JP2007126594A - Olefinic polymer composition of good productivity - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefinic polymer composition excellent in continuous productivity and mechanical strengths. <P>SOLUTION: The crosslinked olefinic polymer composition comprises a rubbery polymer (A) comprising, as an essential ingredient, an ethylene/&alpha;-olefin copolymer (A-1) that is comprised of ethylene and a 3-20C &alpha;-olefin and prepared using a metallocene catalyst and has a melt flow rate (MFR, measured under a condition of 190&deg;C/10 kg) prescribed by ASTM D-1238 of 100-2,000 g/10 min, and, as occasions demand, a rubbery polymer (A-2) other than (A-1), and an olefinic resin (B). <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 (see Patent Documents 1 and 2 below) 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 continuous productivity and mechanical strength, for example, an ethylene / α-olefin copolymer having high fluidity (see Patent Document 3 below) is disclosed, but it is not crosslinked. Therefore, since durability and heat resistance are not sufficient, an olefin polymer composition that can withstand practical use is required in the industry.

JP-A-8-120127 Japanese Patent Laid-Open No. 9-137001 Japanese Patent No. 2963199

  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 studies to obtain an olefin polymer composition excellent in continuous productivity and mechanical strength, the present inventors surprisingly achieved continuous productivity and mechanical strength by combining specific polymers. The present invention has been completed.
That is, the present invention is an olefin polymer composition as described below.

(1) A metallocene catalyst containing ethylene and an α-olefin having 3 to 20 carbon atoms, having a melt flow rate (condition: 190 ° C./10 kg) as defined in ASTM D-1238 of 100 to 2000 g / 10 min. A crosslinked olefin polymer composition comprising a rubbery polymer (A) and an olefin resin (B) containing an ethylene / α-olefin copolymer (A-1) produced as an essential component object.
(2) The olefin polymer composition as described in (1) above, wherein the rubbery polymer (A) further contains a rubbery polymer (A-2) other than (A-1).
(3) An ethylene / α-olefin copolymer produced using a metallocene catalyst, wherein (A-2) contains ethylene and an α-olefin having 3 to 20 carbon atoms, or double in the main chain and side chain That at least 50% of the total olefinic double bonds of the unsaturated rubber composed of a homopolymer and / or copolymer having a bond is one or more rubbery polymers selected from hydrogenated rubbers hydrogenated. The olefin polymer composition as described in (1) or (2) above,
(4) The olefin polymer composition as described in any one of (1) to (3) above, wherein (B) is a propylene resin.
(5) The olefin polymer composition as described in any one of (1) to (4) above, which is crosslinked with a crosslinking agent (C).
(6) The olefin polymer composition according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of a softener (D), a polyorganosiloxane, and a crystallinity improver. object.

  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 an ethylene / α-olefin copolymer (A-1) produced using a specific metallocene catalyst as an essential component, and if necessary, a rubbery polymer other than (A-1). It consists of a rubbery polymer (A) containing (A-2) and an olefin resin (B).
Here, it is important that (A) and (B) be crosslinked while maintaining thermoplasticity. Crosslinking of the above components improves excellent mechanical properties, particularly rubber properties and durability.
And when the said melt flow rate (henceforth MFR. Condition: 190 degreeC / 10kg) of (A-1) is 100-2000g / 10min, the balance characteristic of continuous productivity and mechanical strength is remarkable. improves.
In addition, the numerical value of MFR in this specification is a value measured on condition of 190 degreeC and a 10 kg load, and this condition is described as "190 degreeC / 10kg".
Hereinafter, each component of the present invention will be described in detail.

[(A) component]
In the present invention, the rubber-like polymer (A) has an MFR defined by ASTM D-1238 (condition: 190 ° C./10 kg) of 100 to 2000 g / 10 minutes, and ethylene and α having 3 to 20 carbon atoms. -An ethylene / α-olefin copolymer (A-1) produced using a metallocene catalyst containing an olefin as an essential component, and if necessary, a rubbery polymer (A-) other than (A-1) 2).

  (A-1) in the component (A) is an ethylene / α-olefin copolymer that satisfies the above requirements, and 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.

  Moreover, (A-1) can contain the monomer which has an unsaturated bond as needed, for example, conjugated diolefins, such as butadiene and isoprene, and nonconjugated diolefins, such as 1, 4- hexadiene , Dicyclopentadiene, cyclic diene compounds such as norbornene derivatives, and acetylenes. In particular, ethylidene norbornene (ENB) and dicyclopentadiene (DCP) are most preferable.

The ethylene / α-olefin copolymer in the present invention is produced using a known metallocene catalyst.
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-1) used in the present invention preferably has an α-olefin copolymerization ratio of 1 to 60% by weight, more preferably 10 to 50% by weight, most preferably Preferably it is 20 to 45 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-1) 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 composition of the present invention having excellent flexibility and low hardness can be obtained.

  The ethylene / α-olefin copolymer (A-1) 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. An ethylene / α-olefin copolymer having a long chain branch is described in Patent Document 3 (Japanese Patent No. 2963199) and the like.

  The MFR of the ethylene / α-olefin copolymer (A-1) used in the present invention is in the range of 100 to 2000 g / 10 min (190 ° C./10 kg), preferably 100 to 1000 g. / 10 minutes, more preferably 500 to 1000 g / 10 minutes. 2000 g / 10 min or less is preferable from the viewpoint of crosslinkability of the composition of the present invention, and 100 g / 10 min or more is preferable from the viewpoint of fluidity and workability.

The other component (A-2) of the component (A) in the present invention is not particularly limited as long as it is a rubbery polymer other than (A-1). For example, diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated polymer rubber (hydrogenated copolymer rubber) obtained by hydrogenating the diene rubber, isoprene rubber, chloroprene rubber, Acrylic rubber such as polybutyl acrylate, ethylene / propylene copolymer, ethylene-octene copolymer, ethylene / α-olefin copolymer such as ethylene-propylene-diene monomer terpolymer (EPDM), etc. And a crosslinked elastomer or a non-crosslinked rubber, and a thermoplastic elastomer containing the rubber component.
Further, (A-2) preferably has a glass transition temperature (Tg) of −10 ° C. or lower.
And the Mooney viscosity (ML) (ISO 289-1985 (E) conformity) measured at 100 degreeC of (A-2) has preferable 20-150, More preferably, it is 50-120.

  In the present invention, (A-2) is preferably an ethylene / α-olefin copolymer (A-2-1) produced using a metallocene catalyst, containing ethylene and an α-olefin having 3 to 20 carbon atoms. Or hydrogenated rubber in which 50% or more of all olefinic double bonds of unsaturated rubber comprising a homopolymer and / or copolymer having double bonds in the main chain and side chain are hydrogenated (A-2 -2). One or more rubbery polymers selected from the group (2).

  In the above (A-2-1), the above-mentioned MFR in (A-1) is less than 100 g / 10 min, preferably 0.001 to 99 g / 10 min, more preferably 0.1 to 50 g / min. 10 minutes, most preferably 0.1-20 g / 10 minutes. In the above range, an excellent level of crosslinking can be achieved.

In the present invention, the hydrogenated rubber of (A-2-2), which is another preferred copolymer of (A-2), is a homopolymer rubber of at least one conjugated diene monomer, or a conjugated diene. A copolymer rubber comprising a monomer and an aromatic vinyl monomer, preferably a hydrogenated copolymer rubber having a random copolymer full hydrogen bond hydrogenation rate of 50% or more, Particularly, a hydrogenated copolymer rubber in which 50% or more of all olefinic double bonds of an unsaturated polymer rubber comprising a polymer and / or copolymer having a double bond in the main chain and side chain are hydrogenated. Preferably there is.
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 rubber as (A-2-2), the vinyl bond of the conjugated diene monomer portion before hydrogenation is increased or decreased or decreased along the molecular chain even if it is present uniformly in the molecule. Alternatively, 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, and 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, a method of hydrogenation using a triisobutylborane catalyst described in FLRamp, etal, J. Amer. Chem. Soc., 83, 4672 (1961), Hung Yu Chen, J. Polym. Sci. Polym. Letter Ed , 15, 271 (1977), hydrogenation method using toluenesulfonylhydrazide, or organic cobalt-organic aluminum catalyst or organic nickel-organic aluminum catalyst described in Japanese Patent Publication No. 42-8704 Etc.

  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 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-equivalent molecular weight of 150,000 or less in the rubber-like polymer (A) is preferably 30% by weight or less, more preferably 25% or less, and still more preferably 20%. Hereinafter, it is 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-equivalent molecular weight of 150,000 or less in the rubber-like polymer (A) in the present invention, the total molecular weight is such that the portion having a molecular weight of 150,000 or less is 30% or less Or a method of removing a portion 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.
In the present invention, it is extremely preferable that (A) is a combination of (A-1) and (A-2) in view of the balance between the high crosslinking level and the moldability.

[Component (B)]
The olefin resin (B) in the present invention is a homopolymer resin or copolymer resin containing ethylene or / and α-olefin alone or in combination of 2 to 20 carbon atoms such as ethylene or propylene resin. In particular, a propylene resin is preferable.
Specific examples of the propylene-based resin most preferably used in the present invention include homoisotactic polypropylene, propylene, and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1. And isotactic copolymer resins (including blocks and random).

  In the present invention, among the components (B), (B-1) a propylene random copolymer resin alone such as a random copolymer resin of ethylene and propylene, which is a cross-linked olefin resin, or (B-1) and ( B-2) A combination with a propylene block copolymer resin or a homopolypropylene resin which is a decomposable olefin resin is preferred. The appearance and mechanical strength are further improved by combining two types of olefin resins, such as a crosslinked olefin resin and a decomposable olefin resin.

Examples of (B-1) include a random copolymer resin of ethylene and propylene. When the ethylene component is present in the polymer main chain, it becomes a cross-linking point of the cross-linking reaction, and Show properties.
(B-2) is mainly composed of an α-olefin, and preferably contains no ethylene unit in the polymer main chain. However, when an ethylene-α olefin copolymer is present as a dispersed phase, such as a propylene block copolymer resin, the characteristics of the decomposable olefin resin are exhibited.

(B) may be a combination of a plurality of components (B-1) and (B-2).
Random copolymer resin with α-olefin mainly composed of propylene among (B-1) can be produced by high pressure method, slurry method, gas phase method, bulk method, solution method, etc. As the catalyst, Ziegler-Natta catalyst, single site, metallocene catalyst is preferable. In particular, when a narrow composition distribution and molecular weight distribution are required, a random copolymerization method using a metallocene catalyst is preferable.

  A specific method for producing a random copolymer resin is disclosed in European Patent Application No. 969043 or US Pat. No. 5,1984,401, and after introducing propylene into a reactor equipped with a stirrer, the catalyst is discharged from a nozzle. Add to gas phase or liquid phase. 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.

  In addition, the above (B) can contain an amorphous olefin polymer having neither a crystal melting peak nor a crystallization peak of 1 J / g or more when measured with a differential scanning calorimeter (DSC), Examples thereof include amorphous polypropylene, and amorphous olefin copolymers of propylene and other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1.

  And the thing of the range of 0.1-100 g / 10min (190 degreeC / 10kg) is preferably used for MFR of the olefin resin used suitably by this invention. 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.

In the present invention, each component in 100 parts by weight of the composition comprising (A) and (B), (A) is preferably 1 to 99% by weight, more preferably 10 to 80% by weight, most preferably 20 to 70% by weight, and (B) is preferably 1 to 99% by weight, more preferably 90 to 20% by weight, and most preferably 80 to 30% by weight. Within the above range, the balance between injection moldability and scratch resistance is improved.
In the present invention, the composition comprising (A) and (B) may be one obtained by melting and mixing separate (A) and (B) with an extruder, and (A) and (B). May be a polymerizable composition produced during polymerization. Such a polymerizable composition is a thermoplastic elastomer produced by a polymerization method comprising a dispersed phase of olefinic rubber and a continuous phase of olefinic resin. Usually, it is produced by a multistage polymerization method.
In the present invention, the multistage polymerization method means a polymerization method in which a plurality of types of polymers can be continuously produced by performing multistage polymerization of two or more stages, instead of completing the polymerization once. However, this method is different from the usual polymer blending method in which a mixed resin composed of different kinds of polymers is obtained using a mechanical method.

  The olefinic crosslinkable rubber composition obtained by the multistage polymerization method is a copolymer obtained by multistage polymerization of (1) hard segment and (2) soft segment in a reactor. (1) The hard segment is typically a propylene homopolymer block or a copolymer block of propylene and an α-olefin, such as propylene / ethylene, propylene / 1-butene, propylene / ethylene / 1- Examples include binary or ternary copolymer blocks such as butene. The (2) soft segment is typically an ethylene homopolymer block and a copolymer block of ethylene and α-olefin, such as ethylene / propylene, ethylene / 1-butene, ethylene / propylene / 1-butene. Binary or ternary copolymer blocks such as

[Component (C)]
The composition of the present invention is preferably crosslinked with (C) a 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 Diacyl peroxides such as peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5 -Peroxyesters such as dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate; and t-butylhydro Hydroperoxides such as peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide To mention That.

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'-dibenzoyldioxime, 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 (C) crosslinking agents 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.

[(D) component]
The composition of this invention can contain a softening agent (D) as needed. As the component (D), a process oil composed of hydrocarbons such as paraffinic, naphthenic and aromatic is preferable. 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 the present invention, a thermoplastic resin (E) other than the component (B) can be 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 of the polyorganosiloxane used in the present invention (25 ° C.) are, 5000CS is a (5 × 10-3m ² / sec) or more, more preferably 10,000 ^{CS (1 × 10 -2 m 2} / sec) 10,000,000 ^(10m 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, the crystallinity improvers classified into phosphate ester salts, sorbitols, and carboxylates Can be added.
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 portions of a main feed portion and a side feed portion that are different in distance from the tip portion, and is provided between the plurality of supply portions and between the tip portion and the above It is preferable that a needing portion is provided between the tip portion and the supply portion at a short distance, and the length of the needing portion is 3D to 10D.

  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 screws, 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 type screw is preferred. When slightly larger kneading is required, the same-direction rotating / completely meshing type screw is preferable. When larger kneading is required, a co-rotating and fully meshing screw is preferable.

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) Tensile strength at break [MPa]
Evaluation was performed at 23 ° C. according to JIS K6251.
(2) 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. It shows that continuous productivity is so favorable that the value is small.

The following were used for each component used in Examples and Comparative Examples.
(A-1) Component 1) Copolymer of ethylene and octene-1 (EO)
Manufactured by a method using a metallocene catalyst described in Japanese Patent No. 2963199, and MFR is variously changed at that time. However, the composition ratio of ethylene / octene-1 in the copolymer is constant at 72/28 (weight ratio).

(A-2) Component 1) Ethylene / α-olefin copolymer
a) Ethylene / propylene / ethylidene norbornene (ENB) copolymer (TPE-1)
It was produced by a method using a metallocene catalyst described in JP-A-3-16388. The composition ratio of ethylene / propylene / ENB of the copolymer is 72/24/4 (weight ratio), and the MFR is 3. (Referred to as TPE-1)
b) Ethylene / propylene / ethylidenenorbornene (ENB) copolymer (TPE-2)
It was 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 MFR is 3. (Referred to as TPE-2)
c) Copolymer of ethylene and octene-1 (TPE-3)
It was produced by a method using a metallocene catalyst described in JP-A-3-16388. The composition ratio of ethylene / octene-1 in the copolymer is 72/28 (weight ratio), and the MFR is 3. (Referred to as TPE-3)

2) Hydrogenated conjugated diene rubber a) Hydrogenated butadiene polymer This was produced by hydrogenating a butadiene polymer based on the method described in WO 01/48079. The Mooney viscosity is 100. (Referred to as H-BR)
b) Hydrogenated Styrene / Butadiene Copolymer A styrene / butadiene copolymer was produced by hydrogenation based on the method described in WO 01/48079. 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) Component 1) Polypropylene (PP)
Commercially available isotactic homopolypropylene (referred to as PP)
(C) Component 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 to 9 and Comparative Examples 1 to 4]
A twin screw extruder (40 mmφ, L / D = 47) was used as the extruder. A double screw was used as the screw.
The mixture having the composition shown in Table 1 was introduced into a twin-screw extruder, and melt extrusion was performed at 160 ° C. for 10 hours.
A sheet having a thickness of 2 mm was prepared from the composition thus obtained by compression molding at 200 ° C., and mechanical characteristics and continuous productivity were evaluated.
The results are shown in Table 1.

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

Claims (6)

  Manufactured using a metallocene catalyst containing ethylene and an α-olefin having 3 to 20 carbon atoms having a melt flow rate (condition: 190 ° C./10 kg) as defined in ASTM D-1238 of 100 to 2000 g / 10 min. A crosslinked olefin polymer composition comprising a rubbery polymer (A) and an olefin resin (B) containing the ethylene / α-olefin copolymer (A-1) as an essential component. The olefin polymer composition according to claim 1, wherein the rubber-like polymer (A) further contains a rubber-like polymer (A-2) other than (A-1).   (A-2) contains ethylene and an α-olefin having 3 to 20 carbon atoms, an ethylene / α-olefin copolymer produced using a metallocene catalyst, or a double chain in the main chain and side chain 50% or more of all olefinic double bonds of an unsaturated rubber made of a homopolymer and / or a copolymer is one or more rubbery polymers selected from hydrogenated rubbers hydrogenated. The olefin polymer composition according to claim 1 or 2.   The olefin polymer composition according to any one of claims 1 to 3, wherein (B) is a propylene resin.   The olefin polymer composition according to any one of claims 1 to 4, which is crosslinked with a crosslinking agent (C). The olefin polymer composition according to claim 1, further comprising at least one selected from the group consisting of a softener (D), a polyorganosiloxane, and a crystallinity improver.