JP2005298726A - Polypropylene-based resin composition and molded product made therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polypropylene-based resin composition having high mechanical strengths and impact resistance and also excellent in the effects of modifying these properties, and to provide a molded product made therefrom. <P>SOLUTION: A resin composition is provided, comprising the polypropylene-based resin composition (MB) that comprises 20-70 wt.% of a high molecular weight polypropylene (A) 6-12 dL/g in intrinsic viscosity [η] in 135°C decalin and 30-80 wt.% of an elastomer (D). The molded product made from this resin composition is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a polypropylene-based resin composition, and more particularly to a polypropylene-based resin composition excellent in the effect of modifying strength and impact resistance, and a molded article made of the composition.

  Polypropylene has a wide range of uses as a material excellent in rigidity and impact resistance as a thermoplastic resin. In particular, so-called compound materials in which polypropylene resin is reinforced with an inorganic filler are widely used in the field of industrial material parts such as automobile parts and household appliance parts. However, in order to develop polypropylene compound materials for use in automotive exterior parts such as fenders, it is still impossible to satisfy the required characteristics in terms of strength, rigidity, impact resistance and weight reduction.

  In JP-A-6-57055 and JP-A-6-41814, a resin composition composed of ultrahigh molecular weight polypropylene is proposed as a high-strength polymer, but its use is limited to fibers because the molecular weight is too high. .

Japanese Patent Application Laid-Open No. 6-2347812 proposes a molded article made of an ultrahigh molecular weight polypropylene resin composition, but its fluidity is too low for structural component application.
On the other hand, Japanese Patent Application Laid-Open Nos. 2000-226478 and WO98 / 47995 propose polypropylene having a high-strength polypropylene resin composition and partly containing an ultra-high molecular weight component, but automobile exterior parts such as fenders and door panels. Both mechanical strength and impact resistance are insufficient for the application.
JP-A-6-57055 JP-A-6-41814 JP-A-6-2347812 JP 2000-226478 A WO98 / 47959

  An object of the present invention is to provide a polypropylene resin composition excellent in strength and impact resistance, and excellent in strength and impact resistance modification effects, and a molded product thereof.

As a result of intensive studies, the present inventors have found that the following means [1] to [15] can solve the above problems, and have completed the present invention.
[1] A polypropylene resin composition comprising 20 to 70% by weight of ultrahigh molecular weight polypropylene (A) having an intrinsic viscosity [η] in 135 ° C. decalin of 6 to 12 dl / g and 30 to 80% by weight of elastomer (D) (MB).
[2] In the polypropylene resin composition (MB) of [1] above, the amount of elution component of orthodichlorobenzene (ODCB) at 80 ° C. or less is 30 to 80% by weight, 80 to 80% in the cross fractionation chromatograph (CFC). A polypropylene resin composition (MB ₁ ) having an elution component amount at 135 ° C. of 20 to 70% by weight and a weight average molecular weight Mw of the elution component of 80 to 135 ° C. being 10 ⁶ or more.
[3] Polypropylene resin composition (MB) of [1] to [2] above, wherein the storage elastic modulus G ′ at 1 Hz measured by 220 ° C. melt dynamic viscoelasticity is 3 × 10 ⁴ Pa or more -Based resin composition (MB ₂ ).
[4] A polypropylene resin composition comprising a polypropylene resin composition (MB) and a polypropylene resin (B).
[5] A polypropylene resin composition comprising a polypropylene resin composition (MB) and an elastomer (E).
[6] A polypropylene resin composition comprising a polypropylene resin composition (MB) and an inorganic filler (F).
[7] A polypropylene resin composition comprising a polypropylene resin composition (MB), a polypropylene resin (B), and an elastomer (E).
[8] A polypropylene resin composition comprising a polypropylene resin composition (MB), a polypropylene resin (B), and an inorganic filler (F).
[9] A polypropylene resin composition comprising a polypropylene resin composition (MB), an elastomer (E), and an inorganic filler (F).
[10] A polypropylene resin composition comprising a polypropylene resin composition (MB), a polypropylene resin (B), an elastomer (E), and an inorganic filler (F).
[11] A sheet obtained by molding the polypropylene resin composition described in [1] to [10].
[12] A film obtained by molding the polypropylene resin composition described in [1] to [10] above.
[13] A hollow container obtained by molding the polypropylene resin composition described in [1] to [10] above.
[14] An extruded product obtained by molding the polypropylene resin composition described in [1] to [10] above.
[15] An injection-molded product obtained by molding the polypropylene resin composition described in [1] to [10] above.

According to the present invention, it is possible to obtain a polypropylene resin composition and a polypropylene-based molded article having excellent strength and good impact resistance.

  Hereinafter, the present invention will be described in detail. First, each component which comprises the resin composition of this invention is explained in full detail.

Ultra high molecular weight polypropylene (A)
The ultrahigh molecular weight polypropylene (A) used in the present invention may be a propylene homopolymer or a copolymer with a small amount of other monomers, but a propylene homopolymer is preferred. In the case of a copolymer, it may be a random copolymer or a block copolymer.

  The ultra high molecular weight polypropylene (A) used in the present invention is an ultra high molecular weight polypropylene having a melting point (Tm) measured by a differential scanning calorimeter (DSC) of 150 to 170 ° C., preferably 155 to 170 ° C. The ultrahigh molecular weight polypropylene (A) used in the present invention has an intrinsic viscosity [η] measured in decalin (decahydronaphthalene) at 135 ° C. of 6 to 12 dl / g, preferably 6 to 10 dl / g. Polypropylene.

  In the ultra high molecular weight polypropylene (A), the content of other monomers copolymerized with propylene is usually 10% by weight or less, preferably 5% by weight or less. Examples of other monomers include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, Α-olefins having 2 to 20 carbon atoms such as 1-decene and 1-dodecene, preferably 2 to 10; vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane and vinylnorbornane; vinyl esters such as vinyl acetate; maleic anhydride Unsaturated organic acids or derivatives thereof; conjugated dienes; non-conjugated polyenes such as dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene. Two or more of these may be copolymerized.

  Ultra high molecular weight polypropylene (A) is a branched olefin such as 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 -Methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene , 3-ethyl-1-hexene, 3,5,5-trimethyl-1-hexene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylnorbornane, allylnorbornane, styrene, dimethylstyrene, allylbenzene, allyltoluene, allyl A homopolymer or copolymer such as naphthalene or vinyl naphthalene is used as a prepolymer and is 0.1% by weight or less, Mashiku may contain 0.05 wt% or less. Among these, 3-methyl-1-butene is particularly preferable. Since the prepolymer derived from such branched olefins acts as a nucleating agent for polypropylene, the degree of crystallinity can be increased and the moldability can be improved.

  The ultra high molecular weight polypropylene (A) is produced by a known method in the presence of a known catalyst such as a Ziegler-Natta catalyst composed of titanium trichloride and an alkylaluminum compound, or a composite catalyst composed of a magnesium compound and a titanium compound. be able to. As a preferable production method, for example, a method of producing propylene alone or by polymerizing propylene and another monomer by two-stage polymerization in the presence of a catalyst for producing a highly stereoregular polypropylene can be exemplified.

  Examples of the highly stereoregular polypropylene production catalyst include (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor, (b) an organometallic compound, and (c) an electron donor. The catalyst which consists of these can be used. The solid titanium catalyst component (a) as described above can be prepared by contacting the magnesium compound (a-1), the titanium compound (a-2) and the electron donor (a-3).

  Examples of the magnesium compound (a-1) include a magnesium compound having a reducing ability and a magnesium compound not having a reducing ability. Examples of the magnesium compound having a reducing ability include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specifically, dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy Examples thereof include magnesium, ethyl butyl magnesium, butyl magnesium hydride and the like.

  Examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy Alkoxymagnesium halides such as magnesium chloride; Allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; Alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; Allyloxymagnes such as phenoxymagnesium and dimethylphenoxymagnesium Um; magnesium laurate, it may be mentioned carboxylic acid salts of magnesium such as magnesium stearate.

  These magnesium compounds having no reducing ability may be compounds derived from magnesium compounds having reducing ability, or compounds derived at the time of preparation of the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having a reducing ability, for example, a magnesium compound having a reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen, and the like. What is necessary is just to make it contact with the compound which has active carbon-oxygen bonds, such as a containing compound and a ketone.

  The magnesium compound (a-1) can also be derived from magnesium metal during catalyst preparation. A magnesium compound (a-1) can also be used in combination of 2 or more types. The magnesium compound (a-1) as described above may form a complex compound or a complex compound with other metals such as aluminum, zinc, boron, beryllium, sodium, potassium, or other metal compounds. And a mixture thereof.

  In the present invention, many magnesium compounds can be used in addition to those described above. However, in the finally obtained solid titanium catalyst component (a), it is preferable to take the form of a halogen-containing magnesium compound, and thus a halogen is contained. In the case of using a magnesium compound that is not present, it is preferable to cause a contact reaction with a halogen-containing compound in the course of preparing the catalyst component.

  Among these, magnesium compounds having no reducing ability are preferable, halogen-containing magnesium compounds are more preferable, and magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are particularly preferable. In the present invention, when preparing the catalyst component, the magnesium compound (a-1) is preferably used in a liquid state. Among the magnesium compounds (a-1), the magnesium compound (a-1) is solid. In some cases, an electron donor can be used to bring the liquid state.

  Examples of the liquefying agent include alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and the like as described later as electron donors, tetraethoxy titanium, tetra-n-propoxy titanium, tetra- Metal acid esters such as i-propoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium, and tetraethoxy zirconium can also be used. Among these, alcohols and metal acid esters are particularly preferably used.

  The liquefaction reaction of the solid magnesium compound (a-1) is generally performed by bringing the solid magnesium compound and the liquefying agent into contact with each other and heating as necessary. This contact is usually performed at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C. In this liquefaction reaction, a hydrocarbon solvent or the like may coexist. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, kerosene; cyclopentane, methylcyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclohexane, cyclooctane, and cyclohexene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, and chlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene are used.

  When preparing the solid titanium catalyst component (a), it is preferable to use, for example, a tetravalent titanium compound represented by the following formula (1) as the titanium compound (a-2).

Ti (OR) _g X _4-g (1)
(In the formula (1), R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.)
Specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H ₉ ) Br ₃ and other trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl _{2, Ti (O-n-} C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) _{3 Cl, Ti (O-n} -C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H 5) 4 , Ti (O-n-C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4, Ti (O-2- ethylhexyl) ₄ tetraalkoxy titanium such as And the like. Among these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. Two or more types of titanium compounds (a-2) can be used in combination. In addition, the titanium compound (a-2) can be diluted with a hydrocarbon compound, a halogenated hydrocarbon compound, or the like.

  Examples of the electron donor (a-3) used in the preparation of the solid titanium catalyst component (a) include alcohols, phenols, ketones, aldehydes, esters of organic acids or inorganic acids, organic acid halides, ethers, acids. Examples include amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, and oxygen-containing cyclic compounds. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol; acetone Ketones having 3 to 15 carbon atoms such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone, and benzoquinone; Acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, aldehydes having 2 to 15 carbon atoms such as naphthaldehyde and the like.

  Also methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, cyclohexane Ethyl carboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate Ethyl acetate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexylcyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diiphthalate C2-C30 organic acid esters such as butyl, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate; acetyl chloride, benzoyl chloride, toluyl C2-C15 acid halides such as acid chloride and anisyl chloride; C2-C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-menthane Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride; methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, Amines such as xamethylenediamine, tributylamine and tribenzylamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole, pyrroline, pyrrolidine, indole, pyridine, methylpyridine, ethyl Pyridines such as pyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridine chloride, nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,4-cineole 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran Cyclic oxygen-containing compounds such as dihydropyran and the like.

  As the organic acid ester used as the electron donor (a-3), a polyvalent carboxylic acid ester having a skeleton represented by the following formula (2) can be given as a particularly preferred example.

In the formula (2), R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or unsubstituted group. Preferably, at least one of them is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a cyclic structure. Substituents in the case where the hydrocarbon groups R ^{1 to} R ⁶ are substituted include hetero atoms such as N, O, and S, such as C—O—C, COOR, COOH, OH, SO ₃ H, —C It has a group such as —N—C— or NH ₂ .

  Specific examples of such polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, and butyl. Diethyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, ethyl succinate Aliphatic polycarboxylic acid esters such as diallyl acid, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid; diethyl 1,2-cyclohexanecarboxylate, 1,2-cis Alicyclic polycarboxylic acid esters such as diisobutyl chlorohexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate , Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, Aromatic polycarboxylic acid esters such as didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitic acid, dibutyl trimellitic acid; Cross section ring poly carboxylic acid ester, and the like, such as Njikarubon acid, and the like.

  Examples of polycarboxylic acid esters include esters of long-chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Etc. can also be given.

  Further, as the electron donor (a-3), an organic silicon compound or a polyether compound, which will be described later, used as the electron donor of the component (c), water, an anionic, cationic or nonionic surfactant, etc. Can also be used. As the electron donor (a-3), it is preferable to use a carboxylic acid ester, and it is particularly preferable to use a polyvalent carboxylic acid ester, particularly a phthalic acid ester. Two or more electron donors (a-3) can be used in combination.

When contacting the titanium compound (a-2), magnesium compound (a-1) and electron donor (a-3) as described above, other reaction reagents such as silicon, phosphorus, and aluminum are allowed to coexist. In addition, a carrier-supporting solid titanium catalyst component (a) can be prepared using a carrier. Examples of such carriers include resins such as Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer. . Among these, Al ₂ O ₃ , SiO ₂ , and styrene-divinylbenzene copolymer are preferably used.

The solid titanium catalyst component (a) can be prepared by adopting any method including known methods, but a few examples will be briefly described below.
(1) A hydrocarbon solution of a magnesium compound (a-1) containing an electron donor (liquefaction agent) (a-3) is contacted with an organometallic compound to precipitate a solid, or while depositing A method of causing a contact reaction with the titanium compound (a-2).
(2) A method in which a complex composed of a magnesium compound (a-1) and an electron donor (a-3) is contacted and reacted with an organometallic compound, and then a titanium compound (a-2) is contacted and reacted.
(3) A method in which a titanium compound (a-2) and an electron donor (a-3) are contact-reacted with a contact product between an inorganic carrier and an organomagnesium compound (a-1). At this time, the contact product may be previously contacted with the halogen-containing compound and / or the organometallic compound.
(4) A carrier carrying a magnesium compound (a-1) from a mixture of a liquefying agent and optionally a magnesium compound (a-1) solution containing a hydrocarbon solvent, an electron donor (a-3) and a carrier Then, the titanium compound (a-2) is then contacted.
(5) A method of contacting a carrier with a solution containing a magnesium compound (a-1), a titanium compound (a-2), an electron donor (a-3), and optionally a hydrocarbon solvent.
(6) A method of bringing the liquid organomagnesium compound (a-1) into contact with the halogen-containing titanium compound (a-2). At this time, the electron donor (a-3) is used at least once.
(7) A method in which the liquid organomagnesium compound (a-1) and the halogen-containing compound are contacted, and then the titanium compound (a-2) is contacted. In this process, the electron donor (a-3) is used at least once.
(8) A method of bringing the alkoxy group-containing magnesium compound (a-1) into contact with the halogen-containing titanium compound (a-2). At this time, the electron donor (a-3) is used at least once.
(9) A method of contacting a complex comprising an alkoxy group-containing magnesium compound (a-1) and an electron donor (a-3) with a titanium compound (a-2).
(10) A method in which a complex comprising an alkoxy group-containing magnesium compound (a-1) and an electron donor (a-3) is contacted with an organometallic compound and then contacted with a titanium compound (a-2).
(11) A method in which a magnesium compound (a-1), an electron donor (a-3), and a titanium compound (a-2) are contacted and reacted in an arbitrary order. Prior to this reaction, each component may be pretreated with a reaction aid such as an electron donor (a-3), an organometallic compound, or a halogen-containing silicon compound.
(12) A solid magnesium obtained by reacting a liquid magnesium compound (a-1) having no reducing ability with a liquid titanium compound (a-2) in the presence of an electron donor (a-3) -A method of depositing a titanium composite.
(13) A method of further reacting the titanium compound (a-2) with the reaction product obtained in (12) above.
(14) A method in which the reaction product obtained in (11) or (12) is further reacted with an electron donor (a-3) and a titanium compound (a-2).
(15) A solid material obtained by pulverizing a magnesium compound (a-1), an electron donor (a-3), and a titanium compound (a-2) is converted into a halogen, a halogen compound, or an aromatic carbonization. A method of treatment with any of hydrogen. In this method, only the magnesium compound (a-1), a complex compound composed of the magnesium compound (a-1) and the electron donor (a-3), or the magnesium compound (a-1) and titanium are used. You may include the process of grind | pulverizing a compound (a-2). Further, after the pulverization, it may be pretreated with a reaction aid and then treated with halogen or the like. As the reaction aid, an organometallic compound or a halogen-containing silicon compound is used.
(16) A method of contacting the titanium compound (a-2) after pulverizing the magnesium compound (a-1). When the magnesium compound (a-1) is pulverized and / or contacted, the electron donor (a-3) is used together with a reaction aid as necessary.
(17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon.
(18) A method in which a contact reaction product of a metal oxide, organomagnesium (a-1) and a halogen-containing compound is brought into contact with an electron donor (a-3) and preferably a titanium compound (a-2).
(19) Magnesium compounds (a-1) such as magnesium salts of organic acids, alkoxymagnesium and aryloxymagnesium, titanium compounds (a-2), electron donors (a-3), and optionally halogen-containing carbonization Method of contacting with hydrogen.
(20) A method of contacting a hydrocarbon solution containing a magnesium compound (a-1) and an alkoxytitanium with an electron donor (a-3) and, if necessary, a titanium compound (a-2). In this case, it is preferable that a halogen-containing compound such as a halogen-containing silicon compound coexists.
(21) A liquid magnesium compound (a-1) having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium / metal (aluminum) complex, and then an electron donor (a -3) and a method of reacting the titanium compound (a-2).

  The amount of each component used for contact varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor (a-3) is preferably 0.01 to 10 moles per mole of the magnesium compound (a-1). Is used in an amount of 0.1 to 5 mol, and the titanium compound (a-2) is used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol.

  The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor. In this solid titanium catalyst component (a), halogen / titanium (atomic ratio) is About 2 to 200, preferably about 4 to 100, electron donor / titanium (molar ratio) is about 0.01 to 100, preferably about 0.02 to 10, and magnesium / titanium (atomic ratio) is Desirably it is about 1-100, preferably about 2-50.

  As the organometallic compound (b) used together with the solid titanium catalyst component (a), those containing a metal selected from Group I to Group III of the periodic table are preferable. Examples thereof include aluminum compounds, complex alkyl compounds of Group I metals and aluminum, and organometallic compounds of Group II metals.

Formula: R ¹ _m Al (OR ² ) _n H _p X _q (wherein R ¹ and R ² are hydrocarbon groups usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, 0 <m <3, n is 0 <n <3, p is 0 <p <3, q is a number 0 <q <3, and m + n + p + q = 3). An organoaluminum compound (b-1).

Wherein; M ¹ AlR ¹ ₄ (. Wherein, M ¹ is a Li, Na, K, R ¹ is as defined above) Group I metals and aluminum and the alkylated complex represented by (b-2 ).

Group II or Group III dialkyl compound represented by the formula: R ¹ R ² M ² (wherein R ¹ and R ² are as defined above, and M ² is Mg, Zn or Cd) b-3).

Examples of the organoaluminum compound (b-1) include R ¹ _m Al (OR ² ) _3-m (where R ¹ and R ² are the same as described above, and m is preferably a number satisfying 1.5 ≦ m ≦ 3. A compound represented by:
A compound represented by R ¹ _m AlX _3-m (R ¹ is as defined above, X is a halogen, and m is preferably 0 <m <3);
A compound represented by R ¹ _m AlH _3-m (R ¹ is as defined above, m is preferably 2 ≦ m <3);
R ¹ _m Al (OR ² ) _n X _q (R ¹ and R ² are as defined above, X is halogen, 0 <m <3, 0 <n <3, 0 <q <3, and m + n + q = 3)) and the like.

More specifically, the organoaluminum compound (b-1) is a trialkylaluminum such as triethylaluminum or tributylaluminum; a trialkenylaluminum such as triisoprenylaluminum; a dialkylaluminum alkoxide such as diethylaluminum ethoxide or dibutylaluminum butoxide. Alkyl aluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition such as R ¹ _2.5 Al (OR ² ) _0.5 ; diethylaluminum chloride, dibutyl Dialkylaluminum halides such as aluminum chloride and diethylaluminum bromide; ethylaluminum sesquik Alkyl aluminum sesquihalides such as lolide, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Diethylaluminum Dialkylaluminum hydrides such as hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; Ethylaluminum ethoxychloride, butylaluminum butoxycyclide, ethyl Alcohol partially such as aluminum ethoxy bromide Shi reduction and halogenated alkyl aluminum, and the like.

Further, as a compound similar to (b-1), an organoaluminum compound in which two or more aluminums are bonded through an oxygen atom or a nitrogen atom can be exemplified. For example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H _{5) 2, (C 4 H} 9) 2 AlOAl (C 4 H 9) 2, (C 2 H 5) 2 AlN (C 2 H 5) Al (C 2 H 5) 2, aluminum and methyl aluminoxane Nooxans can be mentioned.

Examples of the complex alkylated product (b-2) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . As the organometallic compound (b), an organoaluminum compound (b-1), particularly a trialkylaluminum is preferably used. Two or more organometallic compounds (b) can be used in combination.

  Specific examples of the electron donor (c) used together with the solid titanium catalyst component (a) and the organometallic compound (b) include an organosilicon compound (c-1) represented by the following formula (3) or Examples thereof include a compound (c-2) having two or more ether bonds existing through a plurality of atoms.

R ¹ _n Si (OR ² ) _4-n (3)
(In the formula (3), n is 1, 2 or 3; when n is 1, R ¹ is a secondary or tertiary hydrocarbon group; and when n is 2 or 3, at least one of R ¹ Is a secondary or tertiary hydrocarbon group, R ¹ may be the same or different, R ² is a hydrocarbon group having 1 to 4 carbon atoms, and 4-n is 2 or 3 And R ² may be the same or different.)
In the organosilicon compound (c-1) represented by the formula (3), the secondary or tertiary hydrocarbon group includes a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, and a group having a substituent. Or the hydrocarbon group etc. whose carbon adjacent to Si is secondary or tertiary are mention | raise | lifted. More specifically, examples of the substituted cyclopentyl group include 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethyl group. Cyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,3,4-triethylcyclopentyl group, tetra Examples thereof include a cyclopentyl group having an alkyl group such as a methylcyclopentyl group and a tetraethylcyclopentyl group.

  Examples of the substituted cyclopentenyl group include 2-methylcyclopentenyl group, 3-methylcyclopentenyl group, 2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4- Dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethylcyclopentenyl group, 2,3,5-trimethylcyclopentenyl group, 2,3,4-triethylcyclopentenyl group, tetramethylcyclo And a cyclopentenyl group having an alkyl group such as a pentenyl group and a tetraethylcyclopentenyl group.

  Examples of the substituted cyclopentadienyl group include 2-methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2,3 -Dimethylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2,5-dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopenta Dienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4 4,5-tetraethylcyclopentadienyl group, 1,2,3,4,5-pentamethylcyclopentadienyl group, 1,2,3,4,5-pentaethyl Black cyclopentadienyl group having alkyl group such as cyclopentadienyl group.

  Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include i-propyl, s-butyl, s-amyl, α-methylbenzyl and the like. Examples of the hydrocarbon group in which the carbon is a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group, an admantyl group, and the like.

  When n is 1, the organosilicon compound (c-1) represented by the formula (3) is cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, Trialkoxysilanes such as cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, etc. I can give you.

  When n is 2, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxy Examples thereof include dialkoxysilanes such as silane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane, and dimethoxy compounds represented by the following formula (4).

In formula (4), R ¹ and R ² are each independently adjacent to a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or Si. It is a hydrocarbon group whose carbon is a secondary carbon or a tertiary carbon.

  Examples of the dimethoxy compound represented by the formula (4) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane, and di (2-methylcyclopentyl) dimethoxy. Silane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane, di (2,3-dimethylcyclopentyl) dimethoxysilane, di (2,4-dimethylcyclopentyl) dimethoxysilane, di (2, 5-dimethylcyclopentyl) dimethoxysilane, di (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethyl Xysilane, di (2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclo Pentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclo) Pentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl) dimethoxysilane, di (2,3,4-trimethylcyclopentenyl) dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysila , Di (2,3,4-triethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl) dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di ( 3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentadienyl) dimethoxy Silane, di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2 , 3,4-Trimethylcyclopentadie Nyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetra Methylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5-pentamethylcyclopentadienyl) dimethoxysilane, Di (1,2,3,4,5-pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane , Madmantyl-t-butyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, diisopropyl Methoxysilane, di -s- butyl dimethoxysilane, di -s- amyl dimethoxysilane, isopropyl -s- butyl dimethoxysilane and the like.

  In the formula (3), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyl Examples thereof include monoalkoxysilanes such as diethylmethoxysilane and cyclopentyldimethylethoxysilane.

  As the electron donor (c), dimethoxysilanes, particularly dimethoxysilanes represented by the above formula (4) are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl). ) Dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane and the like are preferable. The organosilicon compound (c-1) can be used in combination of two or more.

  In a compound having two or more ether bonds (hereinafter sometimes referred to as a polyether compound) (c-2) present via a plurality of atoms used as an electron donor (c), atoms present between ether bonds Is one or more selected from carbon, silicon, oxygen, sulfur, phosphorus and boron, and has 2 or more atoms. Among these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having 2 or more carbon atoms, preferably 3 or more and having a linear, branched or cyclic structure, more preferably a branched group. Those having a substituent having a ring-like or cyclic structure are desirable. Further, a compound in which a plurality of, preferably 3 to 20, more preferably 3 to 10, and particularly preferably 3 to 7 carbon atoms are contained in atoms present between two or more ether bonds is preferable.

  As such a polyether compound (c-2), the compound shown by following formula (5) can be mention | raise | lifted, for example.

In formula (5), n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon. Arbitrary R ^{1 to} R ²⁶ , preferably R ^{1 to} R ²ⁿ may form a ring other than a benzene ring, and atoms other than carbon are contained in the main chain. It may be.

  Specific examples of the polyether compound (c-2) represented by the formula (5) include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl- 1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3 -Dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2 (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1,3-dimethoxypropane, 2 , 2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxy Propane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl -1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl- , 3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3 -Dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl)- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2- Bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-di Isobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) ) -2-s-butyl-1,3-dimethoxypropane, 2,2-di-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2 , 2-Dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s- Butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2-s-butyl-1, -Dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl- 1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-bis (p-chlorophenyl) -1,4- Dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2, 4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1 , 3-Diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diiso Miroxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3- Dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5.5] undecane, 3,7-dioxabicyclo [3. 3.1] Nonane, 3,7-dioxabicyclo [3.3.0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclo Pentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2.2.1] heptane, , 1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxy Methyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl -1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane Methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane, cyclohexyl-t-butylbis (methoxymethyl) silane, i-propyl-t-butylbis (methoxymethyl) silane, and the like.

  Among these, 1,3-diethers are preferably used, particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 2,2-dicyclohexyl. -1,3-Dimethoxypropane and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are preferably used. Two or more kinds of polyether compounds (c-2) can be used in combination. Moreover, an organosilicon compound (c-1) and a polyether compound (c-2) can also be used together.

  Furthermore, an organosilicon compound represented by the following formula (6) can be used in combination.

R _n Si (OR ² ) _4-n (6)
(In the formula (6), R and R ² are hydrocarbon groups, and 0 <n <4. In the organosilicon compound represented by this formula, the organosilicon compound represented by the formula (3) ( c-1) is not included.)

  More specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bism -Tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltri Ethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyl Ethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethyl Examples include phenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), and vinyltriacetoxysilane. Furthermore, as a similar compound, ethyl silicate, butyl silicate, dimethyltetraethoxydicyclohexane, or the like can be used.

  In the present invention, when the polypropylene resin (A) is produced using the catalyst comprising the solid titanium catalyst component (a), the organometallic compound (b), and the electron donor (c) as described above, prepolymerization is performed in advance. Can also be done. In the prepolymerization, the olefin is polymerized in the presence of the solid titanium catalyst component (a), the organometallic compound (b), and, if necessary, the electron donor (c).

  Examples of the prepolymerized olefin include linear olefins such as ethylene, propylene, 1-butene, 1-octene, 1-hexadecene and 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene , 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, etc. Olefin having a branched structure can be used, and these can be copolymerized Good.

  Among these, as described above, branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, and dimethylstyrene are particularly preferable. Used. In particular, it is preferable to use a catalyst obtained by prepolymerizing 3-methyl-1-butene because the resulting polypropylene resin (A) has high rigidity. The prepolymerization is desirably performed so that a polymer of about 0.1 to 1000 g, preferably about 0.3 to 500 g, is produced per 1 g of the solid titanium catalyst component (a). If the amount of prepolymerization is too large, the production efficiency of the (co) polymer in the main polymerization may decrease.

  In the prepolymerization, the catalyst can be used at a considerably higher concentration than the catalyst concentration in the system in the main polymerization. The solid titanium catalyst component (a) is usually used in a concentration of about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atom per 1 liter of polymerization volume. The organometallic compound (b) is usually used in an amount of about 0.1 to 100 mmol, preferably about 0.5 to 50 mmol, per mol of titanium atom in the solid titanium catalyst component (a). The electron donor (c) may or may not be used at the time of prepolymerization, but is 0.1 to 50 mol, preferably 0.5 to 0.1 mol per mol of titanium atom in the solid titanium catalyst component (a). It can be used in an amount of 30 mol, more preferably 1 to 10 mol.

  The prepolymerization is preferably carried out under mild conditions by adding the prepolymerized olefin and the catalyst component to an inert hydrocarbon medium. Examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; benzene Aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. In particular, it is preferable to use an aliphatic hydrocarbon.

  The prepolymerization temperature may be a temperature at which the produced prepolymer does not substantially dissolve in the inert hydrocarbon medium, and is usually -20 to + 100 ° C, preferably -20 to + 80 ° C, more preferably 0. It is about +40 degreeC. The prepolymerization can be carried out batchwise or continuously. During the prepolymerization, the molecular weight can be adjusted using hydrogen or the like.

  When producing ultrahigh molecular weight polypropylene (A), the solid titanium catalyst component (a) (or prepolymerized catalyst) is converted to titanium atoms per 1 liter of polymerization volume, and is about 0.0001 to 50 mmol, preferably about 0.001. It is desirable to use in an amount of -10 mmol. The organometallic compound (b) is desirably used in an amount of about 1 to 2000 moles, preferably about 2 to 500 moles, based on 1 mole of titanium atoms in the polymerization system. The electron donor (c) is desirably used in an amount of about 0.001 to 50 moles, preferably about 0.01 to 20 moles per mole of metal atoms of the organometallic compound (b).

  A well-known method can be employ | adopted in order to manufacture ultra high molecular weight polypropylene (A) using the above catalysts. The polymerization may be performed by any of a gas phase polymerization method or a liquid phase polymerization method such as a solution polymerization method or a suspension polymerization method, and the above steps may be performed by separate methods. Moreover, you may carry out by any system of a batch type, a semi-continuous type, and a continuous type, and you may divide each said stage into several polymerizers, for example, 2-10 polymerizers.

As the polymerization medium, inert hydrocarbons may be used, and liquid propylene may be used as the polymerization medium. The polymerization conditions in each stage are such that the polymerization temperature is in the range of about −50 to 200 ° C., preferably about 20 to 100 ° C., and the polymerization pressure is normal pressure to 9.8 MPa (normal pressure to 100 kgf / cm ² , gauge pressure). ), Preferably within a range of 0.20 to 4.9 MPa (about ^{2 to} 50 kgf / cm ² , gauge pressure).

  When a prepolymerized catalyst is used, a solid titanium catalyst component (a) and an organometallic compound (b) can be newly added as necessary. The organometallic compound (b) at the time of preliminary polymerization and at the time of main polymerization may be the same or different. The electron donor (c) is always used once in either the prepolymerization or the main polymerization and is used only in the main polymerization or in both the prepolymerization and the main polymerization. The electron donor (c) at the time of preliminary polymerization and at the time of main polymerization may be the same or different. Each catalyst component as described above may not be newly added in each subsequent step performed after the completion of the polymerization in the previous stage, but may be added as appropriate. When such a catalyst is used, even when hydrogen is used during polymerization, the crystallinity or stereoregularity index of ultrahigh molecular weight polypropylene (A) does not decrease, and the catalytic activity decreases. Nor.

  In the production method as described above, the ultra high molecular weight polypropylene (A) can be produced in a high yield per unit amount of the solid titanium catalyst component (a). The halogen content can be relatively reduced. Therefore, the operation of removing the catalyst in the ultrahigh molecular weight polypropylene (A) can be omitted, and rusting occurs in the mold when the molded product is molded using the finally obtained crystalline polypropylene resin composition. Hateful.

Elastomer (D)
As the elastomer (D), ethylene / α-olefin random copolymer (D-1), ethylene / α-olefin / non-conjugated polyene random copolymer (D-2), hydrogenated block copolymer (D—) 3) Other elastic polymers and mixtures thereof.

  The ethylene / α-olefin random copolymer (D-1) is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like. These α-olefins can be used alone or in combination. Of these, propylene, 1-butene, 1-hexene and 1-octene are particularly preferably used.

    The ethylene / α-olefin random copolymer (D-1) has a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of 95/5 to 70/30, preferably 90/10 to 75/25. It is desirable that The ethylene / α-olefin random copolymer (D-1) has an MFR at 230 ° C. and a load of 21.2 N of 0.1 g / 10 min or more, preferably 0.5 to 5 g / 10 min.

    The ethylene / α-olefin / non-conjugated polyene random copolymer (D-2) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. The same thing as the above is mention | raise | lifted as said C3-C20 alpha olefin. Examples of the non-conjugated polyethylene include 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, and 5-isopropylidene-2- Acyclic dienes such as norbornene and norbornadiene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1 , 5-heptadiene, 6-methyl-1,7-octadiene, chain-like non-conjugated dienes such as 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene It is done. Among these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used.

  The ethylene / α-olefin / nonconjugated polyene random copolymer (D-2) has a molar ratio of ethylene, α-olefin and nonconjugated polyene (ethylene / α-olefin / nonconjugated polyene) of 90/5/5. 30/45/25, preferably 80/10/10 to 40/40/20.

  The ethylene / α-olefin / non-conjugated polyene random copolymer (D-2) has an MFR of 230 g and a load of 2160 g of 0.05 g / 10 min or more, preferably 0.1 to 10 g / 10 min. Specific examples of the ethylene / α-olefin / non-conjugated polyene random copolymer (D-2) include an ethylene / propylene / diene terpolymer (EPDM).

  The hydrogenated block copolymer (D-3) is a hydrogenated product of a block copolymer whose block form is represented by the following formula (I) or (II), and the hydrogenation rate is 90 mol% or more The hydrogenated block copolymer is preferably 95 mol% or more.

(In the formula, X is a block polymer unit derived from a monovinyl-substituted aromatic hydrocarbon, Y is a block polymer unit derived from a conjugated diene, and n is an integer of 1 to 5.)
Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymer block represented by X in the formula (I) or (II) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, lower alkyl-substituted styrene, vinylnaphthalene. And styrene or its derivatives. These can be used individually by 1 type, and can also be used in combination of 2 or more type.

    Examples of the conjugated diene constituting the polymer block represented by Y in the formula (I) or (II) include butadiene, isoprene, chloroprene and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more type. n is an integer of 1 to 5, preferably 1 or 2.

    Specific examples of the hydrogenated block copolymer (D-3) include styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / ethylene / propylene / styrene block copolymer (SEPS), and styrene. -Styrenic block copolymers such as ethylene / propylene block copolymer (SEP).

  The block copolymer before hydrogenation can be produced, for example, by a method in which block copolymerization is performed in an inert solvent in the presence of a lithium catalyst or a Ziegler catalyst. A detailed production method is described in, for example, Japanese Patent Publication No. 40-23798. The hydrogenation treatment can be performed in an inert solvent in the presence of a known hydrogenation catalyst. Detailed methods are described in, for example, JP-B Nos. 42-8704, 43-6636, and 46-20814.

  When butadiene is used as the conjugated diene monomer, the ratio of the 1,2-bond amount in the polybutadiene block is 20 to 80% by weight, preferably 30 to 60% by weight.

  A commercial item can also be used as a hydrogenated block copolymer (D-3). Specific examples include Kraton G1657 (trade name, manufactured by Shell Chemical Co., Ltd.), Septon 2004 (trade name, manufactured by Kuraray Co., Ltd.), Tuftec H1052 (trade name, manufactured by Asahi Kasei Corporation), and the like. The elastomeric polymer (D) can be used alone or in combination of two or more.

Polypropylene resin (MB)
The polypropylene resin composition (MB) is composed of an ultrahigh molecular weight polypropylene (A) and an elastomer (D). In the total of 100 parts by weight of both, the constituent ratio of the ultrahigh molecular weight polypropylene (A) is 20 to 70 parts by weight, preferably 30 to 65 parts by weight, and more preferably 40 to 60 parts by weight. The composition ratio of the elastomer (D) is 30 to 80 parts by weight, preferably 35 to 70 parts by weight, more preferably 40 to 60 parts by weight, in a total of 100 parts by weight of the ultrahigh molecular weight polypropylene (A) and the elastomer (D). It is.

  The method for preparing the polypropylene-based resin composition (MB) is not particularly limited, such as a melting method or a solution method, but practically a melt-kneading method is preferable. As a melt-kneading method, a kneading method generally used for thermoplastic resins can be applied.

  For example, the powdery or granular components are mixed uniformly with a Henschel mixer, a ribbon blender, a V-type blender, etc., if necessary, together with the additives described in the additional component section, and then uniaxial or multiaxial kneading. It can knead | mix with an extruder, a kneading roll, a batch kneader, a kneader, a Banbury mixer, etc.

  The melt kneading temperature of each component (for example, cylinder temperature in the case of an extruder) is usually 250 to 300 ° C, preferably 260 to 280 ° C.

  Further, the polypropylene resin (MB) in the present invention may be used as a resin composition for various molded products by adding a polypropylene resin (B), an elastomer (E), a filler (F), and other additional components. it can.

Polypropylene resin (B)
The polypropylene resin (B) in the present invention is a homopolymer of propylene, a copolymer of propylene and α-olefin, or a block copolymer of propylene and α-olefin. Specific examples of the α-olefin include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 2-ethyl-1-butene. 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl -1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1- Hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1- Ndesen, 1-dodecene, etc. can be mentioned. Of these, α-olefins of 1-butene, 1-pentene, 1-hexene and 1-octene can be preferably used.
The polypropylene resin (B) has a melting point (Tm) of 150 to 170 ° C, preferably 155 to 167 ° C. The melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the polypropylene resin (B) is usually 0.3 to 200 g / 10 minutes, preferably 2 to 150 g / 10 minutes, more preferably 10 to 100 g / 10 min.

  Polypropylene resin (B), like ultra high molecular weight polypropylene (A), is a known catalyst such as a Ziegler-Natta catalyst composed of titanium trichloride and an alkylaluminum compound, or a composite catalyst composed of a magnesium compound and a titanium compound. Below, it can manufacture by a well-known method.

Elastomer (E)
Elastomer (E), like elastomer (D), ethylene / α-olefin random copolymer (E-1), ethylene / α-olefin / non-conjugated polyene random copolymer (E-2), hydrogenated Examples thereof include a block copolymer (E-3), other elastic polymers, and mixtures thereof.

Filler (F)
Specific examples of the filler (F) used in the present invention include talc, clay, calcium carbonate, mica, silicates, carbonates, and glass fibers. Among these, talc and calcium carbonate are preferable, and talc is particularly preferable. The average particle size of talc is 1 to 5 μm, preferably 1 to 3 μm. A filler (F) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

Additional components In the resin composition of the present invention, various additives such as a dispersant, a lubricant, a plasticizer, a flame retardant, an antioxidant, and the like, within a range that does not significantly impair the purpose and effect thereof, Addition of known additives such as antistatic agents, light stabilizers, UV absorbers, modifying additives such as crystallization accelerators (nucleating agents), colorants such as pigments and dyes, carbon black and titanium oxide can do.

Composition adjustment method and molding method
The method for preparing the polypropylene resin composition in the present invention is not particularly limited, such as a melting method and a solution method, but a melt-kneading method is preferred in practice. As a melt-kneading method, a kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components are mixed uniformly with a Henschel mixer, a ribbon blender, a V-type blender, etc., if necessary, together with the additives described in the additional component section, and then uniaxial or multiaxial kneading. It can knead | mix with an extruder, a kneading roll, a batch kneader, a kneader, a Banbury mixer, etc.

The melt kneading temperature of each component (for example, cylinder temperature in the case of an extruder) is usually 220 to 300 ° C, preferably 240 to 270 ° C. Furthermore, the kneading order and method of each component are not particularly limited.
The molding method of the polypropylene resin composition of the present invention is not particularly limited, and various molding methods generally used for thermoplastic resins, that is, injection molding, extrusion molding, hollow molding, thermoforming, press molding and the like. The molding method can be applied.

The injection molded product according to the present invention can be used without any particular limitation. Specifically, automotive interior parts such as door trims and instrument panels, automotive exterior parts such as bumpers, mudguards, and fenders, hotplates, rice cookers, pot body and household appliance parts such as washing machines, and containers such as battery containers It is suitably used for medical instruments such as syringe barrels, ampules, petri dishes and the like.
There is no restriction | limiting in particular as an extrusion molded product which concerns on this invention, It can use. Specifically, daily miscellaneous goods, electrical products, stationery, toys, cosmetics, sheets for various containers such as foods, automotive interior and exterior materials, home appliances, civil engineering and construction related materials, industrial parts, medical equipment, housings, OA parts and It is suitably used for various types of sheets such as miscellaneous goods, films, extrusion molded products, and profile extrusion molded products.

  The hollow container according to the present invention can be produced using blow molding, foam molding, or vacuum molding means. Although it does not have a restriction | limiting in particular as a hollow container, It can be used suitably for a container for liquid detergents, lotions, a food container, etc. including a solid detergent container.

Confirmation of composition Formation of the polypropylene resin composition of the present invention can be confirmed by cross-fractionation chromatography (CFC) and dynamic melt viscoelasticity measurement.

In the polypropylene resin composition of the present invention, the amount of elution component of orthodichlorobenzene (ODCB) 80 ° C. or less, which is fractionated by cross-chromatography, is 30 to 80% by weight, and the amount of elution component of 80 to 135 ° C. is 20 to 70. % By weight. Here, the weight average molecular weight Mw of the eluted component at 80 to 135 ° C. is 10 ⁶ or more.
CFC was measured under the following conditions using the following apparatus equipped with a temperature rising elution fractionation (TREF) part for composition fractionation and a GPC part for molecular weight fractionation, and the weight average molecular weight (Mw) of the 121 ° C. elution component )
Measuring apparatus: CFC T-150A type, Mitsubishi Yuka Co., Ltd., trademark Column: Shodex AT-806MS (x3)
Dissolved solution: o-dichlorobenzene Flow rate: 1.0 ml / min
Sample concentration: 0.3 wt% / vol% (with 0.1% BHT)
Injection volume: 0.5ml
Solubility: Complete dissolution Detector: Infrared absorption detection method, 3.42 μ (2924 cm ⁻¹ ), NaCl plate Elution temperature: 0 to 135 ° C., 28 fractions
0, 10, 20, 30, 40, 45, 50,
55, 60, 65, 70, 75, 80, 85,
90, 94, 97, 100, 103, 106, 109,
112, 115, 118, 121, 124, 127, 135 (° C)

In addition, the resin composition of the present invention preferably has a storage elastic modulus G ′ at 1 Hz calculated from dynamic melt viscoelasticity measurement at 220 ° C. of 3 × 10 ⁴ Pa or more. The melt viscoelasticity was measured using the following apparatus and the following conditions.
Measuring device: DAR-100 (Jusco International Co., Ltd. (Rheologicala)
Made)
Measurement system: Parallel plate (diameter 1 inch φ), gap 1 mm
Measurement temperature: 220 ° C
Measurement frequency: 1 Hz
Distortion: 0.1%

[Production Example 1] Ultrahigh molecular weight polypropylene (A-1)
(1) Preliminary polymerization Charge 3liters of n-heptane into a reactor equipped with a stirrer with an internal capacity of 6liter, and 30g of solid titanium catalyst component for propylene polymerization and 10 times the titanium atom in the solid titanium catalyst component. Mole and 2,6-dimethyl-3,3-bis (methoxymethyl) heptane were fed at a ratio of 2 moles to the titanium atoms in the solid titanium catalyst component. Next, 48Nliter of propylene was charged, and the temperature in the tank was kept at 15 ° C. or lower to completely react the propylene, thereby obtaining a prepolymer. Isobutane was added thereto and diluted to 1.6 g / liter of a prepolymerized solid to prepare a prepolymer slurry.

(2) Main polymerization In a first stage reactor with an internal capacity of 600 liters, 110 kg of liquefied propylene monomer, 5 liters of prepolymer slurry obtained in (1) above, 0.14 mol of triethylaluminum, 0.14 mol of dicyclopentyldimethoxysilane Then, 5Nliter of hydrogen was charged, and polymerization was performed at a temperature of 70 ° C. for 1 hour to obtain 37 kg of ultrahigh molecular weight crystalline polypropylene (A-1) powder ([η] = 10.2 dl / g, melting point 163 ° C.).

[Production Example 2] Polypropylene resin (B-1)
A polypropylene resin (B-1) was produced according to the production method described in WO99 / 077752 Example 1-13. The intrinsic viscosity of the high molecular weight PP in the polypropylene resin (B-1) was 9.4 dl / g, and the content of the high molecular weight PP was 25 wt%. Moreover, the melt flow rate of the polypropylene resin (B-1) was 4.0 g / 10 min, and the mmmm fraction was 98.2%.

[Production Example 3] Polypropylene resin composition (MB-1)
After mixing 50 parts by weight of ultra high molecular weight polypropylene (A-1) and 50 parts by weight of hydrogenated styrene-ethylene-butadiene-styrene rubber (D3-1) (G1652: trade name, manufactured by Kraton Japan Co., Ltd.) with a tumbler, It melt-kneaded with the twin-screw extruder and prepared the pellet-shaped polypropylene resin composition (MB-1).
<Melting and kneading conditions>
Twin screw extruder: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 280 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 500 rpm

[Production Example 4] Polypropylene resin composition (MB-2)
Production Example except that 50 parts by weight of ultra high molecular weight polypropylene (A-1) and 50 parts by weight of ethylene-octene copolymer rubber (engage 8150: DuPont Dow Elastomer Co., Ltd., trademark) (D1-1) In the same manner as in Example 3, a polypropylene resin composition (MB-2) was prepared.

[Production Example 5] Polypropylene resin composition (MB-3)
Production examples except that 50 parts by weight of polypropylene resin (B101: Trademark) (B-2) manufactured by Mitsui Chemicals, Inc. and 50 parts by weight of hydrogenated styrene-ethylene-butadiene-styrene rubber (D3-1) were used. In the same manner as in Example 3, a polypropylene resin composition (MB-3) was prepared.

[Production Example 6] Polypropylene resin composition (MB-4)
Production Example except that 50 parts by weight of ultrahigh molecular weight polypropylene (A-1) and 50 parts by weight of ethylene-octene copolymer rubber (engage 8100: manufactured by DuPont Dow Elastomer Co., Ltd., trademark) (D1-2) In the same manner as in Example 3, a polypropylene resin composition (MB-4) was prepared.

In the examples and comparative examples, the test methods used for various evaluations are shown below.
(1) MFR
The MFR was measured according to ASTM D 1238 (230 ° C., load 2.16 kg).
(2) Specific gravity The specific gravity was measured according to ASTM D 792.
(3) Bending strength The bending strength was measured under the following conditions in accordance with ASTM D790.
<Measurement conditions>
Test piece: 12.7 mm (width) x 6.4 mm (thickness) x 127 mm (length)
Bending speed: 2.8 mm / min Bending span: 100 mm
Test piece thickness: 1/4 inch (4) Izod impact strength (IZ)
The Izod impact strength (IZ) was measured under the following conditions in accordance with ASTM D256.
<Test conditions>
Temperature: 23 ° C, -30 ° C
Test piece: 12.7 mm (width) x 6.4 mm (thickness) x 64 mm (length)
Notch machined

Polypropylene resin (B-3) (J136: Mitsui Chemicals, Trademark) 60 parts by weight, polypropylene resin composition (MB-1) 30 parts by weight, talc (F-1) (white filler 5000PJ, Matsumura Sangyo Co., Ltd. (trademark) 10 parts, crystal nucleating agent ADK STAB NA-11 (Asahi Denka Kogyo Co., Ltd., trade mark) 0.5 parts by weight was mixed in a tumbler, then melt-kneaded in a twin screw extruder A pellet-shaped polypropylene resin composition was prepared, and an ASTM test piece was molded with an injection molding machine [Part No. IS100, manufactured by Toshiba Machine Co., Ltd.]. Table 2 shows the physical properties of the molded product.
<Melting and kneading conditions>
Same-direction biaxial kneader: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 230 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 500 rpm
<Injection molding conditions>
Injection molding machine: Part number IS100, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 230 ° C
Mold temperature: 40 ℃

  A polypropylene resin composition was prepared in the same manner as in Example 1 except that the polypropylene resin composition (MB-2) was added instead of the polypropylene resin composition (MB-1), and an ASTM test piece was molded. Table 2 shows the physical properties of the molded product.

[Comparative Example 1]
A polypropylene resin composition was prepared in the same manner as in Example 1 except that the polypropylene resin composition (MB-3) was added instead of the polypropylene resin composition (MB-1), and an ASTM test piece was molded. Table 3 shows the physical properties of the molded product.

[Comparative Example 2]
A polypropylene resin composition was prepared in the same manner as in Example 1 except that the polypropylene resin composition (MB-4) was added instead of the polypropylene resin composition (MB-1), and an ASTM test piece was molded. Table 3 shows the physical properties of the molded product.

[Comparative Example 3]
Polypropylene (B-1) 75 parts by weight, hydrogenated styrene-ethylene-butadiene-styrene rubber (D3-1) (G1652: trade name, manufactured by Kraton Japan Co., Ltd.), talc (F-1) (white filler 5000 PJ, Matsumura Sangyo Co., Ltd., Trademark) 10 parts, Crystal Nucleating Agent Adeka Stub NA-11 (Asahi Denka Kogyo Co., Ltd., Trademark) 0.5 part by weight was mixed in a tumbler and then mixed into a twin screw extruder. Then, a polypropylene resin composition in the form of a pellet was prepared by melt-kneading, and an ASTM test piece was molded with an injection molding machine [Part No. IS100, manufactured by Toshiba Machine Co., Ltd.]. Table 3 shows the physical properties of the molded product.

[Comparative Example 4]
Except for using 15 parts by weight of ethylene-octene copolymer rubber (D1-1, engage 8150: trade name, manufactured by DuPont Dow Elastomer Co., Ltd.) instead of hydrogenated styrene-ethylene-butadiene-styrene rubber (D3-1). Prepared a polypropylene resin composition in the same manner as in Comparative Example 3, and molded an ASTM test piece. Table 3 shows the physical properties of the molded product.

[Comparative Example 5]
60 parts by weight of polypropylene (B-3), 15 parts by weight of ultra high molecular weight polypropylene (A-1), hydrogenated styrene-ethylene-butadiene-styrene rubber (D3-1) (G1652: trademark of Kraton Japan Co., Ltd.) 15 parts by weight, 10 parts by weight of talc (F-1) (white filler 5000PJ, manufactured by Matsumura Sangyo Co., Ltd.), crystal nucleating agent ADK STAB NA-11 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) 0.5% by weight After mixing the parts with a tumbler, melt-kneading with a twin-screw extruder (kneading temperature 280 ° C.) to prepare a pellet-shaped polypropylene resin composition, and the injection molding machine [Part No. IS100, manufactured by Toshiba Machine Co., Ltd.] An ASTM test piece was molded. Table 3 shows the physical properties of the molded product.

  The resin composition of the present invention is excellent in strength and impact resistance, and is excellent in strength and impact resistance modification effects, and can be used for various molded products such as injection molding, extrusion molding, hollow molding, thermoforming, and press molding. Can be used.

Claims (9)

  Polypropylene resin composition comprising 20 to 70% by weight of ultrahigh molecular weight polypropylene (A) having an intrinsic viscosity [η] of 6 to 12 dl / g in decalin at 135 ° C. and 30 to 80% by weight of elastomer (D) (MB ). In the cross fractionation chromatograph (CFC), the amount of elution component of orthodichlorobenzene (ODCB) at 80 ° C. or lower is 30 to 80% by weight, the amount of elution component at 80 to 135 ° C. is 20 to 70% by weight, and 80 to 135 The polypropylene resin composition (MB) according to claim 1, wherein the weight average molecular weight Mw of the elution component at 10 ° C is 10 ⁶ or more. The polypropylene-based resin composition (MB) according to claim 1 or 2, wherein a storage elastic modulus G 'at 1 Hz measured by 220 ° C melt dynamic viscoelasticity is 3 x 10 ⁴ Pa or more.   The polypropylene resin composition according to any one of claims 1 to 3, and a polypropylene resin composition comprising at least one selected from a polypropylene resin (B), an elastomer (E) and an inorganic filler (F). Object (D).   The sheet | seat obtained by shape | molding the polypropylene resin composition of Claims 1-4.   The film obtained by shape | molding the polypropylene resin composition of Claims 1-4.   A hollow container obtained by molding the polypropylene resin composition according to claim 1.   An extruded product obtained by molding the polypropylene resin composition according to claim 1.   An injection molded product obtained by molding the polypropylene resin composition according to claim 1.