in the present invention comprises (B-1) an amorphous olefin polymer as an essential component, and optionally contains (B-2) a crystalline olefin polymer. To do. Further, both (B-1) and (B-2) are copolymers of ethylene and / or α-olefins containing 2 or 20 carbon atoms, such as ethylene or propylene polymers. In particular, a propylene-based polymer is preferable.
The (B-1) amorphous olefin polymer in the present invention is characterized in that it has neither a crystal melting peak nor a crystallization peak of 1 J / g or more as measured by a differential scanning calorimeter (DSC). It is. (B-2) and (B-1) are judged by the presence or absence of a crystal melting peak and a crystallization peak.
Specific examples of the propylene polymer most preferably used among the above (B-1) amorphous olefin polymers in the present invention are homopolypropylene, propylene and ethylene, butene-1, pentene- 1, copolymers with other α-olefins such as hexene-1.

(B-1) preferably has a molecular weight distribution non-uniformity index Mw / Mn (weight average molecular weight / number average molecular weight) of 5 or less, more preferably 3.5 or less. In order to satisfy such conditions, it is usually preferable to perform polymerization using a metallocene catalyst. For example, JP-A-9-309982 discloses a catalyst structure and a polymerization method.
The melt index of the olefin polymer suitably used in the present invention is preferably in the range of 0.1 to 100 g / 10 min (230 ° C., 2.16 kg load (0.212 Pa)). From the viewpoint of heat resistance and mechanical strength of the thermoplastic elastomer composition, it is preferably 100 g / 10 min or less, and from the viewpoint of fluidity and moldability, 0.1 g / 10 min or more is preferable.

The (B-2) crystalline olefin polymer in the present invention has both a crystal melting peak and a crystallization peak of 1 J / g or more as measured by a differential scanning calorimeter (DSC). It is a feature.
The most preferred propylene homopolymer in (B-2) or a copolymer with α-olefin mainly composed of propylene is produced by a high pressure method, a slurry method, a gas phase method, a bulk method, a solution method, or the like. The polymerization catalyst is preferably a Ziegler-Natta catalyst, a single site, or a metallocene catalyst. In particular, when a narrow composition distribution and molecular weight distribution are required, a copolymerization method using a metallocene catalyst is preferable.
A specific method for producing such a copolymer is disclosed in European Patent 096943A or US Pat. No. 5,1984,401, and after introducing liquid propylene into a reactor equipped with a stirrer, the catalyst is added to the gas phase or liquid phase from a nozzle. . Next, ethylene gas or α-olefin is introduced into the gas phase or liquid phase of the reactor, and the reaction temperature and reaction pressure are controlled to conditions under which propylene is refluxed. The polymerization rate is controlled by the catalyst concentration and the reaction temperature, and the copolymer composition is controlled by the amount of ethylene or α-olefin added.

(C) Component It is preferable that the composition of this invention is bridge | crosslinked with (C) crosslinking agent.
(C) The crosslinking agent contains (C-1) a crosslinking initiator as an essential component, and contains (C-2) a polyfunctional monomer and (C-3) a monofunctional monomer as necessary. The (C) crosslinking agent is used in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 3 parts by weight, based on 100 parts by weight of the total of (A) and (B). Within the above range, the level of crosslinking increases, and the balance between the appearance and mechanical strength of the composition is improved.

  Here, examples of the (C-1) crosslinking initiator include radical initiators such as organic peroxides and organic azo compounds, and specific examples thereof include 1,1-bis (t-butylperoxy). −3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1- Bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t Peroxyketals such as -butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide, -Butyl cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5 -Dialkyl peroxides such as bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3.

  Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and diacyl peroxides such as m-trioyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl Peroxyesters such as carbonate and cumylperoxyoctate; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide And hydroperoxides such as 1,1,3,3-tetramethylbutyl peroxide.

Among these compounds, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are preferred.
The (C-1) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C). 1% by weight or more is preferable from the viewpoint of crosslinkability, and 80% by weight or less is preferable from the viewpoint of mechanical strength.

  In the present invention, the (C-2) polyfunctional monomer contained in the (C) crosslinking agent as necessary is preferably a radically polymerizable functional group as a functional group, and particularly preferably a vinyl group. Although the number of functional groups is 2 or more, it is effective particularly in the case of having 3 or more functional groups in combination with (C-3). Specific examples include divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinonedioxime, P, P'-dibenzoylkidioxime, phenylmaleimide, allyl methacrylate, N, N'-m-phenylenebismaleimide, diallyl phthalate , Tetraallyloxyethane, 1,2-polybutadiene and the like are preferably used. Triaryl isocyanurate is particularly preferable. These polyfunctional monomers may be used in combination.

The (C-2) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C). 1% by weight or more is preferable from the viewpoint of crosslinkability, and 80% by weight or less is preferable from the viewpoint of mechanical strength.
The (C-3) used in the present invention is a vinyl monomer added to control the crosslinking reaction rate, preferably a radical polymerizable vinyl monomer, and an aromatic vinyl monomer or acrylonitrile. , Unsaturated nitrile monomers such as methacrylonitrile, ester monomers such as acrylic acid ester monomers and methacrylic acid ester monomers, unsaturated carboxylic acids such as acrylic acid monomers and methacrylic acid monomers Examples thereof include unsaturated carboxylic acid anhydrides such as acid monomers and maleic anhydride monomers, and N-substituted maleimide monomers.

The (C-3) is preferably used in an amount of 1 to 80% by weight, more preferably 10 to 50% by weight in the component (C). 1% by weight or more is preferable from the viewpoint of crosslinkability, and 80% by weight is preferable from the viewpoint of mechanical strength.
In the present invention, the most preferable combination of the crosslinking agent (C) is 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (trade name Perhexa 25B, manufactured by NOF Corporation as a crosslinking initiator. ) Or Nippon Oil & Fats Co., Ltd., 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and polyfunctional monomer, manufactured by Nippon Kasei Co., Ltd., triallyl isocyanurate (TAIC) Is excellent in mechanical strength and (D) retention when (D) described later is present.

Component (D) The component (D) is preferably a process oil composed of hydrocarbons such as paraffinic, naphthenic, and aromatic. In particular, naphthenic hydrocarbon-based process oils are preferred from the viewpoint of compatibility with paraffinic hydrocarbons or rubber. From the viewpoint of heat and light stability, the aromatic hydrocarbon content in the process oil is preferably 10% or less, more preferably 5% or less, in terms of the carbon number ratio of ASTM D2140-97. Most preferably, it is 1% or less.
These components (D) are used for adjusting the hardness and flexibility of the composition in an amount of 5 to 500 parts by weight, preferably 10 to 150 parts by weight, based on a total of 100 parts by weight of (A) and (B). Within the above range, the balance between flexibility and bleed resistance is excellent.

(E) component In this invention, thermoplastic resins (E) other than (B) component can be mix | blended. (E) is not particularly limited as long as it can be dispersed with (A) and (B). For example, a polystyrene type, a polyphenylene ether type, a polyvinyl chloride type, a polyamide type, a polyester type, a polyphenylene sulfide type, a polycarbonate type, a polymethacrylate type, etc., or a mixture of two or more types can be used.
In the present invention, (E) is preferably 1 to 99 parts by weight, more preferably 10 to 90 parts by weight, most preferably 20 to 80 parts by weight based on 100 parts by weight of the composition comprising (A) and (B). Parts by weight.

In the present invention, when abrasion resistance is required, a polyorgano having a kinematic viscosity at 25 ° C. of JIS-K2410 as specified in the present invention is 5000 centistokes (5 × 10 ⁻³ m ² / sec) or more. Siloxane can be added.
The polyorganosiloxane is in the form of a viscous syrupy to gum, and is not particularly limited as long as it is a polymer containing an alkyl, vinyl and / or aryl group-substituted siloxane unit. Of these, polydimethylsiloxane is most preferred.
The kinematic viscosity (25 ° C.) of the polyorganosiloxane used in the present invention is 5000 CS (5 × 10 ⁻³ m ² / sec) or more, more preferably 10,000 CS (1 × 10 ⁻² m ² / sec). ) 10,000,000 ⁽¹⁰ m 2 / sec) below, and most preferably less than 50,000 CS (0.05m ² / sec) over 2 million ^(2m 2 / sec).

In this invention, it is preferable that the addition amount of polyorganosiloxane is 0.01-20 weight part with respect to a total of 100 weight part of (A) and (B), More preferably, it is 0.1-10. Parts by weight, most preferably 0.5 to 5 parts by weight.
Among the compositions of the present invention, when high-temperature rubber properties such as high-temperature compression set or mechanical strength are required, a crystal nucleating agent classified into phosphate ester-based, sorbitol-based, or carboxylate-based is used. Can be passed on.

  Specific examples of the crystal nucleating agent include 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, etc. Can be mentioned. Specific examples of the inorganic filler include aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide. , Copper oxide, tungsten oxide, etc. or complex (alloy), aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, zeolite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, hydroxide Hydrates of inorganic metal compounds such as hydrates of zirconium and tin oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate, kaolin, montmorillonite, bentonite , Ku Chromatography, mica, there may be mentioned talc, among them preferably a plate-like filler, talc, mica, kaolin is particularly preferred.

The amount of the crystallinity improver is preferably 0.01 to 200 parts by weight, more preferably 0.1 to 150 parts by weight, and most preferably 0 to 100 parts by weight of the total of (A) and (B). 0.1-100 parts by weight, very preferably 0.1-50 parts by weight.
In addition, the composition of the present invention includes other inorganic fillers, plasticizers, organic / inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicon to the extent that the characteristics are not impaired. Oils, antiblocking agents, foaming agents, antistatic agents and antibacterial agents can be contained.
For the production of the composition of the present invention, it is possible to employ a general method such as a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, etc. used for the production of ordinary resin compositions and rubber compositions. Is possible. In particular, a twin screw extruder is preferably used in order to achieve dynamic crosslinking efficiently. In the twin-screw extruder, (A) and (B) are uniformly and finely dispersed, and other components are added to cause a crosslinking reaction, thereby continuously producing the composition of the present invention. Is more suitable.

As a preferred specific example, the composition of the present invention can be produced through the following processing steps. That is, (A) and (B) are mixed well and put into a hopper of an extruder. (C) may be added from the beginning together with (A) and (B), or may be added in the middle of the extruder. The oil may be added from the middle of the extruder, or may be added separately at the beginning and midway. You may add a part of (A) and (B) from the middle of an extruder. When heated and melted and kneaded in an extruder, the above (A) and (C) undergo a crosslinking reaction, and (D) a softener is added to melt and knead so that the crosslinking reaction and kneading dispersion are sufficient. The pellet of the composition of this invention can be obtained by taking out from an extruder after that.
Further, a particularly preferable melt extrusion method is a case where a twin screw extruder having a length L in the die direction from the raw material addition portion and having an L / D of 5 to 100 (where D is a barrel diameter) is used. is there. The twin-screw extruder has a plurality of supply parts of a main feed part and a side feed part that have different distances from the tip part, and is provided between the supply parts and between the tip part and the tip part. It is preferable that a kneading portion is provided between the supply portion and the supply portion at a short distance from each other, and the length of the kneading portion is 3D to 10D, respectively.

In addition, one twin-screw extruder of the production apparatus used in the present invention may be a twin-screw co-rotating extruder or a bi-shaft counter-rotating extruder. As for the engagement of the screw, there are a non-engagement type, a partial engagement type, and a complete engagement type, and any type may be used. When applying a low shearing force to obtain a uniform resin at a low temperature, a different direction rotation / partial meshing screw is preferred. When slightly larger kneading is required, a co-rotating and complete meshing screw is preferable. When larger kneading is required, a co-rotating and fully meshing screw is preferred.
The most preferred production method of the composition of the present invention is a method in which (A) and (B) are melt-mixed and then crosslinked by (C).
The thermoplastic elastomer composition thus obtained can be produced into various molded products by an arbitrary molding method. Injection molding, extrusion molding, compression molding, blow molding, calendar molding, foam molding and the like are preferably used.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows.
(1) Judgment of crystallinity and amorphousness Measured by a differential scanning calorimetry (DSC method). Specifically, using a thermal analyzer DSC50 manufactured by Shimadzu Corporation, a 5 mg sample was heated from room temperature at 30 ° C./min in a nitrogen stream, and after reaching 200 ° C., immediately 5 ° C./min. The temperature is lowered to −100 ° C., and the crystallization peak detected at this stage is used for determination of crystallinity.
Those having no crystallization peak are determined to be amorphous.
(2) Tensile breaking strength [MPa]
Evaluation was performed at 23 ° C. according to JIS K6251.
(3) Continuous productivity (quality stability)
Using a twin-screw extruder, the composition is continuously melt extruded for 10 hours, and the tensile breaking strength is measured from the composition obtained every hour, and the continuous productivity (quality stability) is evaluated from the strength change. did. The difference between the maximum and minimum tensile rupture strength at 10 hours was used as an indicator of continuous productivity.

The following were used for each component used in Examples and Comparative Examples.
(A) Crosslinkable rubbery polymer 1) Ethylene / α-olefin copolymer a) Ethylene / propylene / ethylidene norbornene (ENB) copolymer (TPE-1)
It is produced by a method using a metallocene catalyst described in JP-A-3-163088. The composition ratio of ethylene / propylene / ENB of the copolymer is 72/24/4 (weight ratio), and the Mooney viscosity is 100. (Referred to as TPE-1)
b) Ethylene / propylene / ethylidenenorbornene (ENB) copolymer (TPE-2)
It is produced by a method using an ordinary Ziegler catalyst. The composition ratio of ethylene / propylene / ENB of the copolymer is 72/24/4 (weight ratio), and the Mooney viscosity is 105. (Referred to as TPE-2)
c) Copolymer of ethylene and octene-1 (TPE-3)
It is produced by a method using a metallocene catalyst described in JP-A-3-163088. The composition ratio of ethylene / octene-1 in the copolymer is 72/28 (weight ratio), and the Mooney viscosity is 100. (Referred to as TPE-3)

2) Hydrogenated conjugated diene rubber a) Hydrogenated butadiene polymer The hydrogenated butadiene polymer is produced by hydrogenating a butadiene polymer based on the method described in WO01 / 48079. The Mooney viscosity is 100. (Referred to as H-BR)
b) Hydrogenated Styrene / Butadiene Copolymer A styrene / butadiene copolymer is produced by hydrogenation based on the method described in WO01 / 48079. The styrene / butadiene composition ratio of the precursor copolymer is 70/30 (weight ratio), and the Mooney viscosity is 100. (Referred to as H-SBR)

(B) Olefin polymer (1) Amorphous polypropylene (a-PP)
It is produced by the method described in JP-A-9-309982.

The amorphous state is confirmed by DSC and is referred to as a-PP.
(2) Crystalline polypropylene (c-PP)
Commercially available isotactic homopolypropylene (referred to as c-PP)
(C) Crosslinking agent 1) Crosslinking initiator (C-1)
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (referred to as POX)
2) Polyfunctional monomer (C-2)
Triallyl isocyanurate (referred to as TAIC)

[Examples 1-8 and Comparative Examples 1-2]
As the extruder, a twin-screw extruder (40 mmφ, L / D = 47) having an inlet at the center of the barrel is used. As the screw, a double screw having a kneading part before and after the injection port is used.
A mixture having the composition described in Table 1 is introduced into a twin screw extruder, and melt extrusion is performed at 160 ° C. for 10 hours.
A sheet having a thickness of 2 mm is prepared from the composition thus obtained by compression molding at 200 ° C., and the mechanical properties and continuous productivity are evaluated. The results are shown in Table 1.
According to Table 1, when amorphous PP is used as the PP in the rubber and PP composition, flexibility is imparted to the composition, so that material defects are reduced, and mechanical strength variation is reduced and stable. Quality. Further, when amorphous and crystalline PP are used in combination, the mechanical strength is further improved while maintaining the quality stability. And when adding a crosslinked structure to a composition, it turns out that one layer mechanical strength and quality stability improve.

  The olefin polymer composition of the present invention includes automotive parts, automotive interior materials, airbag covers, machine parts, electrical parts, cables, hoses, belts, toys, miscellaneous goods, daily necessities, building materials, sheets, films and the like. It can be used in a wide range of applications and plays a major role in the industry.

Claims (7)

  It consists of a crosslinkable rubber-like polymer (A) and an olefin polymer (B), and the component (B) comprises the amorphous olefin polymer (B-1) as an essential component, and if necessary, a crystalline olefin An olefin polymer composition comprising a polymer (B-2).   The olefin polymer composition according to claim 1, wherein the olefin polymer composition is crosslinked comprising the component (A) and the component (B).   (A) An ethylene / α-olefin copolymer (A-1) produced using a metallocene catalyst, wherein the component contains ethylene and an α-olefin having 3 to 20 carbon atoms, or two in the main chain and side chain One or more types of crosslinkability selected from hydrogenated rubber (A-2) in which 50% or more of all olefinic double bonds of unsaturated rubber comprising a homopolymer and / or copolymer having a heavy bond are hydrogenated. The olefin polymer composition according to claim 1, which is a rubber-like polymer.   The olefin polymer composition according to any one of claims 1 to 3, wherein the component (B-1) is produced using a metallocene catalyst.   (B) A component is a propylene polymer, The olefin polymer composition in any one of Claims 1-4.   The olefin polymer composition according to any one of claims 2 to 5, which is crosslinked with a crosslinking agent (C).   Furthermore, the olefin polymer composition in any one of Claims 1-6 containing the agent (D) chosen from a softening agent, polyorganosiloxane, and a crystallinity improvement agent.