JP5221406B2 - Propylene-based resin composition and molded article comprising the composition - Google Patents

Description

  The present invention relates to a propylene-based resin composition and a molded body made of the composition. More specifically, the present invention relates to a propylene-based resin composition from which a molded article having an excellent balance of rigidity, impact resistance, and elongation at break can be obtained.

  Propylene resin is used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automobile parts, etc., and various additives are blended according to the required performance. Has been. Especially in automotive parts, medical / food containers, etc., in order to develop a good balance between the rigidity and impact resistance of the molded product, a propylene-based compound that contains a rubber component such as an ethylene / α-olefin copolymer in a propylene resin A resin composition is used.

  As efforts for 3R (Reduce, Reuse, Recycle) to form a recycling-oriented society, attempts have been made to reduce the weight of thin molded products in each industrial field recently. The propylene resin composition is also being improved so that sufficient rigidity and impact resistance can be obtained even if the molded product is lightened and thinned.

  For example, Patent Document 1 and Patent Document 2 disclose a propylene-based block copolymer produced in the presence of a metallocene-based catalyst and a composition containing the propylene-based block copolymer. Although the propylene-based resin compositions disclosed in these patent documents have improved rigidity and impact resistance, it is necessary to improve the balance of mechanical properties such as elongation at break.

JP 2003-147035 A JP 2007-2111189 A

  An object of the present invention is to provide a propylene-based resin composition from which a molded article having an excellent balance of mechanical properties such as rigidity, impact resistance, and elongation at break can be obtained.

The present inventors are a propylene-based resin composition containing a propylene homopolymer and a propylene-ethylene copolymer, which is a component insoluble in room temperature n-decane (D _insol ) and soluble in room temperature n-decane. It has been found that according to the propylene-based resin composition in which the component (D _sol ) satisfies specific requirements, a molded article having an excellent balance of mechanical properties such as rigidity, impact resistance and elongation at break can be obtained.

That is, the first propylene resin composition (I) of the present invention is a propylene resin composition (I) containing a propylene homopolymer and a propylene-ethylene copolymer,
Components insoluble in room temperature n-decane (hereinafter also referred to as “D _insol ”) are the following requirements (i) to (iii)
And a component soluble in room temperature n-decane (hereinafter also referred to as “D _sol ”) satisfies the following requirements (a) to (e).
(I) the melting point is 156 ° C. or higher,
(Ii) the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 0.6 to 4 dl / g,
(Iii) The ethylene content is 3% by weight or less,
(A) The amount of D _sol in 100% by weight of the propylene-based resin composition (I) is 15 to 50% by weight;
(B) the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 1.8 to 4 dl / g,
(C) The content of a component having a molecular weight of 1.5 million or more in the molecular weight distribution curve calculated by GPC measurement is 1 to 8% by weight with respect to the entire D _sol ,
(D) The ethylene content (C "2 (M150)) in the component having a molecular weight of 1.5 million measured by GPC-IR measurement is 25 to 37 mol%,
(E) The ethylene content (C "2) is 40 to 65 mol%.

In the propylene resin composition (I), D _insol preferably satisfies the following requirement (iv).
(Iv) The molecular weight distribution (Mw / Mn) is 2.5 to 5.0.

The propylene-based resin composition (I) is composed of 50 to 99 parts by weight of a propylene-based block copolymer (A) polymerized under a metallocene compound-containing catalyst and a propylene-based block copolymer polymerized under a Ziegler-Natta catalyst ( B) A propylene-based block copolymer (B) formed from 1 to 50 parts by weight (provided that (A) + (B) = 100 parts by weight) and polymerized under a Ziegler-Natta catalyst is as follows: It is preferable to satisfy the requirements (a) and (b).
(A) The intrinsic viscosity [η] of the component soluble in room temperature n-decane (D _sol ) is 5 to 15 dl / g,
(A) The ethylene content of the component soluble in room temperature n-decane (D _sol ) is 25 to 37 mol%.

  The second propylene-based resin composition (II) of the present invention preferably contains the above-mentioned propylene-based resin composition (I), and further contains an inorganic filler (F) and / or an elastomer (E).

  The propylene resin composition (II) of the present invention comprises 50 to 99 parts by weight of the above-mentioned propylene resin composition (I) and 1 to 50 parts by weight of an inorganic filler (F) (however, (I) + ( F) = 100 parts by weight).

  The propylene resin composition (II) of the present invention comprises 50 to 99 parts by weight of the propylene resin composition (I) and 1 to 50 parts by weight of the elastomer (E) (provided that (I) + (E ) = 100 parts by weight).

  The propylene resin composition (II) of the present invention comprises 50 to 98 parts by weight of the above-mentioned propylene resin composition (I), 1 to 49 parts by weight of an inorganic filler (F), and elastomer (E) 1 to 1 part. 49 parts by weight (however, (I) + (E) + (F) = 100 parts by weight) is preferable.

  The first molded body of the present invention is obtained by molding the above-mentioned propylene-based resin composition (I). The second molded body of the present invention is obtained by molding the above-mentioned propylene-based resin composition (II). These molded bodies are preferably injection molded bodies and can be suitably used for automobile parts.

Since the propylene-based resin composition according to the present invention can provide a molded article having excellent balance of mechanical properties such as rigidity, impact resistance and elongation at break, it can be used for various molded products, particularly large molded products such as automobile parts. It can be preferably used.

  Hereinafter, the propylene-based resin composition of the present invention and a molded article made of the composition will be described in detail.

[Propylene resin composition (I)]
The first propylene resin composition (I) of the present invention is a propylene resin composition (I) containing a propylene homopolymer and a propylene-ethylene copolymer, and is a component insoluble in room temperature n-decane (Hereinafter also referred to as “D _insol ”) satisfies the following requirements (i) to (iii), more preferably (iv), and is soluble in room temperature n-decane (hereinafter also referred to as “D _sol ”). It is characterized by satisfying the following requirements (a) to (e).

[D _insol ]
(I) The melting point is 156 ° C. or higher.
(Ii) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 0.6 to 4 dl / g.
(Iii) The ethylene content is 3% by weight or less.
(Iv) The molecular weight distribution (Mw / Mn) is 2.5 to 5.0.

[D _sol ]
(A) The amount of D _sol in 100% by weight of the propylene-based resin composition (I) is 15 to 50% by weight.
(B) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 1.8 to 4 dl / g.
(C) The content of the component having a molecular weight of 1.5 million or more in the molecular weight distribution curve calculated by GPC measurement is 1 to 8% by weight with respect to the entire D _sol .
(D) The ethylene content (C "2 (M150)) in the component having a molecular weight of 1.5 million measured by GPC-IR measurement is 25 to 37 mol%.
(E) The ethylene content (C "2) is 40 to 65 mol%.

  Hereafter, each said requirement is demonstrated in detail.

<Requirement (i)>
The melting point (Tm) of D _insol is 156 ° C. or higher, preferably 157 ° C. or higher, and more preferably 160 ° C. or higher. If the melting point of D _insol is lower than 156 ° C., the rigidity and heat resistance of the molded product obtained from the propylene-based resin composition may be lowered. D _insol melting point (
The upper limit of Tm) is not particularly limited, but is usually 167 ° C.

<Requirement (ii)>
The intrinsic viscosity [η] of D _insol measured in a decalin solvent at 135 ° C. is 0.6-4 dl / g, preferably 0.7-3 dl / g, more preferably 0.8-2. 5 dl / g. When the intrinsic viscosity [η] of D _insol is lower than 0.6 dl / g, the impact resistance and elongation of the molded product obtained from the propylene-based resin composition are lowered, which is not preferable. In addition, if the intrinsic viscosity [η] of D _insol is higher than 4 dl / g, the fluidity during molding is lowered, which may make it difficult to apply to large injection molded parts.

<Requirement (iii)>
The ethylene content of D _insol is 3% by weight or less, preferably 2% by weight or less, and more preferably 1.5% by weight or less. When the composition distribution of the propylene-ethylene copolymer contained in the propylene-based resin composition is wide, since the polyethylene component by-produced during the polymerization of the propylene-ethylene copolymer is insoluble in n-decane, the ethylene content of D _insol Tend to increase. If the ethylene content of D _insol is more than 3% by weight, the balance between rigidity and impact resistance may be reduced due to the influence of the by-product polyethylene component.

<Requirement (iv)>
The molecular weight distribution (Mw / Mn) of D _insol is 2.5 to 5.0, preferably 2.7 to 4.5, and more preferably 3.0 to 4.0. When the molecular weight distribution (Mw / Mn) of D _insol is larger than 5.0, the weld line becomes conspicuous at the time of injection molding, and may not be suitable for injection molded parts having complicated shapes. Also, if the molecular weight distribution (Mw / Mn) of D _insol is less than 2.5, it is not suitable for molding large parts, such as a decrease in fluidity in the mold during injection molding or drawdown during hollow molding. There is a case.

In the present invention, the molecular weight distribution (Mw / Mn) is a ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC.

<Requirement (a)>
The amount of D _sol in 100% by weight of the propylene-based resin composition (I) is 15 to 50% by weight, preferably 20 to 45% by weight, and more preferably 20 to 40% by weight. If the amount of D _sol is less than 15% by weight, the low temperature impact resistance of the molded product obtained from the propylene resin composition is not preferable. If the amount of D _sol is more than 50% by weight, the rigidity is lowered, so that it may be difficult to apply in some products.

<Requirement (b)>
The intrinsic viscosity [η] of D _sol measured in a decalin solvent at 135 ° C. is 1.8 to 4 dl / g, preferably 2.0 to 3.7 dl / g, more preferably 2.3 to 3. 3.5 dl / g. If the intrinsic viscosity [η] of D _sol is lower than 1.8 dl / g, the impact resistance of the molded product obtained from the propylene-based resin composition is lowered, which is not preferable. On the other hand, if the intrinsic viscosity [η] of D _sol is higher than 4 dl / g, the fluidity of the propylene-based resin composition is lowered, and the moldability may be deteriorated.

<Requirement (c)>
In D _sol, the content of molecular weight 1.5 million or more components in the molecular weight distribution curve calculated by GPC measurement (hereinafter also simply referred to as "molecular weight 1.5 million or more components.") Is 1-8 weight for the entire D _sol %, Preferably 1.5 to 7.5% by weight, more preferably 2 to 7% by weight. When the component having a molecular weight of 1.5 million or more is more than 8% by weight based on the whole D _sol , the fluidity of the propylene-based resin composition may be lowered or the rigidity of the molded product may be lowered. On the other hand, if the component having a molecular weight of 1,500,000 or more is less than 1% by weight based on the entire D _sol , the impact resistance of the molded product obtained from the propylene-based resin composition may be lowered.

<Requirement (d)>
In D _sol , the ethylene content (C "2 (M150)) (hereinafter, also simply referred to as" ethylene content (C "2 (M150))") of the component having a molecular weight of 1.5 million measured by GPC-IR measurement. It is 25-37 mol%, preferably 27-36 mol%, more preferably 28-35 mol%. When the ethylene content (C "2 (M150)) is higher than 37 mol%, the elongation at break of the molded product obtained from the propylene-based resin composition may deteriorate, which is not preferable. When 2 (M150)) is lower than 25 mol%, the rigidity of the molded product obtained from the propylene-based resin composition may be lowered.

<Requirement (e)>
The ethylene content (C "2) of D _sol is 40 to 65 mol%, preferably 41 to 60 mol%, more preferably 42 to 55 mol%.

When the ethylene content (C "2) of D _sol is lower than 40 mol%, the glass transition temperature of the propylene-ethylene copolymer becomes high, so that the low-temperature impact property of the molded product obtained from the propylene-based resin composition is lowered. Moreover, since the propylene-ethylene copolymer becomes hard when the ethylene content (C "2) of D _sol is higher than 65 mol%, the impact resistance of the molded product obtained from the propylene-based resin composition is lowered. There is a case.

According to the propylene-based resin composition (I) that satisfies the above requirements, it is possible to obtain a molded article having an excellent balance of mechanical properties such as rigidity, impact resistance, and elongation at break.

The propylene-based resin composition (I) satisfying each of the above requirements includes a propylene-ethylene copolymer component effective for improving impact resistance at low temperatures as shown in the requirement (e), and the requirements (c) and As shown in (d), it contains an appropriate amount of a propylene-ethylene copolymer component having a low ethylene content and a high molecular weight that is compatible with the propylene homopolymer. Here, the propylene-ethylene copolymer component having a low ethylene content and a high molecular weight acts as an interfacial reinforcing agent between the propylene-based polymer and the propylene-ethylene copolymer component effective for low-temperature impact resistance expression. It is presumed that the impact resistance and the elongation at break are good. In addition, the melting point of the propylene homopolymer portion is high as shown in requirement (i), and there are few crystalline polyethylene components by-produced during propylene-ethylene copolymer polymerization as shown in requirement (iii). Therefore, it is inferred that the rigidity becomes high.

Such a propylene-based resin composition (I) includes, for example, a propylene-based block copolymer (A) (hereinafter simply referred to as “(A)” or “propylene-based block copolymer”) polymerized under a metallocene compound-containing catalyst described later. And a propylene-based block copolymer (B) polymerized under a Ziegler-Natta catalyst described later (hereinafter also simply referred to as “B” or “propylene-based block copolymer (B)”). )).

The propylene resin composition (I) comprises 50 to 99 parts by weight of a propylene block copolymer (A) polymerized under a metallocene compound-containing catalyst, and a propylene block copolymer polymerized under a Ziegler-Natta catalyst. (B) 1 to 50 parts by weight (provided that (A) + (B) = 100 parts by weight), and the propylene-based block copolymer (B) has the following requirements (A) and (I) It is preferable to satisfy.
(A) The intrinsic viscosity [η] of the component (D _sol ) soluble in room temperature n-decane is 5 to 15 dl / g.
(A) The ethylene content of the component soluble in room temperature n-decane (D _sol ) is 25 to 37 mol%.

According to such a propylene-based resin composition (I), a molded article having an excellent balance of mechanical properties such as rigidity, impact resistance, and elongation at break can be obtained.

  In the present invention, the intrinsic viscosity [η] is a value measured in a decalin solvent at 135 ° C.

When the proportion of the propylene block copolymer (A) and (B) is (A) + (B) = 100 parts by weight, the propylene block copolymer (A) is 60 to 99 parts by weight. More preferably, the propylene-based block copolymer (B) is 1 to 40 parts by weight, the propylene-based block copolymer (A) is 70 to 99 parts by weight, and the propylene-based block copolymer (B ) Is more preferably 1 to 30 parts by weight.

When the amount of the propylene-based block copolymer (A) is less than 50 parts by weight and the amount of the propylene-based block copolymer (B) is more than 50 parts by weight, the room temperature n of the propylene-based resin composition (I) _-The molecular weight distribution (Mw / Mn) of the component insoluble in decane (D _insol ) is increased, and the weld appearance of the injection molded product may be deteriorated.

  When the amount of the propylene-based block copolymer (A) is more than 99 parts by weight and the amount of the propylene-based block copolymer (B) is less than 1 part by weight, the propylene-based block copolymer (B) is derived. As the amount of low ethylene content and high molecular weight propylene-ethylene copolymer rubber component decreases, problems such as lower elongation at break and lower impact resistance of molded products obtained from propylene-based resin compositions occur There is a case.

  Hereinafter, the propylene block copolymer (A) polymerized under the metallocene compound-containing catalyst and the propylene block copolymer (B) polymerized under the Ziegler-Natta catalyst will be described in detail.

[Propylene block copolymer (A)]
The propylene-based block copolymer (A) is produced by polymerizing a propylene homopolymer and then polymerizing a propylene-ethylene copolymer in the presence of a metallocene compound-containing catalyst.

In addition, the propylene-based block copolymer (A) usually has a portion soluble in room temperature n-decane (D _sol ) 10 to 80% by weight and a portion insoluble in room temperature n-decane (D _insol ) 20 to 90% by weight. It consists of.

In the propylene-based block copolymer (A), experience indicates that the propylene homopolymer mainly corresponds to a component (D _insol ) insoluble in room temperature n-decane, and the propylene-ethylene copolymer is soluble in room temperature n-decane. This corresponds to a major component (D _sol ).

  The propylene-based block copolymer (A) used in the present invention preferably has the following requirements (1) to (6).

<Requirement (1)>
The molecular weight distribution (Mw / Mn) of D _sol is 3.5 or less, preferably 1.0 to 3.0, and more preferably 1.0 to 2.5. When the molecular weight distribution of D _sol (Mw / Mn) is greater than 3.5, for the low molecular weight component in the D _sol is increased, the impact resistance of a molded article obtained from the propylene resin composition is lowered.

<Requirement (2)>
The molecular weight distribution (Mw / Mn) of D _insol is usually 1.5 to 3.5, preferably 2.0 to 3.0. When the molecular weight distribution (Mw / Mn) of D _insol is smaller than 1.5, the fluidity of the propylene-based resin composition at the time of injection molding is deteriorated, and the productivity is lowered.

<Requirement (3)>
The melting point (Tm) of D _insol measured by DSC is 145 ° C. or higher, preferably 150 ° C. or higher, more preferably 155 ° C. or higher. If the melting point (Tm) of D _insol is less than 145 ° C., the rigidity of the molded product obtained from the propylene-based resin composition is lowered, and it may be difficult to apply a large product.

<Requirement (4)>
The intrinsic viscosity [η] of D _insol measured in a decalin solvent at 135 ° C. is usually 0.7-4.
0 dl / g, preferably 0.8 to 3.0 dl / g, more preferably 0.9 to 2.5 dl / g, and particularly preferably 0.9 to 2.0 dl / g. If the intrinsic viscosity [η] of D _insol is lower than 0.7 dl / g, the molecular weight of the propylene homopolymer portion is small, and the elongation at break and impact resistance of the molded product obtained from the propylene-based resin composition are lowered. Is not preferable. Moreover, when the intrinsic viscosity [η] of D _insol is higher than 4.0 dl / g, the fluidity of the propylene-based resin composition is lowered, and it may be difficult to apply it to a large injection molded product or the like.

<Requirement (5)>
The intrinsic viscosity [η] of D _sol measured in a decalin solvent at 135 ° C. is 1.0 to 4.0 dl.
/ G, preferably 1.5 to 3.5 dl / g, more preferably 1.8 to 3.0 dl / g, and particularly preferably 2.0 to 2.5 dl / g. D _sol intrinsic viscosity [η
] Is lower than 1.0 dl / g, the low molecular weight component in D _sol increases, the impact resistance of the molded product obtained from the propylene-based resin composition decreases, and it becomes difficult to apply to various molded products There is. Further, if the intrinsic viscosity [η] of D _sol is higher than 4.0 dl / g, the fluidity of the propylene-based resin composition is lowered, and it may be difficult to apply to a large injection molded part.

<Requirement (6)>
The amount of ethylene (M _E ) in D _sol is 37 to 70 mol%, preferably 40 to 65 mol%, more preferably 45 to 60 mol%. When the amount of ethylene (M _E ) in D _sol is less than 37 mol%, the glass transition temperature of the propylene-ethylene copolymer portion increases, and the low temperature impact property of the molded product obtained from the propylene resin composition decreases. Therefore, it is not preferable. When the amount of ethylene (M _E ) in D _sol is more than 70 mol%, the propylene-ethylene copolymer becomes hard, and the impact resistance of the molded product obtained from the propylene-based resin composition may be lowered.

<Metallocene compound-containing catalyst>
The metallocene compound-containing catalyst used in the present invention includes at least one compound selected from metallocene compounds, and compounds capable of reacting with organometallic compounds, organoaluminum oxy compounds and metallocene compounds to form ion pairs. Furthermore, a metallocene catalyst which can be subjected to stereoregular polymerization such as an isotactic or syndiotactic structure, if necessary, is preferably a metallocene catalyst comprising a particulate carrier. 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 as or different from each other, 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 ', 4 ', 7', 7 ', 10', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a- Tetrahydropentalene)] zirconium Ride (compound represented by the following formula [II]), it is preferably mentioned compounds represented by the following formula [III].

  In addition, in the metallocene compound-containing catalyst used for the production of the propylene-based block copolymer (A), an organometallic compound, an organoaluminum oxy compound, which is used together with the Group 4 transition metal compound represented by the general formula [I], As for the compound that reacts with the transition metal compound to form an ion pair, and the particulate carrier used as necessary, the above-mentioned publications (WO01 / 27124 pamphlet) and JP-A-11-315109. The compounds disclosed in can be used without limitation.

[Producing method of propylene-based block copolymer (A)]
When the propylene-based block copolymer (A) is produced, a polymerization apparatus in which two or more reactors are connected in series is used, and the following two steps ([Step 1] and [Step 2]) are continuously performed. To implement. In the present invention, using a polymerization apparatus in which two or more reactors are connected in series, [Step 1] can be performed in each polymerization apparatus, and a polymerization apparatus in which two or more reactors are connected in series is provided. And [Step 2] can be carried out in each polymerization apparatus.

[Step 1] is a step of propylene homopolymerization or copolymerization of ethylene and propylene as necessary 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] becomes the main component of D _insol by propylene homopolymerization or by _reducing the amount of ethylene fed to propylene to a small amount. Can be adjusted.

[Step 2] is a step of copolymerizing propylene and 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-ethylene copolymer produced in [Step 2] becomes the main component of D _sol by increasing the amount of ethylene fed to propylene than in [Step 1]. Can be adjusted.

By adjusting the polymerization conditions in [Step 1], the above requirements (2) to (4) relating to D _insol of the propylene-based block copolymer (A) can be satisfied.

Further, by adjusting the polymerization conditions in [Step 2], the above requirements (1), (5) and (6) relating to D _sol of the propylene-based block copolymer (A) can be satisfied.

After completion of the polymerization, the propylene-based block polymer (A) 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.

[Propylene block copolymer (B)]
The propylene-based block copolymer (B) used in the present invention is produced by polymerizing a propylene homopolymer and then polymerizing a propylene-ethylene copolymer in the presence of a Ziegler-Natta catalyst.

In addition, the propylene-based block copolymer (B) usually has a portion soluble in room temperature n-decane (D _sol ) 10 to 80% by weight and a portion insoluble in room temperature n-decane (D _insol ) 20 to 90% by weight. It consists of.

In the propylene-based block copolymer (B), a component insoluble in room temperature n-decane (D _insol ) is a crystal similar to polyethylene produced as a by-product during the polymerization of propylene homopolymer and propylene-ethylene copolymer. A component (D _sol ) that corresponds to a highly soluble component and is soluble in n-decane at room temperature corresponds to a propylene-ethylene copolymer from experience.

  The propylene-based block copolymer (B) used in the present invention has the following requirements (a) and (b).

<Requirements (A)>
The intrinsic viscosity [η] of the component (D _sol ) soluble in n-decane at room temperature is 5 to 15 dl / g, preferably 5.2 to 10 dl / g, more preferably 5.4 to 8 dl / g. It is.

When the intrinsic viscosity [η] of D _sol is lower than 5 dl / g, in the propylene-based resin composition,
The interface between the propylene-based polymer part and the propylene-ethylene copolymer part becomes weak, and the elongation at break and impact resistance of the molded product obtained from the propylene-based resin composition may be reduced. When the intrinsic viscosity [η] of D _sol is higher than 15 dl / g, the fluidity of the propylene-based resin composition is lowered, and it may be difficult to apply the resin composition to a large injection molded part.

<Requirement (I)>
The ethylene content of the component (D _sol ) soluble in room temperature n-decane is 25 to 37 mol%, preferably 26 to 36 mol%, particularly preferably 28 to 35 mol%.

If the ethylene content of D _sol is lower than 25 mol%, the rigidity of the molded product obtained from the propylene-based resin composition may decrease, which is not preferable. If the ethylene content is higher than 37 mol%, the elongation at break of the molded product obtained from the propylene-based resin composition decreases, which is not preferable.

  Furthermore, the propylene block copolymer (B) preferably satisfies the following requirements (c) and (d).

<Requirement (U)>
The melting point (Tm) of D _insol measured by DSC is 160 ° C. or higher, more preferably 1
It is 62 ° C. or higher. When the melting point (Tm) of D _insol is lower than 160 ° C., the rigidity of the molded body obtained from the propylene-based resin composition is lowered, and it may be difficult to apply the resin composition to a partially molded product. The upper limit of the melting point (Tm) of D _insol is not particularly limited, but is usually 167
° C.

<Requirement (D)>
The intrinsic viscosity [η] of D _insol measured in a decalin solvent at 135 ° C. is usually 0.7 to 4.0.
dl / g, preferably 0.8 to 3.0 dl / g, more preferably 0.9 to 2.5 dl / g, and particularly preferably 0.9 to 2.0 dl / g. When the intrinsic viscosity [η] of D _insol is lower than 0.7 dl / g, the molecular weight of the propylene homopolymer portion is low, and the fracture elongation and impact resistance of the molded product obtained from the propylene-based resin composition are reduced. There is. Moreover, when the intrinsic viscosity [η] of D _insol is higher than 4.0 dl / g, the fluidity of the propylene-based resin composition is lowered, and it becomes difficult to apply the resin composition to a large-sized injection-molded product or the like. There is.

<Ziegler Natta catalyst>
The propylene block copolymer (B) can be produced by using a highly stereoregular Ziegler-Natta catalyst. Various known catalysts can be used as the highly stereoregular Ziegler-Natta catalyst. For example, (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor, (b) an organometallic compound catalyst component, (c) a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group and A catalyst comprising an organosilicon compound catalyst component having at least one group selected from the group consisting of these derivatives can be used.

  The solid titanium catalyst component (a) can be prepared by contacting a magnesium compound (a-1), a titanium compound (a-2) and an electron donor (a-3). Examples of the magnesium compound (a-1) include a magnesium compound having a reducing ability such as a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond, and a magnesium halide, an alkoxymagnesium halide, an allyloxymagnesium halide, an alkoxymagnesium, Examples thereof include magnesium compounds having no reducing ability, such as allyloxy magnesium and magnesium carboxylate.

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

Ti (OR) _g X _4-g (1)
(In the formula (1), R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.)
Specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H ₉ ) Br ₃ and other trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl _{2, Ti (O-n-} C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) ₃ Cl, T
_{i (O-n-C 4} H 9) 3 Cl, Ti (OC 2 H 5) monohalide trialkoxy titanium such as _{3 Br; Ti (OCH 3)} 4, Ti (OC 2 H 5) 4, Ti ( _{O-n-C 4 H 9} ) 4, Ti (O-iso-
And tetraalkoxytitanium such as C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

  Examples of the electron donor (a-3) used in the preparation of the solid titanium catalyst component (a) include alcohols, phenols, ketones, aldehydes, esters of organic acids or inorganic acids, organic acid halides, ethers, acids. Examples include amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, and oxygen-containing cyclic compounds.

  When contacting the magnesium compound (a-1), titanium compound (a-2) and electron donor (a-3) as described above, other reaction reagents such as silicon, phosphorus, and aluminum are allowed to coexist. In addition, a carrier-supporting solid titanium catalyst component (a) can be prepared using a carrier.

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

As the organometallic compound catalyst component (b), those containing a metal selected from Group I to Group III of the periodic table are preferable. Specifically, an organoaluminum compound, a Group I metal and aluminum as shown below And a complex alkyl compound, and an organometallic compound of a Group II metal.

Formula R ²¹ _m Al (OR ²² ) _n H _p X _q (wherein R ²¹ and R ²² are hydrocarbon groups usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which are identical to each other) X is a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.) An organoaluminum compound (b-1).

Complex alkylated product of group I metal and aluminum represented by the formula M ¹ AlR ²¹ ₄ (wherein M ¹ is Li, Na or K, and R ²¹ is the same as above) (b-2) .

Group II or Group III dialkyl compound of formula R ²¹ R ²² M ² (wherein R ²¹ and R ²² are as defined above, and M ² is Mg, Zn or Cd) (b -3).

Examples of the organoaluminum compound (b-1) include R ²¹ _m Al (OR ²² ) _3-m (R ²¹ and R ²² are the same as described above, and m is preferably a number satisfying 1.5 ≦ m ≦ 3. A compound represented by R ²¹ _m AlX _3-m (wherein R ²¹ is as defined above, X is a halogen, and m is preferably 0 <m <3), A compound represented by R ²¹ _m AlH _3-m (R ²¹ is as defined above, m is preferably 2 ≦ m <3), R ²¹ _m Al (OR ²² ) _n X _q (
R ²¹ and R ²² are the same as above, X is halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3. ) And the like.

  Specific examples of the organosilicon compound catalyst component (c) include an organosilicon compound represented by the following formula (2).

SiR ²³ R ²⁴ _a (OR ²⁵ ) _3-a (2)
(In the formula (2), a is 0, 1 or 2, R ²³ is a group selected from the group consisting of a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group and derivatives thereof, and R ²⁴ and R ²⁵ are hydrocarbons. Group.)
In the formula (2), specific examples of R ²³ include cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 3-propylcyclopentyl group, 3-isopropylcyclopentyl group, 3 -Butylcyclopentyl group, 3-tert-butylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-
Dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,2,5-trimethylcyclopentyl group, 2,3,4,5-tetramethylcyclopentyl group, 2,2,5,5-tetramethylcyclopentyl group, 1- Cyclopentyl group such as cyclopentylpropyl group, 1-methyl-1-cyclopentylethyl group or derivatives thereof; cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl -3-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 2-ethyl-3-cyclopentenyl group, 2,2-dimethyl-3-cyclopentenyl group, 2,5-dimethyl-3-cyclopentenyl group 2,3,4,5-tetramethyl-3-cyclopentenyl group, 2,2,5,5-tetramethyl-3-cycl Cyclopentenyl group such as pentenyl group or derivatives thereof; 1,3-cyclopentadienyl group, 2,4-cyclopentadienyl group, 1,4-cyclopentadienyl group, 2-methyl-1,3-cyclo Pentadienyl group, 2-methyl-2,4-cyclopentadienyl group, 3-methyl-2,4-cyclopentadienyl group, 2-ethyl-2,4-cyclopentadienyl group, 2,2 -Dimethyl-2,4-cyclopentadienyl group, 2,3-dimethyl-2,4-cyclopentadienyl group, 2,5-dimethyl-2,4-cyclopentadienyl group, 2,3,4 Cyclopentadienyl group such as 1,5-tetramethyl-2,4-cyclopentadienyl group or a derivative thereof; and a derivative of cyclopentyl group, cyclopentenyl group or cyclopentadienyl group as indenyl group, 2-methyl Indenyl group, 2-ethyl-indenyl group, 2-indenyl group, 1-methyl-2-indenyl group, 1,
3-dimethyl-2-indenyl group, indanyl group, 2-methylindanyl group, 2-indanyl group, 1,3-dimethyl-2-indanyl group, 4,5,6,7-tetrahydroindenyl group, 4, 5,6,7-tetrahydro-2-indenyl group, 4,5,6,7-tetrahydro-1-methyl-2-indenyl group, 4,5,6,7-tetrahydro-1,3-dimethyl-2- Indenyl group, fluorenyl group and the like can be mentioned.

In formula (2), specific examples of the hydrocarbon group represented by R ²⁴ and R ²⁵ include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. When two or more R ²⁴ or R ²⁵ are present, R ²⁴ or R ²⁵ may be the same or different, and R ²⁴ and R ²⁵ may be the same or different. In the formula (2), R ²³ and R ²⁴ may be cross-linked with an alkylene group or the like.

The Among the organic silicon compound represented by the formula (2) is R ²³ is cyclopentyl, R ²⁴ is an alkyl group or a cyclopentyl group, an organic silicon compound R ²⁵ is an alkyl group, especially a methyl or ethyl group Is preferred.

Specific examples of the organosilicon compound represented by the formula (2) include cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and 2,5-dimethylcyclopentyltrimethoxy. Trialkoxysilanes such as silane, cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane, fluorenyltrimethoxysilane Dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (3-tert-butylcyclopentyl) dimethoxysilane, bis (2,3-
Dimethylcyclopentyl) dimethoxysilane, bis (2,5-dimethylcyclopentyl)
Dimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentenyldimethoxysilane, di (3-cyclopentenyl) dimethoxysilane, bis (2,5-dimethyl-3-
Cyclopentenyl) dimethoxysilane, di-2,4-cyclopentadienyldimethoxysilane, bis (2,5-dimethyl-2,4-cyclopentadienyl) dimethoxysilane, bis (1-methyl-1-cyclopentylethyl) Dimethoxysilane, cyclopentylcyclopentenyldimethoxysilane, cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane, bis (1,3-dimethyl-2-indenyl) dimethoxysilane, cyclopentadienylindenyldimethoxysilane, difluorenyl Dialkoxysilanes such as dimethoxysilane, cyclopentylfluorenyldimethoxysilane, indenylfluorenyldimethoxysilane; tricyclopentylmethoxysilane, tricyclopentenylmethoxysilane, Cyclopentadienylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, bis (2,5 -Dimethylcyclopentyl) monoalkoxysilanes such as cyclopentylmethoxysilane, dicyclopentylcyclopentenylmethoxysilane, dicyclopentylcyclopentadienylmethoxysilane, diindenylcyclopentylmethoxysilane; and other examples include ethylenebiscyclopentyldimethoxysilane .

[Producing method of propylene-based block copolymer (B)]
The production of the propylene-based block copolymer (B) can be obtained by continuously performing the following two steps ([Step i] and [Step ii]).

[Step i] is a step of propylene homopolymerization or copolymerization of ethylene and propylene as necessary at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step i], propylene homopolymerization is carried out or the amount of ethylene fed to propylene is made small so that the propylene-based (co) polymer produced in [Step i] becomes the main component of D _insol. Can be adjusted.

[Step ii] is a step of copolymerizing propylene and ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step ii], the propylene-ethylene copolymer produced in [Step ii] becomes the main component of D _sol by increasing the amount of ethylene fed to propylene than in [Step i]. Can be adjusted.

In [Step ii], due to the hydrogen concentration in the polymerization system, the intrinsic viscosity of the propylene-ethylene copolymer [
η] can be controlled. For example, the intrinsic viscosity [η] of the propylene-ethylene copolymer can be controlled to be high by reducing the hydrogen concentration in the polymerization system. Therefore, by adjusting the polymerization conditions in [Step ii], it becomes possible to satisfy the requirements (a) and (b) related to the propylene-based block copolymer (B) D _sol .

By adjusting the polymerization conditions in [Step i], the above requirements (c) and (d) relating to D _insol of the propylene-based block copolymer (B) can be satisfied.

  After completion of the polymerization, a propylene block polymer (B) 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 addition, when polymerizing propylene using the catalyst comprising the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and the organosilicon compound catalyst component (c) as described above, a preliminary polymerization is performed in advance. It can also be done. In the prepolymerization, the olefin is polymerized in the presence of the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and, if necessary, the organosilicon compound catalyst component (c).

As the prepolymerized olefin, an α-olefin having 2 to 8 carbon atoms can be used. Specifically, linear olefins such as ethylene, propylene, 1-butene and 1-octene; 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene,
4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1- Olefin having a branched structure such as hexene can be used. These may be copolymerized.

  The prepolymerization is desirably performed so that a polymer of about 0.1 to 1000 g, preferably about 0.3 to 500 g, is produced per 1 g of the solid titanium catalyst component (a). If the amount of prepolymerization is too large, the production efficiency of the (co) polymer in the main polymerization may decrease. In the prepolymerization, the catalyst can be used at a considerably higher concentration than the catalyst concentration in the system in the main polymerization.

The production of the propylene-based block copolymer (B) can also be produced by continuously performing the above-mentioned two steps ([Step i] and [Step ii]) in a multistage polymerization.

  In the case of continuous multistage polymerization, in each stage, propylene is homopolymerized or propylene and ethylene are copolymerized to produce polypropylene. In the main polymerization, the solid titanium catalyst component (a) (or the prepolymerized catalyst) is converted to titanium atoms per liter of polymerization volume of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol. It is desirable to use in quantity. The organometallic compound catalyst component (b) is desirably used in an amount of about 1 to 2000 moles, preferably about 2 to 500 moles, based on 1 mole of titanium atoms in the polymerization system. The organosilicon compound catalyst component (c) is desirably used in an amount of about 0.001 to 50 moles, preferably about 0.01 to 20 moles per mole of metal atoms of the organometallic compound catalyst component (b).

  The polymerization may be performed by any of a gas phase polymerization method, a liquid polymerization method such as a solution polymerization method and a suspension polymerization method, and each stage may be performed by a separate method. Moreover, you may carry out by any system of a continuous type and a semi-continuous type, and you may divide each stage into several polymerizers, for example, 2-10 polymerizers. Industrially, it is most preferable to polymerize by a continuous method. In this case, it is preferable to carry out the polymerization in the second and subsequent stages separately into two or more polymerization vessels, thereby suppressing the generation of gel. .

  As the polymerization medium, inert hydrocarbons may be used, and liquid propylene may be used as the polymerization medium. The polymerization conditions in each stage are such that the polymerization temperature is in the range of about −50 to + 200 ° C., preferably about 20 to 100 ° C., and the polymerization pressure is normal pressure to 10 MPa (gauge pressure), preferably about 0.2 to 5 MPa. It is appropriately selected within the range of (gauge pressure).

[Production Method of Propylene Resin Composition (I)]
As a manufacturing method of the said propylene-type resin composition (I), if the propylene-type resin composition (I) which contains a propylene homopolymer and a propylene-ethylene copolymer and satisfy | fills said each requirement can be obtained especially, Although it does not restrict | limit, For example, the method of manufacturing by melt-kneading after mixing the said propylene-type block copolymer (A) and the said propylene-type block copolymer (B) is mentioned. When pelletized further, a pellet-like propylene resin composition (I) can be obtained.

In addition to the propylene block copolymers (A) and (B), the propylene resin composition (I) includes an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an anti Various additives such as a blocking agent, a colorant, an inorganic or organic filler, and various synthetic resins can be blended as necessary.

As a method of mixing the propylene-based block copolymers (A) and (B) and various additives used as necessary, a method using a normal kneading apparatus such as a Henschel mixer, a ribbon blender, a Banbury mixer, or the like. Can be mentioned. Further, examples of the method of melt kneading and pelletizing include a method of using a normal single-screw extruder, a twin-screw extruder, a brabender, or a roll. The temperature at the time of melt kneading and pelletizing is usually 170 to 300 ° C, preferably 190 to 250 ° C.

  When the proportion of the propylene-based block copolymers (A) and (B) is (A) + (B) = 100 parts by weight, the propylene-based block copolymer (A) is usually 50 to 99 weights. The propylene-based block copolymer (B) is usually 1 to 50 parts by weight, and the propylene-based block copolymer (A) is 60 to 99 parts by weight. More preferably, the blend (B) is 1 to 40 parts by weight, the propylene block copolymer (A) is 70 to 99 parts by weight, and the propylene block copolymer (B) is 1 to 30 parts by weight. Part by weight is particularly preferred.

When the amount of the propylene-based block copolymer (A) is less than 50 parts by weight and the amount of the propylene-based block copolymer (B) is more than 50 parts by weight, the resulting propylene-based resin composition (I) The molecular weight distribution (Mw / Mn) of the component (D _insol ) insoluble in room temperature n-decane is increased, and the weld appearance of the injection molded product may be deteriorated.

  When the amount of the propylene-based block copolymer (A) is more than 99 parts by weight and the amount of the propylene-based block copolymer (B) is less than 1 part by weight, the propylene-based block copolymer (B) is derived. As the amount of low ethylene content and high molecular weight propylene-ethylene copolymer rubber component decreases, problems such as lower elongation at break and lower impact resistance of molded products obtained from propylene-based resin compositions occur There is a case.

  The blending ratio of various additives used as necessary is preferably 0.01 to 5 parts by weight, and 0.05 to 2 parts by weight when (A) + (B) = 100 parts by weight. More preferably, it is 0.1-1 part by weight.

The propylene-based resin composition (I) obtained by the production method as described above can satisfy the above requirements.

[Propylene resin composition (II)]
The second propylene-based resin composition (II) of the present invention preferably contains the above-mentioned propylene-based resin composition (I), and further contains an inorganic filler (F) and / or an elastomer (E). A molded body obtained from such a propylene-based resin composition (II) has an excellent balance of mechanical properties such as rigidity, impact resistance and elongation at break.

<Composite of propylene resin composition (I) and inorganic filler (F)>
The propylene-based resin composition (II) may contain an inorganic filler (F) in addition to the above-described propylene-based resin composition (I), depending on the necessity for improving rigidity and heat resistance.

  Examples of such inorganic filler (F) include talc, clay, calcium carbonate, mica, silicates, carbonates, glass fibers, and carbon 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.

The content of the inorganic filler (F) is 1 to 50 parts by weight, preferably 3 to 40 parts by weight with respect to 100 parts by weight of the propylene-based resin composition (I) and the inorganic filler (F). Yes, more preferably 5 to 25 parts by weight. Content of the above-mentioned propylene-based resin composition (I) is 50 to 99 parts by weight, preferably 60 to 97 parts by weight, and more preferably 75 parts by weight to 95 parts by weight.

<Composite of propylene resin composition (I) and elastomer (E)>
The propylene-based resin composition (II) may contain an elastomer (E) for the purpose of adjusting the molding shrinkage rate and imparting paintability in addition to the above-described propylene-based resin composition (I).

  Examples of such elastomer (E) include ethylene / α-olefin random copolymer (E-a), ethylene / α-olefin / non-conjugated polyene random copolymer (E-b), and hydrogenated block copolymer. (Ec), other elastic polymers, and mixtures thereof.

The content of the elastomer (E) in the propylene-based resin composition is usually 1 to 50 parts by weight, preferably 100 parts by weight of the propylene-based resin composition (I) and the elastomer (E). Is 1 to 30 parts by weight, more preferably 1 to 15 parts by weight. Content of the above-mentioned propylene-type resin composition (I) is 50-99 weight part normally, Preferably it is 70-99 weight part, More preferably, it is 85-99 weight part. With such a blending ratio, the high rigidity and high impact resistance of the molded product obtained from the propylene-based resin composition (II) can be maintained.

  The ethylene / α-olefin random copolymer (E-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.

  In the ethylene / α-olefin random copolymer (E-a), the molar ratio of ethylene to α-olefin (ethylene / α-olefin) is usually 95/5 to 70/30, preferably 90/10 to 75 /. 25 is desirable. The ethylene / α-olefin random copolymer (Ea) 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 (E-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 Non-conjugated dienes such as 1,5-heptadiene, 6-methyl-1,7-octadiene, 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene It is done. Among these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used.

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

  The ethylene / α-olefin / non-conjugated polyene random copolymer (E-b) 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 (E-b) include an ethylene / propylene / diene terpolymer (EPDM).

  The hydrogenated block copolymer (Ec) is a hydrogenated block copolymer having a block form represented by the following formula (a) or (b), 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)
In the formula (a) or (b), X represents a monovinyl-substituted aromatic hydrocarbon, and Y represents a conjugated diene. n is an integer of 1 to 5, preferably 1 or 2.

  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.

  Specific examples of the hydrogenated block copolymer (E-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 manufacturing 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, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, and Japanese Patent Publication No. 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 commercial item can also be used as a hydrogenated block copolymer (Ec). 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 (E) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

<Combination of propylene resin composition (I), elastomer (E) and inorganic filler (F)>
In addition to the propylene resin composition (I) described above, the propylene resin composition (II) is an elastomer (E) for the purpose of highly balancing physical properties such as rigidity, heat resistance, dimensional accuracy improvement, and paintability. And an inorganic filler (F).

Total of propylene resin composition (I), elastomer (E) and inorganic filler (F) 1
The propylene-based resin composition (I) is 50 to 98 parts by weight with respect to 00 parts by weight, preferably 6
0 to 98 parts by weight, more preferably 70 to 98 parts by weight, and elastomer (E) is 1 to 49 parts by weight, preferably 1 to 39 parts by weight, more preferably 1 to 29 parts by weight, and an inorganic filler ( F) is 1 to 49 parts by weight, preferably 1 to 39 parts by weight, more preferably 1 to 29 parts by weight.

[Production Method of Propylene Resin Composition (II)]
The method for producing the propylene-based resin composition (II) is not particularly limited as long as the propylene-based resin composition (I) is contained. For example, the propylene-based resin composition (I) and necessary The elastomer (E), inorganic filler (F), and various additives that are used according to the above are mixed and then melt-kneaded for production. When pelletized further, a pellet-shaped propylene resin composition (II) can be obtained.

  Examples of the various additives include antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, lubricants, flame retardants, antiblocking agents, colorants, inorganic or organic fillers, various synthetic resins, and the like. Can do.

As a method of mixing the propylene-based resin composition (I), the elastomer (E), the inorganic filler (F), and various additives used as necessary, ordinary kneading such as a Henschel mixer, a ribbon blender, and a Banbury mixer The method of using an apparatus is mentioned. Further, examples of the method of melt kneading and pelletizing include a method of using a normal single-screw extruder, a twin-screw extruder, a brabender, or a roll. The temperature at the time of melt kneading and pelletizing is usually 170 to 300 ° C, preferably 190 to 250 ° C.

The propylene-based resin composition (I) and an elastomer (E) used as necessary,
The blending ratio with the inorganic filler (F) is as described above.

The blending ratio of various additives used as necessary is the propylene resin composition (I).
Is 100 to 5 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and particularly preferably 0.1 to 1 part by weight.

[Molded body]
The first molded body of the present invention is obtained by molding the above-mentioned propylene-based resin composition (I). The second molded body of the present invention is obtained by molding the above-mentioned propylene-based resin composition (II).

These molded products are obtained by various known molding methods such as injection molding, extrusion molding, hollow molding, film molding, sheet molding, foam molding, injection foam molding, stretch molding, injection stretch blow molding, vacuum molding, press molding and the like. be able to. Among these, an injection molded body obtained by injection molding is preferable. The injection-molded product can exhibit a high balance of physical properties such as high rigidity, high impact resistance, and elongation. Therefore, the injection molded article can be suitably used for food containers, medical containers, home appliances, automobile parts and the like. Among these, it can be suitably used for automobile parts. In particular, automotive parts can be molded into bumpers, instrument panels, door trims, side seal garnishes, fenders, and the like. Large injection molded bodies represented by these automobile parts are required to have high rigidity for maintaining the shape, and at the same time, high impact resistance is required. Further, in the case of a large injection molded body, a load may be easily applied to the component mounting clip portion when mounting the component, and there may be a problem that the component mounting clip portion is torn off in a material having a low elongation at break. Here, the molded body obtained from the propylene-based resin composition (I) or (II) of the present invention has high rigidity and high impact resistance and good elongation at break. It can be suitably used as a large injection molded body.

  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] Fractionation of n-decane 200 ml of n-decane was added to 5 g of a sample of the propylene resin composition, and the mixture was heated and dissolved at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (α) was filtered off. The filtrate was placed in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate (β) and acetone were separated by filtration, and the precipitate (β) was dried. This precipitate (β) is converted into an n-decane-soluble component (D _sol ) in the propylene-based resin composition.
It was. Even when the filtrate side was concentrated to dryness, no residue was observed.

The precipitate (α) was again dissolved by heating at 145 ° C. for 30 minutes to obtain a solution. The resulting solution was filtered and the filler was filtered off. The filtrate was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (γ) was filtered off. This precipitate (γ) was used as an n-decane insoluble component (D _insol ) in the propylene resin composition.

In the fractionation of n-decane in the propylene-based block copolymer, since the precipitate (α) corresponds to the n-decane-insoluble component (D _insol ) in the propylene-based block copolymer, the n-decane-soluble component (D _The amount of _sol ) was calculated as follows.

D _sol amount (% by weight) = [precipitate (β) amount (g) / (precipitate (α) amount (g) + precipitate (β) amount (g))] × 100

[m2] Mw / Mn measurement [weight average molecular weight (Mw), number average molecular weight (Mn)]
Mw / Mn of the sample was measured as follows using GPC-150C Plus manufactured by Waters.

The separation columns were TSKgel GMH6-HT and TSK gel GMH6-HTL, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase. Industrial) and 0.025 wt% BHT (Wako Pure Chemical Industries) as an antioxidant, moved at 1.0 ml / min, sample concentration 0.1 wt%, sample injection volume 500 microliters, differential refraction as detector A total was used. For standard polystyrene, molecular weight Mw <1000 and Mw> 4 × 10 ⁶ is manufactured by Tosoh Corporation, and molecular weight 1000 ≦ Mw ≦ 4 × 10 ⁶ is manufactured by Pressure Chemical Co. 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)), respectively. Was used.

[m3] Melting point (Tm)
The measurement was performed as follows using a differential scanning calorimeter (DSC, manufactured by PerkinElmer). Here, the endothermic peak at the third step was defined as the melting point (Tm).

<Create sample sheet>
The sample was sandwiched between aluminum foils and press-molded under the following conditions using a mold (thickness: 0.2 mm).

Molding temperature: 240 ° C (heating temperature 240 ° C, preheating time: 7 minutes)
Press pressure: 300 kg / cm ²
Press time: 1 minute After press molding, the mold was cooled to near room temperature with ice water to obtain a sample sheet.

<Measurement>
About 0.4 g of the obtained sample sheet was sealed in the following measurement container, and DSC measurement was performed under the following measurement conditions.

(Measurement container)
Aluminum PAN (DSC PANS 10 μl BO-14-3015)
Aluminum COVER (DSC COVER BO14-3003)
(Measurement condition)
1st step: Temperature is raised to 240 ° C. at 30 ° C./min and held for 10 minutes. 2nd step: Temperature is lowered to 30 ° C. at 10 ° C./min. 3rd step: Temperature is raised to 240 ° C. at 10 ° C./min.

[m4] Intrinsic viscosity [η]
It measured at 135 degreeC using the decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η _sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (η _sp / C) (C → 0)

[m5] Content of skeleton derived from ethylene D _insol , In order to measure the content of skeleton derived from ethylene in D _sol , 20 to 30 mg of a sample was subjected to 1,2,4-trichlorobenzene / heavy benzene (2 : 1) Carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed after dissolving in 0.6 ml of the solution. 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 + Sαβ, EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ are used, and the following equations (Eq-1) and (Eq-2) ).

Propylene (mol%) = (PP + 1 / 2EP) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE) (Eq-1)
Ethylene (mol%) = (1 / 2EP + EE) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE) (Eq-2)
In this example, the _units of ethylene amount and α-olefin amount in D _insol were expressed in terms of% by weight.

[m6] GPC-IR Measurement Using a GPC-FTIR apparatus manufactured by Idemitsu Kosan Co., Ltd., the ethylene content was calculated as follows.

Millipore / Waters model 150C was used as the high-temperature high-speed GPC apparatus, and the developing solvent used was trichlorobenzene (TCB) purified and added with a stabilizer and the like. The separation column uses Showa Denko non-aqueous GPC columns (Shodex UT-806L (2)), and the eluate after column separation is a FTIR liquid controlled at the same temperature by a transfer tube controlled at 145 ° C from the GPC device. Led to the flow cell. Then, the infrared spectrum was measured with Nicolay Magna560FTIR, and SE
The ethylene content was calculated by analyzing the C-CH ₃ stretching vibration of 2955 cm ^{-1 and} the CH ₂ stretching vibration of 2920 cm ^-1 using C-FTIR analysis software (Nicollet). The content of components having a molecular weight of 1.5 million or more was calculated by the GPC measurement.

(GPC measurement conditions)
GPC column: Shodex UT-806L (2 pieces)
Solvent: TCB (Temperature: 145 ° C, flow rate 1.0 ml / min)
Molecular weight conversion: General calibration method (PP conversion)
(FT-IR measurement conditions)
Detector: MGNA-IR560 (Nikolay)
Injection concentration: 0.3w / v%
Injection volume: 750μl

[m7] MFR (melt flow rate)
The MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).

[m8] Bending elastic modulus of injection molded article The bending elastic modulus (hereinafter also referred to as "FM") of the injection molded article was measured according to JIS K7171 under the following conditions.

<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Bending span: 64 mm

[m9] Charpy impact strength of injection molded article The Charpy impact test of the injection molded article was measured according to JIS K7111 under the following conditions.

<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length) (cutting notch)
Measurement temperature: 23 ° C., −30 ° C.

[m10] Tensile elongation at break of injection-molded article The tensile test was measured according to JIS K7162.

<Measurement conditions>
Test piece: JIS K7162-BA dumbbell
5mm (width) x 2mm (thickness) x 75mm (length)
Tensile speed: 20 mm / min Distance between spans: 58 mm

[m11] Heat deformation temperature of injection molded body The heat deformation temperature of the injection molded body (hereinafter also referred to as "HDT") was measured according to JIS K7191 under the following conditions.

<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Load: 0.45 MPa
[Production Example 1]
(1) Production of solid catalyst carrier In a reaction vessel with a stirrer having an internal volume of 200 L, 27 L of toluene and 7.5 kg of SiO ₂ (Carriert P10 manufactured by Fuji Silysia Chemical) were put into a slurry. Next, while maintaining the temperature in the tank at 0 to 5 ° C., 73 L of MAO-toluene solution (10 wt% solution) was introduced over about 30 minutes and stirred for 30 minutes. Then, it heated up to 95 degreeC in 1 hour, and reacted for 4 hours. After completion of the reaction, it was cooled to 60 ° C. 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 carrier)
7.9 L of MAO / SiO ₂ / toluene slurry prepared in the above (1) (1030 g as a solid component) was placed in a reaction tank equipped with a stirrer having an internal volume of 14 L, and the temperature was maintained at 30 to 35 ° C. while stirring. In the glove box, place the [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 10.3 g
Weighed. The flask was taken out, diluted with 0.5 liter of toluene, added to the reaction tank, and toluene was added until the liquid volume in the reaction tank reached 10 L. Then, it was supported by stirring for 60 minutes. 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 was cooled to room temperature and then 92% substituted with n-heptane, The final slurry volume was 10L.

(3) Production of pre-polymerization catalyst 1040 g of the solid catalyst component prepared in (2) above was transferred to an autoclave with a stirrer having an internal volume of 200 L in which 18 L of n-heptane had been put in advance, and the internal temperature was maintained at 15 to 20 ° C. , 554 g of triisobutylaluminum was added, and the liquid volume was adjusted to 62 L with n-heptane. While stirring, the temperature was kept at 30 to 35 ° C., 3120 g of ethylene was inserted at 630 g / h, and the reaction was allowed to proceed for 300 minutes with stirring. 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 8 g / L to obtain a catalyst slurry. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization An internal capacity 58L jacketed circulation type tubular polymerizer is supplied with 52 kg / hour of propylene, 52 NL / hour of hydrogen, 5.1 g / hour of the catalyst slurry prepared in the above (3) as a solid catalyst component, triethyl 2.9 ml / hour of aluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.50 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 2.9 hours to obtain 17.1 kg of a propylene-based block polymer (A-1).

  The resulting propylene block copolymer (A-1) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-1).

[Production Example 2]
A propylene-based block polymer (A-2) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.50 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 3.0 hours to obtain 17.4 kg of a propylene-based block polymer (A-2).

  The resulting propylene block copolymer (A-2) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-2).

[Production Example 3]
A propylene-based block polymer (A-3) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.50 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was carried out for 2.7 hours at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G to obtain 16.7 kg of a propylene-based block polymer (A-3).

  The resulting propylene block copolymer (A-3) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-3).

[Production Example 4]
A propylene-based block polymer (A-4) was obtained in the same manner as in Production Example 1 except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.50 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was performed for 3.4 hours at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G to obtain 18.5 kg of a propylene-based block polymer (A-4).

  The resulting propylene block copolymer (A-4) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-4).

[Production Example 5]
A propylene-based block polymer (A-5) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.40 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 3.4 hours to obtain 17.1 kg of a propylene-based block polymer (A-5).

  The resulting propylene block copolymer (A-5) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-5).

[Production Example 6]
A propylene-based block polymer (A-6) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.77 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 1.5 hours to obtain 17.1 kg of a propylene-based block polymer (A-6).

  The resulting propylene block copolymer (A-6) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-6).

[Production Example 7]
A propylene-based block polymer (A-7) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerizer was ethylene / (ethylene + propylene) = 0.27 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 4.7 hours to obtain 17.1 kg of a propylene-based block polymer (A-7).

  The resulting propylene block copolymer (A-7) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-7).

[Production Example 8]
A propylene-based block polymer (A-8) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.15 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 6.0 hours to obtain 17.1 kg of a propylene-based block polymer (A-8).

  The resulting propylene block copolymer (A-8) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-8).

[Production Example 9]
(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 is 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 2 L of heptane was charged in advance into a reaction tank with a stirrer having an internal volume of 14 L, 53.4 mL of triethylaluminum, 18.3 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 60 g of the solid titanium catalyst component prepared in (1) was charged, and heptane was added so that the amount of heptane was 6.5 L. After maintaining the internal temperature at 10 ° C. or lower and stirring for 10 minutes, 560 g of propylene was charged over about 50 minutes, and then reacted 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 transferred to a reaction tank equipped with a 200 L stirrer and then adjusted with heptane so that the solid titanium catalyst component was 0.8 g / L to obtain a catalyst slurry. This prepolymerized catalyst contained 10 g of polypropylene per 1 g of the solid titanium catalyst component.

(3) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.4 mol%. 0.8 g of the catalyst slurry produced in the above (2) was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.4 mol%.

  The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.21 (molar ratio) and hydrogen / ethylene = 0.007 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G for 1.0 hour to obtain 24.7 kg of a propylene-based block polymer (B-1).

  The resulting propylene block copolymer (B-1) was vacuum dried at 80 ° C. Table 2 shows the physical properties of the resulting propylene-based block copolymer (B-1).

[Production Example 10]
A propylene-based block copolymer (B-2) was obtained in the same manner as in Production Example 9 except that the polymerization method was changed as follows.

(1) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 13.2 mol%. 0.8 g of the catalyst slurry produced in (2) of Production Example 9 was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.0 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 13.2 mol%.

  The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerizer would be ethylene / (ethylene + propylene) = 0.21 (molar ratio) and hydrogen / ethylene = 0.06 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.5 MPa / G for 0.5 hours to obtain 18.2 kg of a propylene-based block polymer (B-2).

  The resulting propylene block copolymer (B-2) was vacuum dried at 80 ° C. Table 2 shows the physical properties of the resulting propylene-based block copolymer (B-2).

[Production Example 11]
A propylene-based block copolymer (B-3) was obtained in the same manner as in Production Example 9 except that the polymerization method was changed as follows.

(1) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.5 mol%. 0.8 g of the catalyst slurry produced in (2) of Production Example 9 was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.5 mol%.

  The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene = 0.008 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G for 0.8 hours to obtain 21.1 g of a propylene-based block polymer (B-3).

  The resulting propylene block copolymer (B-3) was vacuum dried at 80 ° C. Table 2 shows properties of the obtained propylene block copolymer (B-3).

[Production Example 12]
A propylene-based block copolymer (B-4) was obtained in the same manner as in Production Example 9 except that the polymerization method was changed as follows.

(1) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.4 mol%. 0.8 g of the catalyst slurry produced in (2) of Production Example 9 was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.4 mol%.

  The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.23 (molar ratio) and hydrogen / ethylene = 0.005 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G for 3.2 hours to obtain 23.3 g of a propylene-based block polymer (B-4).

  The resulting propylene block copolymer (B-4) was vacuum dried at 80 ° C. Table 2 shows the physical properties of the resulting propylene-based block copolymer (B-4).

[Production Example 13]
A propylene-based block copolymer (B-5) was obtained in the same manner as in Production Example 9 except that the polymerization method was changed as follows.

(1) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.4 mol%. 0.8 g of the catalyst slurry produced in (2) of Production Example 9 was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.4 mol%.

  The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.21 (molar ratio) and hydrogen / ethylene = 0.004 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G for 3.9 hours to obtain 24.2 g of a propylene-based block polymer (B-5).

  The resulting propylene block copolymer (B-5) was vacuum dried at 80 ° C. Table 2 shows physical properties of the resulting propylene-based block copolymer (B-5).

[Production Example 14]
A propylene-based block copolymer (B-6) was obtained in the same manner as in Production Example 9 except that the polymerization method was changed as follows.

(1) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.4 mol%. 0.8 g of the catalyst slurry produced in (2) of Production Example 9 was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.4 mol%.

  The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.18 (molar ratio) and hydrogen / ethylene = 0.004 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G for 4.5 hours to obtain 30.1 g of a propylene-based block polymer (B-6).

  The resulting propylene block copolymer (B-6) was vacuum dried at 80 ° C. Table 2 shows the physical properties of the resulting propylene-based block copolymer (B-6).

[Production Example 15]
A propylene-based block copolymer (B-7) was obtained in the same manner as in Production Example 9 except that the polymerization method was changed as follows.

(1) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.4 mol%. 0.8 g of the catalyst slurry produced in (2) of Production Example 9 was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.4 mol%.

The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.28 (molar ratio) and hydrogen / ethylene = 0.008 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G for 0.7 hours to obtain 21.6 g of a propylene-based block polymer (B-7).

  The resulting propylene block copolymer was vacuum dried at 80 ° C. Table 2 shows the physical properties of the resulting propylene-based block copolymer (B-7).

[Production Example 16]
A propylene-based block copolymer (B-8) was obtained in the same manner as in Production Example 9 except that the polymerization method was changed as follows.

(1) Main polymerization 70 L of propylene, 7.0 mL of triethylaluminum, and 2.5 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 10.1 mol%. 0.9 g of the catalyst slurry produced in (2) of Production Example 9 was charged as a solid titanium catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 2.9 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 10.1 mol%.

  The obtained slurry was gasified and subjected to gas-solid separation, and then the entire amount of propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.42 (molar ratio) and hydrogen / ethylene = 0.08 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.5 MPa / G for 0.8 hours to obtain 21.6 g of a propylene-based block polymer (B-8).

  The resulting propylene block copolymer (B-8) was vacuum dried at 80 ° C. Table 2 shows the physical properties of the resulting propylene-based block copolymer (B-8).

[Production Example 17]
A propylene-based block copolymer (A-9) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.50 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 1.2 hours to obtain 13.8 kg of a propylene-based block polymer (A-9).

  The resulting propylene block copolymer (A-9) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-9).

[Production Example 18]
A propylene-based block copolymer (A-10) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerizer was ethylene / (ethylene + propylene) = 0.27 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 2.9 hours to obtain 13.8 kg of a propylene block polymer (A-10).

  The resulting propylene block copolymer (A-10) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-10).

[Production Example 19]
A propylene-based block copolymer (A-11) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerizer was ethylene / (ethylene + propylene) = 0.27 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 3.2 hours to obtain 14.1 kg of a propylene-based block polymer (A-11).

  The resulting propylene block copolymer (A-11) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-11).

[Production Example 20]
A propylene-based block copolymer (A-12) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

  After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.50 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G for 5.3 hours to obtain 26.7 kg of a propylene-based block polymer (A-12).

  The resulting propylene block copolymer (A-12) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-12).

[Production Example 21]
A propylene-based block copolymer (A-13) was obtained in the same manner as in Production Example 1, except that the polymerization method was changed as follows.

(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 52 kg / hour, hydrogen is 52 NL / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component, 5.1 g / During this time, 2.9 ml / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 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 70 ° C. and a pressure of 3.0 MPa / G.

After the obtained slurry was gasified and subjected to gas-solid separation, propylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L for 1 hour to carry out ethylene / propylene block copolymerization. Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerizer was ethylene / (ethylene + propylene) = 0.27 (molar ratio) and hydrogen / ethylene = 0.0002 (molar ratio). Polymerization was performed for 6.8 hours at a polymerization temperature of 70 ° C. and a pressure of 2.5 MPa / G to obtain 26.7 kg of a propylene-based block polymer (A-13).

  The resulting propylene block copolymer (A-13) was vacuum dried at 80 ° C. Table 1 shows the physical properties of the resulting propylene-based block copolymer (A-13).

[Example 1]
19 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9 with respect to 81 parts by weight of the propylene-based block copolymer (A-1) produced in Production Example 1, a heat stabilizer IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, calcium stearate 0.1 parts by weight were mixed in a tumbler and then twin screw extrusion The mixture was melt-kneaded with a machine to prepare a propylene-based resin composition (I-1) in the form of pellets. Table 3 shows various analysis results of the propylene-based resin composition (I-1). Using the propylene-based resin composition (I-1), a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 4 shows the physical properties of the obtained molded body.

<Melting and kneading conditions>
Same-direction twin-screw kneader: Product number KZW-15, manufactured by Technobel Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 500rpm
Feeder rotation speed: 50 rpm
<Injection molding conditions>
Injection molding machine: Part number EC40, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 190 ° C
Mold temperature: 40 ℃

[Example 2]
10 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9 with respect to 90 parts by weight of the propylene-based block copolymer (A-2) produced in Production Example 2, and a heat stabilizer Example 1 after mixing 0.1 part by weight of IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler. In the same manner as above, melt-kneading was performed with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-2). Table 3 shows various analysis results of the propylene-based resin composition (I-2). Except for using the propylene-based resin composition (I-2), a molded body was produced in the same manner as in Example 1 by using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 4 shows the physical properties of the obtained molded body.

[Comparative Example 1]
40 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9 with respect to 60 parts by weight of the propylene-based block copolymer (A-3) produced in Production Example 3, a heat stabilizer Example 1 after mixing 0.1 part by weight of IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler. In the same manner as above, melt-kneading was performed with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-3). Table 3 shows various analysis results of the propylene-based resin composition (I-3). Except for using the propylene-based resin composition (I-3), a molded body was produced in the same manner as in Example 1 using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 4 shows the physical properties of the obtained molded body.

[Comparative Example 2]
32 parts by weight of the propylene-based block copolymer (B-2) produced in Production Example 10 with respect to 68 parts by weight of the propylene-based block copolymer (A-4) produced in Production Example 4, a heat stabilizer Example 1 after mixing 0.1 part by weight of IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler. In the same manner as above, melt-kneading was performed with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-4). Table 3 shows various analysis results of the propylene-based resin composition (I-4). Except for using the propylene resin composition (I-4), the injection molding machine [Part No.
EC40, manufactured by Toshiba Machine Co., Ltd.] was used to produce a molded body. Table 4 shows the physical properties of the obtained molded body.

[Example 3]
19 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9 with respect to 81 parts by weight of the propylene-based block copolymer (A-5) produced in Production Example 5, a heat stabilizer Example 1 after mixing 0.1 part by weight of IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler. In the same manner as above, melt-kneading was carried out with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-5). Table 3 shows various analysis results of the propylene-based resin composition (I-5). Except for using the propylene-based resin composition (I-5), a molded body was produced in the same manner as in Example 1 using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 4 shows the physical properties of the obtained molded body.

[Comparative Example 3]
19 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9 with respect to 81 parts by weight of the propylene-based block copolymer (A-6) produced in Production Example 6, a heat stabilizer Example 1 after mixing 0.1 part by weight of IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler. In the same manner as above, melt-kneading was performed with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-6). Table 3 shows various analysis results of the propylene-based resin composition (I-6). Except for using the propylene-based resin composition (I-6), a molded body was produced in the same manner as in Example 1 using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 4 shows the physical properties of the obtained molded body.

[Comparative Example 4]
19 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9 with respect to 81 parts by weight of the propylene-based block copolymer (A-7) produced in Production Example 7, a heat stabilizer Example 1 after mixing 0.1 part by weight of IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler. In the same manner as above, melt-kneading was carried out with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-7). Various analysis results of the propylene-based resin composition (I-7) are shown in Table 3. Except for using the propylene-based resin composition (I-7), a molded body was produced in the same manner as in Example 1 with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 4 shows the physical properties of the obtained molded body.

[Comparative Example 5]
For 81 parts by weight of the propylene-based block copolymer (B-8) produced in Production Example 16,
19 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9, 0.1 part by weight of thermal stabilizer IRGANOX 1010 (trademark, Ciba-Geigy Corp.), thermal stabilizer IRGAFOS168 (trademark, Ciba-Geigy Corp.) )) 0.1 parts by weight and 0.1 parts by weight of calcium stearate were mixed with a tumbler and melt-kneaded with a twin screw extruder in the same manner as in Example 1 to form a pellet-shaped propylene resin composition (I-8) ) Was prepared. Table 3 shows various analysis results of the propylene-based resin composition (I-8). Except for using the propylene-based resin composition (I-8), a molded body was produced in the same manner as in Example 1 using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 4 shows the physical properties of the obtained molded body.

[Example 4]
79 parts by weight of the propylene-based resin composition (I-1) prepared in Example 1, 21 parts by weight of talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), thermal stabilizer IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat 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 and then melted in a twin screw extruder. A pellet-shaped propylene-based resin composition was prepared by kneading, and a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 5 shows the physical properties of the obtained molded body.

<Melting and kneading conditions>
Same-direction biaxial kneader: Product No. KZW-15, manufactured by Technobel Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 500rpm
Feeder rotation speed: 50 rpm
<Injection molding conditions>
Injection molding machine: Part number EC40, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 190 ° C
Mold temperature: 40 ℃

[Example 5]
In Example 4, instead of 79 parts by weight of the propylene-based resin composition (I-1), a molded body was similarly obtained except that 79 parts by weight of the propylene-based resin composition (I-2) prepared in Example 2 was used. Produced. Table 5 shows the physical properties of the obtained molded body.

[Comparative Example 6]
In Example 4, instead of 79 parts by weight of the propylene-based resin composition (I-1), a molded body was similarly obtained except that 79 parts by weight of the propylene-based resin composition (I-3) prepared in Comparative Example 1 was used. Produced. Table 5 shows the physical properties of the obtained molded body.

[Comparative Example 7]
In Example 4, instead of 79 parts by weight of the propylene-based resin composition (I-1), a molded body was similarly obtained except that 79 parts by weight of the propylene-based resin composition (I-4) prepared in Comparative Example 2 was used. Produced. Table 5 shows the physical properties of the obtained molded body.

[Example 6]
In Example 4, instead of 79 parts by weight of the propylene-based resin composition (I-1), a molded body was similarly obtained except that 79 parts by weight of the propylene-based resin composition (I-5) prepared in Example 3 was used. Produced. Table 5 shows the physical properties of the obtained molded body.

[Comparative Example 8]
In Example 4, instead of 79 parts by weight of the propylene-based resin composition (I-1), a molded body was similarly obtained except that 79 parts by weight of the propylene-based resin composition (I-6) prepared in Comparative Example 3 was used. Produced. Table 5 shows the physical properties of the obtained molded body.

[Comparative Example 9]
In Example 4, instead of 79 parts by weight of the propylene-based resin composition (I-1), a molded body was similarly obtained except that 79 parts by weight of the propylene-based resin composition (I-7) prepared in Comparative Example 4 was used. Produced. Table 5 shows the physical properties of the obtained molded body.

[Comparative Example 10]
In Example 4, instead of 79 parts by weight of the propylene-based resin composition (I-1), a molded body was similarly obtained except that 79 parts by weight of the propylene-based resin composition (I-8) prepared in Comparative Example 5 was used. Produced. Table 5 shows the physical properties of the obtained molded body.

[Example 7]
23 parts by weight of the propylene block copolymer (B-3) produced in Production Example 11 with respect to 77 parts by weight of the propylene block copolymer (A-2) produced in Production Example 2, a heat stabilizer IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat 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 and then twin screw extrusion The mixture was melt-kneaded in a machine to prepare a pellet-shaped propylene resin composition (I-9). Table 6 shows various analysis results of the propylene-based resin composition (I-9).

Furthermore, 79 parts by weight of the propylene-based resin composition (I-9), 21 parts by weight of talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), thermal stabilizer IRGANOX1010 (trademark,
Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat 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 and then melted in a twin screw extruder. A pellet-shaped propylene-based resin composition was prepared by kneading, and a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 7 shows the physical properties of the obtained molded body.

<Melting and kneading conditions>
Same-direction biaxial kneader: Product No. KZW-15, manufactured by Technobel Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 500rpm
Feeder rotation speed: 50 rpm
<Injection molding conditions>
Injection molding machine: Part number EC40, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 190 ° C
Mold temperature: 40 ℃

[Example 8]
20 parts by weight of the propylene-based block copolymer (B-4) produced in Production Example 12 with respect to 80 parts by weight of the propylene-based block copolymer (A-2) produced in Production Example 2, and a heat stabilizer Example 7 After mixing 0.1 part by weight of IRGANOX 1010 (trademark, Ciba Geigy Corp.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Corp.) and 0.1 part by weight of calcium stearate with a tumbler In the same manner as described above, melt-kneading was performed with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-10). Table 6 shows various analysis results of the propylene-based resin composition (I-10).

Furthermore, 79 parts by weight of propylene resin composition (I-10), 21 parts by weight of talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), heat stabilizer IRGANOX1010 (trademark, Ciba Geigy Corp.) ) 0.1 parts by weight, heat 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, and then the same as in Example 7, twin screw extruder The mixture was melt-kneaded to prepare a propylene-based resin composition in a pellet form, and a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 7 shows the physical properties of the obtained molded body.

[Example 9]
19 parts by weight of the propylene block copolymer (B-5) produced in Production Example 13 with respect to 81 parts by weight of the propylene block copolymer (A-1) produced in Production Example 1, a heat stabilizer Example 7 After mixing 0.1 part by weight of IRGANOX 1010 (trademark, Ciba Geigy Corp.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Corp.) and 0.1 part by weight of calcium stearate with a tumbler In the same manner as described above, melt-kneading was performed using a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-11). Table 6 shows various analysis results of the propylene-based resin composition (I-11).

Furthermore, 79 parts by weight of the propylene-based resin composition (I-11), 21 parts by weight of talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), heat stabilizer IRGANOX1010 (trademark, Ciba Geigy Corp.) ) 0.1 parts by weight, heat 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, and then the same as in Example 7, twin screw extruder The mixture was melt-kneaded to prepare a propylene-based resin composition in a pellet form, and a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 7 shows the physical properties of the obtained molded body.

[Example 10]
14 parts by weight of the propylene-based block copolymer (B-6) produced in Production Example 14 with respect to 86 parts by weight of the propylene-based block copolymer (A-3) produced in Production Example 3, and a heat stabilizer Example 7 After mixing 0.1 part by weight of IRGANOX 1010 (trademark, Ciba Geigy Corp.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Corp.) and 0.1 part by weight of calcium stearate with a tumbler In the same manner as described above, melt-kneading was performed using a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-12). Table 6 shows various analysis results of the propylene-based resin composition (I-12).

Furthermore, 79 parts by weight of propylene-based resin composition (I-12), 21 parts by weight of talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), heat stabilizer IRGANOX1010 (trademark, Ciba Geigy Corp.) ) 0.1 parts by weight, heat 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, and then the same as in Example 7, twin screw extruder The mixture was melt-kneaded to prepare a propylene-based resin composition in a pellet form, and a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 7 shows the physical properties of the obtained molded body.

[Comparative Example 11]
23 parts by weight of the propylene block copolymer (B-7) produced in Production Example 15 with respect to 77 parts by weight of the propylene block copolymer (A-2) produced in Production Example 2, a heat stabilizer IRGA
Example 7 after mixing 0.1 part by weight of NOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler In the same manner as described above, melt-kneading was carried out using a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-13). Table 6 shows various analysis results of the propylene-based resin composition (I-13).

Furthermore, 79 parts by weight of the propylene-based resin composition (I-13), 21 parts by weight of talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), heat stabilizer IRGANOX1010 (trademark,
Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, calcium stearate 0.1 parts by weight, after mixing in a tumbler, A propylene-based resin composition in the form of pellets was prepared by melt-kneading with a twin screw extruder, and a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 7 shows the physical properties of the obtained molded body.

[Comparative Example 12]
75 parts by weight of the propylene-based block copolymer (A-8) produced in Production Example 8 with respect to 25 parts by weight of the propylene-based block copolymer (A-1) produced in Production Example 1, a heat stabilizer Example 7 After mixing 0.1 part by weight of IRGANOX 1010 (trademark, Ciba Geigy Corp.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Corp.) and 0.1 part by weight of calcium stearate with a tumbler In the same manner as described above, melt-kneading was performed using a twin-screw extruder to prepare a propylene-based resin composition (I-14) in the form of pellets. Table 6 shows various analysis results of the propylene-based resin composition (I-14).

Furthermore, 79 parts by weight of propylene-based resin composition (I-14), 21 parts by weight of talc (E) (white filler 5000PJ (trademark), manufactured by Matsumura Sangyo Co., Ltd.), heat stabilizer IRGANOX1010 (trademark, Ciba Geigy Corp.) ) 0.1 parts by weight, heat 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, and then the same as in Example 7, twin screw extruder The mixture was melt-kneaded to prepare a propylene-based resin composition in a pellet form, and a molded body was produced with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 7 shows the physical properties of the obtained molded body.

[Example 11]
For 91 parts by weight of the propylene-based block copolymer (A-9) produced in Production Example 17,
9 parts by weight of the propylene-based block copolymer (B-1) produced in Production Example 9, 0.1 part by weight of thermal stabilizer IRGANOX 1010 (trademark, Ciba-Geigy Corp.), thermal stabilizer IRGAFOS168 (trademark, Ciba-Geigy Corp.) )) 0.1 parts by weight and 0.1 parts by weight of calcium stearate were mixed with a tumbler and melt-kneaded with a twin-screw extruder in the same manner as in Example 1 to produce a pellet-shaped propylene resin composition (I-15). ) Was prepared. Table 8 shows various analysis results of the propylene-based resin composition (I-15). Except for using the propylene-based resin composition (I-15), a molded article was produced in the same manner as in Example 1 using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 8 shows the physical properties of the obtained molded body.

[Comparative Example 13]
In Example 11, the same procedure except that 91 parts by weight of the propylene block copolymer (A-10) produced in Production Example 18 was used instead of 91 parts by weight of the propylene block copolymer (A-9). A pellet-shaped propylene resin composition (I-16) was prepared to produce a molded body. Table 8 shows various analysis results and physical properties of the molded product of the resulting propylene-based resin composition (I-16).

[Comparative Example 14]
With respect to 100 parts by weight of the propylene-based block copolymer (A-11) produced in Production Example 19, 0.1 part by weight of thermal stabilizer IRGANOX 1010 (trademark, Ciba Geigy Co., Ltd.), 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 and melt-kneaded in a twin-screw extruder in the same manner as in Example 1 to form a pellet-shaped propylene resin composition ( I-17) was prepared. Table 8 shows various analysis results of the propylene-based resin composition (I-17). Except for using the propylene-based resin composition (I-17), a molded product was produced in the same manner as in Example 1 using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 8 shows the physical properties of the obtained molded body.

[Example 12]
33 parts by weight of the propylene block copolymer (B-1) produced in Production Example 9 with respect to 67 parts by weight of the propylene block copolymer (A-12) produced in Production Example 20, a heat stabilizer Example 1 after mixing 0.1 part by weight of IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.), 0.1 part by weight of heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) and 0.1 part by weight of calcium stearate with a tumbler. In the same manner as above, melt-kneading was carried out with a twin-screw extruder to prepare a pellet-shaped propylene resin composition (I-18). Table 8 shows various analysis results of the propylene-based resin composition (I-18). Except for using the propylene-based resin composition (I-18), a molded body was produced in the same manner as in Example 1 using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 8 shows the physical properties of the obtained molded body.

[Comparative Example 15]
In Example 12, the same procedure except that 67 parts by weight of the propylene-based block copolymer (A-13) produced in Production Example 21 was used instead of 67 parts by weight of the propylene-based block copolymer (A-12). A pellet-shaped propylene resin composition (I-19) was prepared, and a molded body was produced. Table 8 shows various analysis results and physical properties of the molded product of the obtained propylene-based resin composition (I-19).

[Comparative Example 16]
For 100 parts by weight of the propylene-based block copolymer (A-2) produced in Production Example 2,
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, and melt-kneaded in a twin-screw extruder in the same manner as in Example 1 to form a pellet-shaped propylene resin. Composition (I-20) was prepared. Table 8 shows various analysis results of the propylene-based resin composition (I-20). Except for using the propylene-based resin composition (I-20), a molded body was produced in the same manner as in Example 1 by using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.]. Table 8 shows the physical properties of the obtained molded body.

[Comparative Example 17]
In Comparative Example 16, instead of 100 parts by weight of the propylene-based block copolymer (A-2),
A pellet-shaped propylene-based resin composition (I-21) was similarly prepared except that 100 parts by weight of the propylene-based block copolymer (A-7) produced in Production Example 7 was used, and a molded body was produced. . Table 8 shows various analysis results and physical properties of the molded product of the obtained propylene-based resin composition (I-21).
Shown in

  According to the propylene-based resin composition according to the present invention, a molded article having excellent balance of mechanical properties such as rigidity, impact resistance, and elongation can be obtained. Therefore, various molded products having excellent physical properties, particularly large-scale molding of automobile parts and the like. A product can be suitably obtained.

Claims (14)

50 to 99 parts by weight of a propylene-based block copolymer (A) polymerized under a metallocene compound-containing catalyst and a propylene-based block copolymer that is polymerized under a Ziegler-Natta catalyst and satisfies the following requirements (A) and (I) (B) 1 to 50 parts by weight (provided that (A) + (B) = 100 parts by weight),
A component insoluble in room temperature n-decane (hereinafter also referred to as “D _insol ”) satisfies the following requirements (i) to (iii) and is soluble in room temperature n-decane (hereinafter also referred to as “D _sol ”). Satisfies the following requirements (a) to (e): a propylene-based resin composition (I);
(A) The intrinsic viscosity [η] of the component soluble in room temperature n-decane (D _sol ) is 5 to 15 dl / g,
(A ) The ethylene content of the component soluble in room temperature n-decane (D _sol ) is 25 to 37 mol%,
(I) the melting point is 156 ° C. or higher,
(Ii) the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 0.6 to 4 dl / g,
(Iii) The ethylene content is 3% by weight or less,
(A) The amount of D _sol in 100% by weight of the propylene-based resin composition (I) is 15 to 50% by weight;
(B) the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 1.8 to 4 dl / g,
(C) The content of the component having a molecular weight of 1.5 million or more in the molecular weight distribution curve calculated by GPC measurement is 1 to 8% by weight with respect to the entire D _sol ,
(D) The ethylene content (C ″ 2 (M150)) in the component having a molecular weight of 1.5 million measured by GPC-IR measurement is 25 to 37 mol%.
(E) The ethylene content (C ″ 2) is 40 to 65 mol%. The propylene-based resin composition (I) according to claim 1, wherein the propylene-based block copolymer (A) has the following requirements (1) and (2):
Requirement (1): A component soluble in room temperature n-decane (D _sol ) Molecular weight distribution (Mw / Mn) is 3.5 or less,
Requirement (2): Component insoluble in room temperature n-decane (D _insol ) Has a molecular weight distribution (Mw / Mn) of 1.5 to 3.5. In the requirement (c), the content of the component having a molecular weight of 1.5 million or more is D _sol It is 1.5 to 7.5 weight% with respect to the whole, The propylene-type resin composition (I) of Claim 1 or 2 characterized by the above-mentioned. The propylene resin composition (I) according to any one of claims 1 to 3, wherein D _insol in the propylene resin composition (I) satisfies the following requirement (iv):
(Iv) The molecular weight distribution (Mw / Mn) is 2.5 to 5.0. A propylene resin composition (II) comprising the propylene resin composition (I) according to any one of claims 1 to 4 . The propylene-based resin composition (II) according to claim 5 , further comprising an inorganic filler (F). The propylene-based resin composition (II) according to claim 5 or 6 , further comprising an elastomer (E). 50 to 99 parts by weight of the propylene-based resin composition (I) according to any one of claims 1 to 4 and 1 to 50 parts by weight of an inorganic filler (F) (however, (I) + (F) = 100 Propylene-based resin composition (II), characterized in that 50 to 99 parts by weight of the propylene-based resin composition (I) according to any one of claims 1 to 4 and 1 to 50 parts by weight of an elastomer (E) (where (I) + (E) = 100 parts by weight) A propylene-based resin composition (II). 50 to 98 parts by weight of the propylene-based resin composition (I) according to any one of claims 1 to 4 , 1 to 49 parts by weight of an inorganic filler (F), and 1 to 49 parts by weight of an elastomer (E) ( However, (I) + (E) + (F) = 100 parts by weight.) Propylene-based resin composition (II), The molded object obtained by shape | molding the propylene-type resin composition (I) as described in any one of Claims 1-4 . Molded article obtained by molding the propylene resin composition (II) according to any one of claims 5-10. The molded article according to claim 11 or 12 , which is an injection molded article. Molded body according to any one of claims 11 to 13, which comprises using the auto parts.