JP2008115262A - Automotive part comprising propylene-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide automotive parts having few molded appearance defects such as a flow mark or a weld line, and having good rigidity and impact resistance. <P>SOLUTION: The automotive parts comprise a specific ratio of a propylene-based resin (A) polymerized in the presence of a metallocene catalyst, an elastomer (D) and an inorganic filler (E), wherein the propylene-based resin (A) satisfies the following (i) to (iii). (i) The resin (A) comprises 10-50 wt.% room temperature n-decane-soluble part (D<SB>sol</SB>) and 50-90 wt.% room temperature n-decane-insoluble part (D<SB>insol</SB>). (ii) The resin (A) comprises a polymer obtained from propylene (M<SB>p</SB>) and at least one olefin (M<SB>x</SB>) selected from ethylene and ≥4C α-olefin. (iii) The D<SB>sol</SB>has Mw/Mn, intrinsic viscosity [η], and M<SB>x</SB>, each in a specific range, and D<SB>insol</SB>has Mw/Mn, a melting point, the sum of 2,1-inserted bond amount and 1,3-inserted bond amount, and intrinsic viscosity [η], each in a specific range. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an automobile part made of a polypropylene resin composition, and more particularly to an automobile part having a good molded appearance and good rigidity and impact resistance.

  Polypropylene resin is used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automotive parts, etc., and various additives are blended according to the required performance. Has been. Especially in automotive parts applications, a composition in which an α-olefin copolymer rubber and an inorganic filler such as talc are blended with polypropylene resin has an excellent balance between the rigidity and impact resistance of the molded product. Is used.

Automotive interior / exterior parts are often molded by injection molding because of their productivity. When injection molding is performed using the above-described polypropylene resin composition, a plurality of periodic striped patterns called flow marks and tiger marks are generated in a direction intersecting with the flow direction of the surface of the injection-molded product, which is conspicuous. If the flow mark generated on the surface of the molded product is conspicuous, the appearance of the molded product is impaired. Therefore, the flow mark is erased by performing painting or the like as necessary. For example, Japanese Patent Application Laid-Open No. 9-87482 discloses a propylene resin composition comprising a propylene block copolymer containing a high molecular weight propylene-ethylene copolymer. In the above invention, an injection-molded product with few flow marks can be obtained, but an appearance defect called a weld line that occurs at the joining point of the molten resin flow may occur. A pretreatment step for erasing is required. Here, as a method for improving the weld line, JP-A-11-279369 discloses a propylene-based resin composition obtained by treating a propylene-based block copolymer, a resin composition comprising rubber and an inorganic filler with an organic peroxide. ing. However, Japanese Patent Application Laid-Open No. 11-279369 has a problem that mechanical strength such as rigidity may be lowered due to organic peroxide treatment.
JP-A-9-87482 Japanese Patent Laid-Open No. 11-279369

  An object of the present invention is to provide an automobile part made of a polypropylene resin composition that has few molding appearance defects such as a flow mark and a weld line, and has good rigidity and impact resistance.

That is, the present invention comprises 20 to 98 parts by weight of a propylene resin (A) polymerized under a metallocene compound-containing catalyst, 1 to 40 parts by weight of an elastomer (D) and 1 to 40 parts by weight of an inorganic filler (E) (however, ( A), (D), and (E) total 100 parts by weight), and the propylene resin (A) satisfies the following (i) to (iii): Auto parts.
(I) A portion soluble in room temperature n-decane (D _sol ) 10 to 50% by weight and a portion insoluble in room temperature n-decane (D _insol ) 50 to 90% by weight.
(Ii) propylene (M _P) and is a resin composed of a polymer derived from ethylene and one or more olefins selected from C4 or more [α- olefin carbon (M _X).
(Iii) D _sol and D _insol satisfy the following requirements (1) to (6) simultaneously.

(1) The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of D _sol and D _insol is 3.
5 or less.
(2) The melting point (Tm) of D _insol is 156 ° C or higher.

(3) The sum of 2,1-insertion bond amount and 1,3-insertion bond amount in D _insol is 0.05 mol% or less.
(4) The intrinsic viscosity [η] of D _insol is 0.8 to 1.5 dl / g.
(5) The intrinsic viscosity [η] of D _sol is 2.0 to 4.0 dl / g.

(6) The total amount of olefin (M _X ) selected from ethylene and α-olefin having 4 or more carbon atoms in D _sol is 25 to 80 mol%.

  The automobile part according to the present invention has few molding appearance defects such as a flow mark and a weld line, and has good rigidity and impact resistance.

The automotive part comprising the propylene resin composition of the present invention comprises 20 to 98 parts by weight of a propylene resin (A) polymerized under a metallocene compound-containing catalyst, 1 to 40 parts by weight of an elastomer (D), and an inorganic filler (E). 1 to 40 parts by weight (however, the total of (A), (D), and (E) is 100 parts by weight), and the propylene resin (A) is soluble in room temperature n-decane (D _sol ) consists of 10 to 50 wt% and an insoluble portion to room temperature n- decane (D _insol) 50 to 90 wt%, propylene (M _P) and one or more selected from ethylene and C4 or more α- olefins carbon It is a resin composed of a polymer obtained from olefin (M _X ).

  Hereinafter, the propylene-based resin (A) in the components constituting the propylene-based resin composition of the present invention will be described in detail, and then the elastomer (D) and the inorganic filler (E) will be sequentially described.

Propylene resin (A)
The propylene-based resin (A) used in the present invention is polymerized under a metallocene compound-containing catalyst, and is one or more olefins (M _X ) selected from propylene (M _P ) and ethylene and α-olefins having 4 or more carbon atoms. And consists of 10 to 50% by weight of a part soluble in room temperature n-decane (D _sol ) and 50 to 90% by weight of a part insoluble in room temperature n-decane (D _insol ).

The α-olefin having 4 or more carbon atoms used in the present invention is preferably an α-olefin having 4 to 20 carbon atoms, such as 1-butene, 1-pentene, 3-methyl-1-butene, and 1-hexene. 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-
Examples include dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene.

  The propylene-based resin (A) used in the present invention is preferably a propylene-based block copolymer, but a composition of a propylene-based (co) polymer (B) and a propylene-based random copolymer (C). It may be.

When the propylene-based resin (A) is a propylene-based block copolymer, the propylene homopolymer part is empirically found to be insoluble mainly in a component insoluble in room temperature n-decane (D _insol ) or in orthodichlorobenzene at 90 ° C. Corresponding to components soluble in orthodichlorobenzene at 0 ° C, the copolymer part consisting of propylene, ethylene and α-olefin having 4 or more carbon atoms is a component soluble in n-decane at room temperature (D _sol ) or ortho at 40 ° C Corresponds to components soluble in dichlorobenzene. Hereinafter, requirements (1) to (6) included in the propylene-based resin (A) used in the present invention will be described in detail.
[Requirement (1)]
The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of D _sol and D _insol is 3.5 or less. Mw / Mn of D _sol is preferably 1.0 to 3.0, more preferably 1.0 to 2.5. When Mw / Mn of D _sol is larger than 3.5, impact resistance is lowered due to an increase in low molecular weight components in D _sol .

Mw / Mn of D _insol is preferably 1.5 to 3.5, more preferably 2.0 to 3.0. D _insol
If the Mw / Mn of the steel is greater than 3.5, the weld line of the auto part becomes conspicuous. If the Mw / Mn of the D _insol is smaller than 1.5, the fluidity of the propylene resin composition at the time of injection molding becomes worse and the productivity is reduced. descend.
[Requirement (2)]
The melting point (Tm) of D _insol is 156 ° C. or higher. If the melting point (Tm) of D _insol is less than 156 ° C., the rigidity of the propylene-based resin composition is lowered, and the rigidity as an automobile structural part may be insufficient.
[Requirement (3)]
The sum of the 2,1-insertion bond amount and the 1,3-insertion bond amount in D _insol is 0.05 mol% or less. If the sum of the 2,1-insertion bond amount and the 1,3-insertion bond amount in D _insol is greater than 0.05 mol%, the rigidity of the propylene-based resin composition is lowered, and the rigidity may be insufficient as an automobile structural part. is there. Further, the sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds in D _insol is often determined by the metallocene compound-containing catalyst. Here, when the sum of the 2,1-insertion bond amount and the 1,3-insertion bond amount in D _insol is larger than 0.05 mol%, the metallocene compound-containing catalyst propylene ( _MP ), ethylene, and 4 or more carbon atoms One or more olefins selected from α-olefins of
May copolymerizability performance of the M _X) is poor. In this case, the composition distribution of propylene (M _P ) and olefin (M _X ) in D _sol becomes wider, the low temperature impact resistance of the propylene resin composition is lowered, and the impact resistance as an automobile part may be insufficient. is there.
[Requirement (4)]
D _insol has an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of 0.8 to 1.5 dl / g, preferably 0.8 to 1.3 dl / g, and more preferably 1.0 to 1.2 dl / g. When the intrinsic viscosity [η] of D _insol is lower than 0.8 dl / g, the molecular weight of the propylene homopolymer part is low, and the elongation at break and impact resistance of the propylene resin composition are lowered. There are cases where it is not possible. On the other hand, when the intrinsic viscosity [η] of D _insol is higher than 1.5 dl / g, the molecular weight of the propylene homopolymerized portion becomes high, and the productivity at the time of automobile part injection molding is lowered.
[Requirement (5)]
The intrinsic viscosity [η] of D _sol measured at 135 ° C. in a decalin solvent is 2.0 to 4.0 dl / g, preferably 2.2 to 3.5 dl / g, and more preferably 2.4 to 3.0 dl / g. When the intrinsic viscosity of the D _sol [η] is lower than 2.2 dl / g, more low molecular weight components in the D _sol, the impact resistance of the propylene resin composition is lowered, which may not be suitable as automotive parts . Further, if the intrinsic viscosity [η] of D _sol is higher than 4.0 dl / g, the weld line of the automobile part is easily noticeable, and the molded appearance may not be suitable as the automobile part.
[Requirement (6)]
The total amount of olefins (M _x ) selected from ethylene and α-olefins having 4 or more carbon atoms in D _sol is 25 to 80 mol%, preferably 27 to 50 mol%, more preferably 28 to 45 mol%. is there. If the total amount of olefins (M _x ) selected from ethylene and α-olefins having 4 or more carbon atoms in D _sol is less than 25 mol%, the impact resistance and rigidity of the propylene-based resin composition are reduced, and automobiles It may not be suitable as a part. If the amount of one or more olefins (M _x ) selected from ethylene and α-olefins having 4 or more carbon atoms in D _sol is more than 80 mol%, the impact resistance of the propylene-based resin composition decreases, and automobile parts May not be suitable.

Hereinafter, one or more olefins selected from ethylene and an α-olefin having 4 or more carbon atoms may be abbreviated as “olefin (M _X )”.
<Production method of copolymer>
Among the propylene-based resins (A) used in the present invention, a propylene-based block copolymer is, for example, a propylene-based random copolymer from propylene and a small amount of olefin (M _X ) in the first polymerization step in the presence of a metallocene compound-containing catalyst. After producing the copolymer, it can be obtained by producing propylene-ethylene copolymer rubber by copolymerizing propylene and a larger amount of olefin (M _X ) than in the first step in the second polymerization step.

<Metalocene catalyst>
The metallocene compound-containing catalyst used in the present invention is at least one or more selected from metallocene compounds and compounds capable of reacting with organometallic compounds, organoaluminum oxy compounds and metallocene compounds to form ion pairs. The metallocene catalyst which can perform stereoregular polymerization of an isotactic or syndiotactic structure etc. with the metallocene catalyst which consists of this compound, and also a particulate carrier as needed, Preferably it can be mentioned. Among the metallocene compounds, crosslinkable metallocene compounds exemplified in WO 01/27124 filed by the present applicant are preferably used.

In the general formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different. Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Linear hydrocarbon groups such as nonyl group and n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1 A branched hydrocarbon group such as a methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; Cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, tolyl group, naphthyl group, biphenyl group, A cyclic unsaturated hydrocarbon group such as an enanthryl group and an anthracenyl group; a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group such as a benzyl group, a cumyl group, a 1,1-diphenylethyl group and a triphenylmethyl group; a methoxy group And hetero atom-containing hydrocarbon groups such as ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group, and thienyl group. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. Moreover, the adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [I], R ¹ , R ² , R ³ and R ⁴ substituted on the cyclopentadienyl ring are preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. More preferably, R ¹ and R ³ are hydrocarbon groups having 1 to 20 carbon atoms (others are hydrogen).

In the general formula [I], R ⁵ to R ¹² substituted on the fluorene ring are preferably hydrocarbon groups having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring.

In the general formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element of the periodic table, more preferably carbon, silicon, or germanium, and even more preferably a carbon atom. . R ¹³ and R ¹⁴ substituted for Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. More preferably, R ¹³ and R ¹⁴ are aryl groups having 6 to 20 carbon atoms. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

In the general formula [I], M is preferably a Group 4 transition metal of the periodic table, more preferably Ti, Zr, or Hf. Q is selected from the same or different combinations from halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include those described above. Specific examples of anionic ligands include methoxy, tert-
Examples thereof include alkoxy groups such as butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen or an alkyl group.

Such bridged metallocene compounds include diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl). ) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride , (Methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3- (1 ', 1', 4 ', Four',
7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene )] Zirconium dichloride (a compound represented by the following formula [II]), a compound represented by the following formula [III], and the like are preferable.

In the metallocene catalyst used for the production of the propylene-based resin (A), an organometallic compound, an organoaluminum oxy compound, and a transition metal compound used together with the Group 4 transition metal compound represented by the general formula [I] Regarding at least one compound selected from compounds that react to form an ion pair, and further, the particulate carrier used as necessary, the above-mentioned publications (WO01 / 27124 pamphlet) and The compounds disclosed in Japanese Patent No. 315109 can be used without limitation.

<Production method>
The propylene-based block copolymer that is the propylene-based resin (A) uses a polymerization apparatus in which two or more reactors are connected in series, and the following two steps ([Step 1] and [Step 2]) are continuously performed. It is obtained by carrying out automatically. In the present invention, [Step 1] can be performed in each polymerization apparatus using a polymerization apparatus in which two or more reactors are connected in series, and a polymerization apparatus in which two or more reactors are connected in series is used. [Step 2] can be performed in each polymerization apparatus.

[Step 1] copolymerizes propylene and, if necessary, olefin (M _X ) (preferably ethylene) at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 1], the propylene-based (co) polymer produced in [Step 1] is a main component of D _{insol by reducing} the feed amount of olefin (M _X ) relative to propylene. To do.

[Step 2] copolymerizes propylene and olefin (M _X ) (preferably ethylene) at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 2], the propylene-olefin (M _X ) copolymer rubber produced in [Step 2] is produced by increasing the feed amount of olefin (M _X ) relative to propylene as compared with [Step 1]. _Be the main component of _sol .

By doing in this way, the requirements (1) to (4) related to D _insol are the requirements (1) and (5) to (6) related to D _sol by adjusting the polymerization conditions in [Step 1]. It can be satisfied by adjusting the polymerization conditions in [Step 2].

After completion of the polymerization, a propylene polymer is obtained as a powder by performing post-treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step as necessary.
In the propylene resin composition of the present invention, the amount of the propylene resin (A) is 20 to 98 parts by weight, preferably 40 to 94 parts by weight, and more preferably 50 to 90 parts by weight.

The propylene-based resin (A) used in the present invention may be a composition of a propylene-based (co) polymer (B) and a propylene-based random copolymer (C).
Preferable examples of the propylene-based (co) polymer (B) include a propylene homopolymer or a copolymer of propylene and a small amount of olefin (M _X ).

In the propylene-based (co) polymer (B), the content of the olefin (M _X ) is 0 to 4 mo.
1%. If the content of olefin (M _X ) is more than 4 mol%, the propylene-based (co) polymer (B) has a reduced rigidity, so that the propylene-based resin composition may not be suitable as an automobile part.

In the propylene-based resin composition of the present invention, the amount of the propylene-based (co) polymer (B) is 10 to 97 parts by weight, preferably 20 to 93 parts by weight, and the propylene-based (co) polymer (B The portion insoluble in room temperature n-decane (D _insol ) in () preferably satisfies the following requirements (1 ′) to (4 ′).
The propylene-based (co) polymer (B) is usually a portion insoluble in room temperature n-decane (D _insol ).
Is 99% by weight or more.
(1 ′) The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3.5 or less.
(2 ′) Melting point (Tm) is 156 ° C. or higher.
(3 ′) The sum of the 2,1-insertion bond amount and the 1,3-insertion bond amount is 0.05 mol% or less.
(4 ′) The intrinsic viscosity [η] is 0.8 to 1.5 dl / g.

Preferred examples of the propylene random copolymer (C) include a random copolymer of propylene and an olefin (M _X ), and a propylene-ethylene random copolymer is more preferable.

In the propylene resin composition of the present invention, the amount of the propylene random copolymer (C) is 0.2 to 49 parts by weight, preferably 0.4 to 47 parts by weight, and the amount of the propylene-ethylene random copolymer (C) is The portion soluble in room temperature n-decane (D _sol ) preferably satisfies the following requirements (1 ") to (3"). The propylene random copolymer (C) usually has a portion soluble in room temperature n-decane (D _sol ) of 99% by weight or more.
(1 ") The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3.5 or less.
(2 ") The intrinsic viscosity [η] is 2.0 to 4.0 dl / g.
(3 ") one or more olefins selected from ethylene and α-olefins having 4 or more carbon atoms (M
The amount of x) is 25-80 mol%.

  The propylene-based (co) polymer (B) and the propylene-based random copolymer (C) can be produced using the same catalyst as exemplified as the catalyst for producing the propylene-based block copolymer.

  In addition, the propylene-based resin composition of the present invention includes a propylene-based resin (A), an elastomer (D) and an inorganic filler (E), a propylene-based (co) polymer (B), a propylene-based random copolymer ( C), an elastomer (D), and an inorganic filler (E), and any of them can provide an automobile part excellent in flow mark and weld appearance.

Elastomer (D)
As the elastomer (D), ethylene / α-olefin random copolymer (Da), ethylene / α-olefin / nonconjugated polyene random copolymer (Db), hydrogenated block copolymer (D−) c), other elastic polymers, and mixtures thereof.

The content of the elastomer (D) in the propylene-based resin composition is 1 to 40 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight, from the viewpoint of impact strength and rigidity.

  The ethylene / α-olefin random copolymer (D-a) 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-eicocene 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 (Da) 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 (Da) has an MFR at 230 ° C. and a load of 2.16 kg 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-b) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. As said C3-C20 alpha-olefin, the same thing as the above is mentioned. 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, 7-methyl-1,6-octadiene and other chain non-conjugated dienes; 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 / non-conjugated polyene random copolymer (D-b) has a molar ratio of ethylene, α-olefin and non-conjugated polyene (ethylene / α-olefin / non-conjugated polyene) of 90/5/5. ~ 30/45/25, preferably 80/10/10 to 40/40/2
0 is desirable.

  The ethylene / α-olefin / non-conjugated polyene random copolymer (Db) has an MFR of 0.05 g / 10 min or more, preferably 0.1 to 10 g / 10 min at 230 ° C. and a load of 2.16 kg. desirable. Specific examples of the ethylene / α-olefin / non-conjugated polyene random copolymer (D-b) include an ethylene / propylene / diene terpolymer (EPDM).

  The hydrogenated block copolymer (Dc) is a hydrogenated product of a block copolymer represented by the following formula (a) or (b) in the form of a block, and the hydrogenation rate is 90 mol% or more The hydrogenated block copolymer is preferably 95 mol% or more.

X (YX) n (a)
(XY) n (b)
Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymerization block represented by X in the formula (a) or (b) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, lower alkyl-substituted styrene, and 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 (a) or (b) 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-c) include styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / ethylene / propylene / styrene block copolymer (SEPS), and styrene. -Styrene-type block copolymers, such as ethylene propylene block copolymer (SEP), etc. are mentioned.

  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 proportion of 1,2-bonds in the polybutadiene block is 20 to 80% by weight, preferably 30 to 60% by weight.

  A commercially available product can also be used as the hydrogenated block copolymer (D-c). Specific examples include Kraton G1657 (trademark, manufactured by Shell Chemical Co., Ltd.), Septon 2004 (trademark, manufactured by Kuraray Co., Ltd.), Tuftec H1052 (trademark, manufactured by Asahi Kasei Corporation), and the like. Elastomer (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

Inorganic filler (E)
Examples of the inorganic filler (E) 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 can also be used individually by 1 type and can also be used in combination of 2 or more type. Content of an inorganic filler (E) is 1 to 40 weight%, Preferably it is 3 to 30 weight%, More preferably, it is 5 to 25 weight%.

Other Components The propylene resin composition of the present invention may further contain a propylene polymer (A ′) other than the propylene resin (A). Such a propylene polymer (A ′) is a homopolymer of propylene, a copolymer of propylene, ethylene and α-olefin, or a block copolymer of propylene, ethylene 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, and the like can be given. Of these, α-olefins of 1-butene, 1-pentene, 1-hexene and 1-octene can be preferably used.

The propylene polymer (A ′) has a melting point (Tm) of 145 to 170 ° C., preferably 155.
It is desirable to be ˜167 ° C. Further, the melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the polypropylene-based polymer (A ′) is usually 0.00.
It is 3 to 200 g / 10 minutes, preferably 2 to 150 g / 10 minutes, and more preferably 10 to 100 g / 10 minutes.

  Along with the propylene-based resin composition obtained as described above, an antioxidant, ultraviolet absorber, antistatic agent, nucleating agent, lubricant, flame retardant, antiblocking agent, colorant, inorganic or organic filling Various additives such as an agent and various synthetic resins are blended as necessary, melt-kneaded, and pelletized into pellets for use in the production of various molded products.

Molding Method To blend the propylene-based resin composition of the present invention with a predetermined amount of the various additives, a conventional kneading apparatus such as a Henschel mixer, a ribbon blender, or a Banbury mixer can be used. The melt-kneading and pelletizing are performed by melt-kneading at 170 to 300 ° C., preferably 190 to 250 ° C., using a normal single-screw extruder or twin-screw extruder, Brabender or roll, and pelletizing. The obtained propylene-based resin composition can be molded into a target automobile part, for example, a bumper, an instrument panel, a side seal garnish, or the like by an injection molding method. Since the propylene-based resin composition used in the present invention has high rigidity and excellent impact resistance, it can be suitably used particularly for bumpers and instrument panels. In these large parts, in order to shorten the flow length at the time of injection molding, there are cases where injection molding is performed with a mold having a multi-point gate, but automobile parts obtained from the propylene-based resin composition of the present invention have a weld appearance. Very good. The automobile part according to the present invention is manufactured using a mold having, for example, two or more gates, for example, 3 to 10 points.

[Example]
EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example. The analysis method employed in the present invention is as follows.
[m1] Room temperature n-decane soluble part (D _sol )
200 ml of n-decane was added to 5 g of a sample of the final product (that is, propylene-based resin (A)) and dissolved by heating at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble part: D _insol ) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate (A) and acetone were separated by filtration, and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following equation.

n-decane soluble part amount (wt%) = [precipitate (A) weight / sample weight] × 100
[m2] Mw / Mn measurement (weight average molecular weight (Mw), number average molecular weight (Mn))
Measurement was performed as follows using GPC-150C Plus manufactured by Waters. Separation columns are TSKgel GMH6-HT and TSK gel GMH6-HTL, and column sizes are 7.5 mm in inner diameter and 600 mm in length, respectively.
The column temperature was 140 ° C., o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase and 0.025 wt% BHT (Wako Pure Chemical Industries) was used as the antioxidant, and the column was moved at 1.0 ml / min. The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene is converted to PP using a general-purpose calibration method using Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ^{6 and} pressure chemicals for 1000 ≦ Mw ≦ 4 × 10 ⁶ did. The Mark-Houwink coefficients of PS and PP are the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)). Was used.
[m3] Melting point (Tm)
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak in the third step was defined as the melting point (Tm).
(Measurement condition)
First step: The temperature is raised to 240 ° C. at 10 ° C./min and held for 10 min.

Second step: Decrease the temperature to 60 ° C at 10 ° C / min.
Third step: The temperature is raised to 240 ° C at 10 ° C / min.
[m4] Measurement of 2,1-insertion bond and 1,3-insertion bond 20-30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, and then carbon nuclei. Magnetic resonance analysis ( ¹³ C-NMR) was performed. Here, the partial structure including the position irregular unit based on 2,1-insertion and 1,3-insertion is represented by the following (i) and (ii).

The monomer formed by 2,1-insertion forms a position irregular unit represented by the partial structure (i) in the polymer chain. The frequency of 2,1-propylene monomer insertion relative to total propylene insertion was calculated by the following formula.

In this formula, ΣICH ₃ represents the area of all methyl groups. Further, Iαδ and Iβγ indicate the area of the αβ peak (resonance around 37.1 ppm) and the area of the βγ peak (resonance around 27.3 ppm), respectively. These methylene peaks were named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781).

  Similarly, the frequency of 1,3-propylene monomer insertion represented by the partial structure (ii) with respect to total propylene insertion was calculated by the following formula.

[m5] Intrinsic viscosity [η]
Measurement was performed at 135 ° C. using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. Repeat this dilution operation two more times,
The value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (ηsp / C) (C → 0)
[m6] Content of skeleton derived from ethylene
To measure the skeleton concentration derived from ethylene in D _insol and D _sol , 20-30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, and then carbon nuclear magnetism. Resonance analysis ( ¹³ C-NMR) was performed. Propylene, ethylene, and α-olefin were quantitatively determined from the dyad chain distribution. For example, in the case of a propylene-ethylene copolymer, PP = Sαα, EP = Sαγ + S
Using αβ, EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ, the following formulas (Eq-1) and (Eq-2) were used.

Propylene (mol%) = (PP + 1 / 2EP) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)
Ethylene (mol%) = (1 / 2EP + EE) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)
In this example, the _units of ethylene and α-olefin in D _insol are expressed in terms of% by weight.
[m7] MFR (melt flow rate)
MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).
[m8] Flexural Modulus of Injection Molded Article The flexural modulus (FM) was measured according to ASTM D790 under the following conditions.
<Measurement conditions>
Test piece: 12.7mm (width) x 6.4mm (thickness) x 127mm (length)
Bending speed: 2.8mm / min Bending span: 100mm
[m9] Izod impact strength (IZ) of injection molded products
Izod impact strength (IZ) was measured under the following conditions in accordance with ASTM D256.
<Test conditions>
Temperature: -30 ℃
Test piece: 12.7mm (width) x 6.4mm (thickness) x 64mm (length)
Notch machined
[m10] Weld Appearance Evaluation Method An injection mold having a gate at the center (50 mm) having a width of 350 mm, a width of 100 mm, and a thickness of 3 mm and having a width of 100 mm was used (FIG. 1). A weir was installed at a position 25 mm directly below the flow direction from the gate to prevent the flow of resin with a diameter of 45 mm and a thickness of 3 mm centered on that point. The weld length was determined by measuring the length until the weld that cannot be discriminated by visual inspection of the weld generated after the weir when the mold was used for injection molding.
<Test piece injection molding conditions>
Injection molding machine: Product number M200, Cylinder temperature manufactured by Meiki Seisakusho Co., Ltd .: 210 ° C
Mold temperature: 20 ℃
Molded product shape: as shown in FIG.
[m11] Flow Mark Appearance Evaluation Method The appearance of the flow mark was visually determined for the molded product whose weld appearance was evaluated. Here, the distance from where the flow mark began to occur from the gate and how the flow mark was conspicuous (10 points: no flow mark, 0 point: flow mark generated on the entire molded product) were evaluated.

[Production Example 1]
(1) Production of a solid catalyst carrier 300 g of SiO ₂ was sampled in a 1 L branch flask, and 800 mL of toluene was added.
Slurried. Next, the solution was transferred to a 5 L four-necked flask, and 260 mL of toluene was added. 2830 mL of a methylaluminoxane (hereinafter also referred to as “MAO”)-toluene solution (10 wt% solution) was introduced. The mixture was stirred for 30 minutes while remaining at room temperature. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on support)
[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl in a 5 L four-necked flask in a glove box ) (1,1,3-trimethyl-5-tert-
2.0 g of butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride was weighed. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The resulting [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]
Zirconium dichloride / MAO / SiO ₂ / toluene slurry is 99 in n-heptane.
% Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (2) above, 218 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C., and 1212 g of ethylene. Inserted and allowed to react with stirring for 180 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization A tubular polymerization vessel having an internal volume of 58 L was charged with propylene at 40 kg / hour, hydrogen at 5 NL / hour, the catalyst slurry produced in (3) as a solid catalyst component at 0.8 g / hour, and triethylaluminum at 4 ml / hour. The polymer was continuously fed and polymerized in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G. The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-1). The resulting propylene block copolymer (A-1) was vacuum dried at 80 ° C.
[Production Example 2]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 0.8 g / hour as a solid catalyst component, and 4 ml of triethylaluminum. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.26 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.26 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.26 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-2). The resulting propylene block copolymer (A-2) was vacuum dried at 80 ° C.
[Production Example 3]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 0.7 g / hour as a solid catalyst component, and 4 ml of triethylaluminum. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.27 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.27 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.27 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-3). The resulting propylene block copolymer (A-3) was vacuum dried at 80 ° C.
[Production Example 4]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 0.7 g / hour as a solid catalyst component, and 4 ml of triethylaluminum. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.28 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.28 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.28 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-4). The resulting propylene block copolymer (A-4) was vacuum dried at 80 ° C.
[Production Example 5]
(1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Production of prepolymerization catalyst 56 g of transition metal catalyst component, 63.8 mL of triethylaluminum, 21.5 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, and 80 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L. Then, maintaining the internal temperature at 5 ° C., 560 g of propylene was inserted, and the reaction was carried out with stirring for 60 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the concentration of the transition metal catalyst component was 0.8 g / L. This prepolymerization catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization Propylene is 30 kg / hour, hydrogen is 56 NL / hour, catalyst slurry is used as a solid catalyst component, 0.3 g / hour, triethylaluminum 3.8 ml / hour, dicyclopentyldimethoxysilane in a cyclic polymerization vessel having an internal volume of 58 L 1.3 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the annular reactor was 70 ° C., and the pressure was 3.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 L, and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 3.5 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.3 MPa / G.

The obtained slurry is transferred to a sandwiching tube having an internal volume of 2.4 L, and the slurry is gasified and subjected to gas-solid separation. After that, a polypropylene homopolymer powder is sent to a 480 L gas phase polymerization vessel, and an ethylene / propylene block Copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.32 (molar ratio) and hydrogen / ethylene = 0.14 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.9 MPa / G.

The resulting propylene block copolymer (A-5) was vacuum dried at 80 ° C.
[Production Example 6]
Thermal stabilizer IRGANOX 1010 (registered trademark, Ciba Geigy Co., Ltd.) 0.1 part by weight, thermal stabilizer IRGAFOS168 (registered trademark, Ciba Geigy Co., Ltd.) per 100 parts by weight of the propylene polymer (A-5) produced in Production Example 5 ) 0.1 parts by weight, 0.1 parts by weight of calcium stearate, and 0.3 parts by weight of degraving agent Perhexa 25B-40 (trademark, Nippon Oil & Fats Co., Ltd.) were mixed in a Henschel mixer, then melt-kneaded in a twin screw extruder and pelletized propylene A system block copolymer (A-6) was prepared.
<Melting and kneading conditions>
Same-direction twin-screw kneader: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 210 ° C
Screw rotation speed: 200 rpm
Feeder speed: 400 rpm
[Production Example 7]
The polymerization was performed in the same manner as in Production Example 5 except that the polymerization method was changed as follows.

(1) Main polymerization Propylene is 30 kg / hour, hydrogen is 180 NL / hour, and the catalyst slurry produced in Production Example 5 (3) is 0.4 g / hour as a solid catalyst component in a 58 L cyclic polymerizer. Polymerization was carried out in a liquid state in which no gas phase was present by continuously supplying 1.8 ml / hour of ethyl (perhydroisoquinolino) dimethoxysilane at 9 ml / hour. The temperature of the annular reactor was 70 ° C., and the pressure was 3.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 L, and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 8.0 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 3.3 MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 L, and the slurry was gasified and subjected to gas-solid separation. After that, a polypropylene homopolymer powder was sent to a 480 L gas phase polymerizer, and an ethylene / propylene block Copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.28 (molar ratio) and hydrogen / ethylene = 0.12 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.

The resulting propylene block copolymer (A-7) was vacuum dried at 80 ° C.
[Production Example 8]
The polymerization was performed in the same manner as in Production Example 5 except that the polymerization method was changed as follows.

(1) Main polymerization In a vessel polymerization vessel with a stirrer having an internal volume of 1000 L, propylene was used at 162 kg / hour, the catalyst slurry produced in Production Example 5 (3) was used as a solid catalyst component, 1.1 g / hour, and triethylaluminum 24.5 ml / hour. Time, dicyclopentyldimethoxysilane was 2.5 ml / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 13.8 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 3.6 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene is 51 kg / hour, hydrogen is in the gas phase with a hydrogen concentration of 10.7 m.
ol% was supplied. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 3.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 20 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 5.9 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 3.4 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. Propylene was supplied to the polymerization vessel at 15 kg / hour, ethylene was supplied at 18 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.3 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 3.3 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-8). The resulting propylene block copolymer (A-8) was vacuum dried at 80 ° C.
[Production Example 9]
The polymerization was performed in the same manner as in Production Example 5 except that the polymerization method was changed as follows.

(1) Main polymerization Propylene is 30 kg / hour, hydrogen is 200 NL / hour, and the catalyst slurry produced in Production Example 5 (3) is 0.4 g / hour as a solid catalyst component in a cyclic polymerization vessel having an internal capacity of 58 L. Triethylaluminum 4 Then, 1.8 ml / hour of ethyl (perhydroisoquinolino) dimethoxysilane was continuously fed at a rate of 8 ml / hour, and polymerization was carried out in a full liquid state without a gas phase. The temperature of the annular reactor was 70 ° C., and the pressure was 3.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 L, and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 9.0 mol%. Polymerization was performed at a polymerization temperature of 65 ° C. and a pressure of 3.3 MPa / G.

The obtained slurry is transferred to a sandwiching tube having an internal volume of 2.4 L, and the slurry is gasified and subjected to gas-solid separation. After that, a polypropylene homopolymer powder is sent to a 480 L gas phase polymerization vessel, and an ethylene / propylene block Copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.18 (molar ratio) and hydrogen / ethylene = 0.27 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.

The resulting propylene block copolymer (A-9) was vacuum dried at 80 ° C.
[Production Example 10]
Using the solid catalyst carrier produced in Production Example 1 (1), the following method was used.
(1) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 2.0 g of diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride was weighed in a 5 L four-necked flask. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in Production Example 1 (1) were added under nitrogen, 30
The mixture was stirred for a minute and carried. The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% in n-heptane. Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.
(2) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (1) above, 218 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C. to 606 g of ethylene. Inserted and allowed to react with stirring for 180 minutes. After polymerization is complete,
The solid component was allowed to settle, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.
(3) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 40 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in Production Example 10 (2) is 1.7 g / hour as a solid catalyst component, and triethylaluminum 4 ml. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.20 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.20 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.20 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.08 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-10). The resulting propylene block copolymer (A-10) was vacuum dried at 80 ° C.
[Production Example 11]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 0.8 g / hour as a solid catalyst component, and 4 ml of triethylaluminum. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.29 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-11). The resulting propylene block copolymer (A-11) was vacuum dried at 80 ° C.
[Production Example 12]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 40 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in Production Example 1 (3) is 1.7 g / hour as a solid catalyst component, and triethylaluminum 4 ml. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.14 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.14 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.14 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.0 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-12). The resulting propylene block copolymer (A-12) was vacuum dried at 80 ° C.
[Production Example 13]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 1.3 g / hour as a solid catalyst component, and 4 ml of triethylaluminum in a tubular polymerization vessel having an internal volume of 58 L. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.18 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.18 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.18 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.0 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-13). The resulting propylene block copolymer (A-13) was vacuum dried at 80 ° C.
[Production Example 14]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 0.6 g / hour as a solid catalyst component in a tubular polymerization vessel having an internal volume of 58 L, and triethylaluminum 4 ml. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.29 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.29 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.29 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L to carry out copolymerization. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied at 5.1 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-based block copolymer (A-14). The resulting propylene block copolymer (A-14) was vacuum dried at 80 ° C.
Table 1 shows the physical properties of the propylene block copolymers (A-1) to (A-14) produced in Production Examples 1 to 14.
[Production Example 15]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 0.8 g / hour as a solid catalyst component, and 4 ml of triethylaluminum. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (B-1). The resulting propylene block copolymer (B-1) was vacuum dried at 80 ° C.
[Production Example 16]
The polymerization was performed in the same manner as in Production Example 10 except that the polymerization method was changed as follows.
(1) Main polymerization 9 kg of liquid propylene was charged into a 30 L SUS autoclave sufficiently purged with nitrogen and brought to 10 ° C., and 0.5 MPa was charged with ethylene as a partial pressure. The mixture was heated to 45 ° C. with sufficient stirring, and a mixed solution of 0.6 g / 300 ml of heptane and 0.5 ml of triethylaluminum as a solid catalyst component was pressure-inserted into the autoclave with nitrogen from the catalyst insertion pot. After carrying out the polymerization at 60 ° C. for 20 minutes, methanol was added to stop the polymerization. After completion of the polymerization, the propylene was purged and sufficiently purged with nitrogen to fractionate the propylene-ethylene copolymer (C-1). Vacuum drying was performed at 80 ° C.
[Production Example 17]
The polymerization was performed in the same manner as in Production Example 10 except that the polymerization method was changed as follows.
(1) Main polymerization 9 kg of liquid propylene was charged into a 30 L SUS autoclave sufficiently purged with nitrogen and brought to 10 ° C., and 0.9 MPa was charged with ethylene as a partial pressure. The mixture was heated to 45 ° C. with sufficient stirring, and a mixed solution of 0.6 g / 300 ml of heptane and 0.5 ml of triethylaluminum as a solid catalyst component was pressure-inserted into the autoclave with nitrogen from the catalyst insertion pot. After carrying out the polymerization at 60 ° C. for 20 minutes, methanol was added to stop the polymerization. After completion of the polymerization, the propylene was purged and sufficiently purged with nitrogen to fractionate the propylene-ethylene copolymer (C-2). Vacuum drying was performed at 80 ° C.
[Production Example 18]
The polymerization was performed in the same manner as in Production Example 10 except that the polymerization method was changed as follows.
(1) Main polymerization 9 kg of liquid propylene was charged into an SUS autoclave of 30 L with sufficient nitrogen substitution and 10 ° C., and 1.7 MPa was charged with ethylene as a partial pressure. The mixture was heated to 45 ° C. with sufficient stirring, and a mixed solution of 0.6 g / 300 ml of heptane and 0.5 ml of triethylaluminum as a solid catalyst component was pressure-inserted into the autoclave with nitrogen from the catalyst insertion pot. After carrying out the polymerization at 60 ° C. for 20 minutes, methanol was added to stop the polymerization. After completion of the polymerization, the propylene was purged and sufficiently purged with nitrogen to fractionate the propylene-ethylene copolymer (C-3). Vacuum drying was performed at 80 ° C.

Table 1 shows the physical properties of the propylene polymers (B-1) and propylene-ethylene copolymers (C-1) to (C-3) produced in Production Examples 15 to 18.

Ethylene-butene copolymer rubber (Tuffmer A-0550 (trademark), manufactured by Mitsui Chemicals) with respect to 67 parts by weight of the propylene-based block copolymer (A-1) produced in Production Example 1 (D- 1
) 12 parts by weight, talc (E) (white filler 5000PJ (trademark), Matsumura Sangyo Co., Ltd.
21 parts by weight, heat stabilizer IRGANOX 1010 (trademark, Ciba Geigy) 0.1 part by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy) 0.1 part by weight, calcium stearate 0.1 part by weight After mixing with a tumbler, a polypropylene resin composition in the form of a pellet was prepared by melting and kneading with a twin screw extruder, 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.
<Melting and kneading conditions>
Same-direction biaxial kneader: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 500 rpm
<Injection molding conditions>
Injection molding machine: Part number IS100, cylinder machine manufactured by Toshiba Machine Co., Ltd .: 190 ° C
Mold temperature: 40 ℃

Ethylene-butene copolymer rubber (Tuffmer A-1050 (trademark), manufactured by Mitsui Chemicals, Inc.) (D-2) 12 parts by weight, talc with respect to 67 parts by weight of the propylene-based block copolymer (A-1) (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.) 21 parts by weight, heat stabilizer IRGANOX 1010 (trademark, Ciba Geigy) 0.1 part by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Corp.) )) 0.1 parts by weight and 0.1 parts by weight of calcium stearate were mixed in a tumbler and then melt-kneaded in a twin screw extruder to prepare a polypropylene resin composition in a pellet form, and an injection molding machine [Part No. IS100, An ASTM test piece was molded by Toshiba Machine Co., Ltd.]. Table 3 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: 190 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 500 rpm
<Injection molding conditions>
Injection molding machine: Part number IS100, cylinder machine manufactured by Toshiba Machine Co., Ltd .: 190 ° C
Mold temperature: 40 ℃

The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-2) produced in Production Example 2. Table 3 shows the physical properties of the molded product.

The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-3) produced in Production Example 3. Table 3 shows the physical properties of the molded product.

The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-4) produced in Production Example 4. Table 3 shows the physical properties of the molded product.

Production Example 1 with respect to 54 parts by weight of the propylene homopolymer (B-1) produced in Production Example 12
13 parts by weight of propylene-ethylene copolymer (C-2) produced in No. 4, ethylene-butene copolymer rubber (Tuffmer A-0550 (trademark), manufactured by Mitsui Chemicals) (D-1) 12 parts by weight Part,
Talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.) 21 parts by weight,
Thermal stabilizer IRGANOX1010 (Trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, thermal stabilizer IRGAFOS168
(Trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight and calcium stearate 0.1 parts by weight were mixed in a tumbler, then melt-kneaded in a twin screw extruder to prepare a pellet-shaped polypropylene resin composition, and injected ASTM test specimens were molded using a molding machine [Part No. IS100, manufactured by Toshiba Machine Co., Ltd.]. Table 3 shows the physical properties of the molded product.

In Example 6, it carried out similarly except having replaced 13 weight part of propylene-ethylene copolymer (C-2) with 13 weight part of propylene-ethylene copolymer (C-3) manufactured in manufacture example 15. .
Table 3 shows the physical properties of the obtained molded article.
[Comparative Example 1]
The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-6) produced in Production Example 6. . Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 2]
The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-7) produced in Production Example 7. . Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 3]
In Example 1, 67 parts by weight of the propylene-based block copolymer (A-1) and 20 parts by weight of the propylene-based block copolymer (A-8) produced in Production Example 8 and the propylene produced in Production Example 9 The procedure was the same except that the amount of the system block copolymer (A-9) was changed to 47 parts by weight. Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 4]
The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-10) produced in Production Example 10. . Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 5]
The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-11) produced in Production Example 11. . Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 6]
The same procedure as in Example 6 was carried out except that 13 parts by weight of the propylene-ethylene copolymer (C-2) was replaced with 13 parts by weight of the propylene-ethylene copolymer (C-1) produced in Production Example 13. .
Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 7]
The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-12) produced in Production Example 12. . Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 8]
The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-13) produced in Production Example 13. . Table 4 shows the physical properties of the obtained molded article.
[Comparative Example 9]
The same procedure as in Example 1 was conducted except that 67 parts by weight of the propylene-based block copolymer (A-1) was replaced with 67 parts by weight of the propylene-based block copolymer (A-14) produced in Production Example 14. . Table 4 shows the physical properties of the obtained molded article.

  The injection-molded article obtained from the composition containing a propylene-based resin satisfying specific properties of the present invention is excellent in weld appearance, flow mark appearance, and has good rigidity and impact resistance. It can be suitably used for automobile parts.

It is drawing explaining the weld appearance evaluation method and the flow mark appearance evaluation method.

Claims (3)

20 to 98 parts by weight of propylene-based resin (A) polymerized under a metallocene compound-containing catalyst, 1 to 40 parts by weight of elastomer (D) and 1 to 40 parts by weight of inorganic filler (E) (however, (A), (D ), (E) total 100 parts by weight), and the propylene resin (A) satisfies the following (i) to (iii):
(I) 10 to 50% by weight of a part soluble in room temperature n-decane (D _sol ) and 50 to 90% by weight of a part insoluble in room temperature n-decane (D _insol ) (ii) Propylene ( _MP ), And a resin composed of a polymer obtained from one or more olefins (M _X ) selected from ethylene and an α-olefin having 4 or more carbon atoms (iii) D _sol and D _{insol satisfy the} following requirements (1 ) To (6) are satisfied simultaneously
(1) The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of D _sol and D _insol is 3.5 or less.
(2) The melting point (Tm) of D _insol is 156 ° C or higher
(3) The sum of 2,1-insertion bond amount and 1,3-insertion bond amount in D _insol is 0.05 mol% or less
(4) The intrinsic viscosity [η] of D _insol is 0.8 to 1.5 dl / g
(5) The intrinsic viscosity [η] of D _sol is 2.0 to 4.0 dl / g
(6) The total amount of olefin (M _X ) selected from ethylene and α-olefin having 4 or more carbon atoms in D _sol is 25 to 80 mol%.   The automobile part according to claim 1, wherein the automobile part is injection-molded using a mold having two or more gates.   The automobile part according to claim 2, wherein the number of gates is 3 to 10 points.

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