JP2002234976A - Propylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene resin composition having excellent transparency, heat resistance, softness, and low-temperature impact resistance. SOLUTION: The propylene resin composition comprises 1-99 mass% propylene homopolymer [I] which meets (1) a meso-pentad fraction (mmmm) of 20-60 mol%, (2) a ratio [(rrrr)/(1-mmmm)] of a racemic pentad fraction (rrrr) to (1-mmmm) of <=0.1, (3) a pentad fraction (rmrm) of more than 2.5 mol%, (4) a relationship among a mesotriad fraction (mm), a racemic triad fraction (rr), and a triad fraction (mr) being (mm)×(rr)/(mr)2<=2.0, and (5) an amount (W25) of components to be eluted at not higher than 25 deg.C in temperature-programmed chromatography of 20-100 mass%, and 99-1 mass% propylene-ethylene block copolymer which meets (6) an MFI, measured at 230 deg.C under a load of 21.18 N, of 0.01-1,000 g/10 min, and (7) an amount of components soluble in xylene at normal temperatures (25 deg.C) of 3-60 mass%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a propylene-based resin composition, and more particularly, to a propylene-based resin composition having excellent transparency, heat resistance, softness and low-temperature impact resistance.

[0002]

2. Description of the Related Art Many studies have been made on improvements in propylene-ethylene block copolymers for the purpose of improving the balance between physical properties of rigidity and impact resistance. In addition, a propylene-ethylene random copolymer has been developed to control the elastic modulus of the homopolypropylene. The propylene-ethylene block copolymer is inferior in transparency because the crystal component and the elastomer component form a so-called sea-island structure, and the use thereof is limited.
On the other hand, although a propylene-ethylene random copolymer having good transparency has been developed, there is a problem that the melting point is lowered and thus the heat resistance is lowered. Further, when softness is imparted by lowering the regularity of polypropylene, there is a problem that the melting point is lowered and the heat resistance is lowered.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a propylene-based resin composition having excellent transparency, heat resistance, softness and low-temperature impact resistance.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that
It has been found that by blending a low-order polypropylene with an ethylene block copolymer, a resin composition having softness and transparency can be obtained while maintaining heat resistance and impact resistance at low temperatures. The present invention has been completed based on such findings. That is, the present invention provides the following (1) to (5) (1) a mesopentad fraction (mmmm) of 20 to 60 mol%, and (2) a racemic pentad fraction (rrrr).
And (1-mmmm) satisfy [rrrr / (1-mmmm)] ≦ 0.1, (3) a pentad fraction (rmrm) exceeds 2.5 mol%, and (4) a mesotriad fraction (mm). , Racemic triad fraction (rr), triad fraction (mr)
Satisfies the following relationship (mm) × (rr) / (mr) ² ≦ 2.0.
Propylene homopolymer [I] 1 to 99 that satisfies that the amount of the component (W25) eluted at a temperature of not more than 20 ° C is 20 to 100% by mass.
Mass%, and the following (6) and (7) (6) 230 ° C,
The melt flow rate (MFR) measured under the condition of a load of 21.18 N is 0.01 to 1000 g / 10 min.
(7) The soluble component in normal temperature (25 ° C.) xylene is 3 to
An object of the present invention is to provide a propylene-based resin composition comprising 99 to 1% by mass of a propylene-ethylene block copolymer [II] satisfying 60% by mass.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene homopolymer [I] blended in the propylene resin composition of the present invention satisfies the above (1) to (5). Mesopentad fraction (mmmm) needs to be 20 to 60 mol%
[(1)] is preferably from 30 to 60 mol%, more preferably from 40 to 50 mol%. Racemic pentad fraction (rrr
r) and (1-mmmm) are [rrrr / (1-mmmm)
m)] ≦ 0.1 [(2)] is [rrrr]
/(1-mmmm)]≦0.08,
More preferably, [rrrr / (1-mmmm)] ≦ 0.06, and [rrrr / (1-mmmm)] ≦ 0.
Particularly preferred is 05.

In the present invention, the mesopentad fraction (mm
mm fraction) means A. Zambell (A. Zambell)
i) et al., "Macromolecules, 6, 9
25 (1973) "and ¹³ C-
It is a meso fraction in pentad units in a polypropylene molecular chain measured by a signal of a methyl group in an NMR spectrum. When this is increased, it means that stereoregularity is increased. The propylene homopolymer [I] of the present invention has a mesopentad fraction (mmmm) of 20 mol%.
If it is less than 5, it may cause stickiness. If it exceeds 60 mol%, the modulus of elasticity will increase, which may be undesirable. Similarly, the racemic pentad fraction (rrrr fraction) is a racemic fraction in pentad units in a polypropylene molecular chain.
[Rrrr / (1-mmmm)] is an index that is determined from the fraction of the pentad unit and represents the uniformity of the regular distribution of the propylene homopolymer. As this value increases, the regularity distribution expands, and high stereoregularity PP and AP like conventional polypropylenes produced using existing catalyst systems are obtained.
It becomes a mixture of P, which means that stickiness increases and transparency decreases. If the [rrrr / (1-mmmm)] of the propylene homopolymer [I] in the present invention exceeds 0.1, it may cause stickiness. In addition, ¹³ C-N
The measurement of the MR spectrum was performed by A. Zamberg (A. Zam).
belli) et al. “Macromolecule
s, 8, 687 (1975) ", according to the following apparatus and conditions.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / mL Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10000 times <Calculation formula> M = m / S × 100 R = γ / S × 100 S = Pββ + Pαβ + Pαγ S: Signal intensity of side chain methyl carbon atom in all propylene units Pββ: 19. 8 to 22.5 ppm Pαβ: 18.0 to 17.5 ppm Pαγ: 17.5 to 17.1 ppm γ: Racemic pentad chain: 20.7 to 20.3 ppm m: Mesopentad chain: 21.7 to 22.5 ppm

In the propylene homopolymer [I], the pentad fraction (rmrm) must exceed 2.5 mol% [(3)]. The pentad fraction (rmrm) is 2.
If it exceeds 5 mol%, the randomness increases and the transparency further improves. The propylene homopolymer [I] requires that the mesotriad fraction (mm), the racemic triad fraction (rr), and the triad fraction (mr) satisfy the following relationship.
[(4)]. (Mm) × (rr) / (mr) ² ≦ 2.0 This relationship indicates an index of the randomness of the polymer. The closer to 1, the higher the randomness, the higher the transparency, the higher the flexibility and the elastic recovery. Excellent balance. Propylene homopolymer [I]
As the value on the left side of the above equation is preferably 1.8 to 0.5,
More preferably, it is in the range of 1.5 to 0.5. The triad fraction is determined in the same manner as the pentad fraction. Further, in the propylene homopolymer [I], the component amount (W25) of the propylene-based polymer eluted at 25 ° C. or lower in temperature rising chromatography needs to be 20 to 100% by mass [(5)], Preferably, 30 to 10
0 mass%, particularly preferably 50 to 100 mass%. W25 is an index indicating whether or not the propylene homopolymer [I] is soft. When this value is small, it means that the component having a high elastic modulus is increased and / or the non-uniformity of the stereoregularity distribution is widened. In the present invention, if W25 is less than 20%, flexibility may be lost, which is not preferable. W25 is defined as TREF in an elution curve obtained by measurement by temperature-raising chromatography using the following operation method, apparatus configuration, and measurement conditions.
Is the amount (% by mass) of the component eluted without being adsorbed by the packing material at a column temperature of 25 ° C.

(A) Operation method A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and placed on the surface of the filler. To crystallize. Then, the column was heated at a heating rate of 40 ° C./hour.
The temperature is raised to 35 ° C. to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6 mm x 150 mm) manufactured by GL Sciences Flow cell: 1 mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C.

The propylene homopolymer [I] further includes the following (8) and (9) in addition to the above (1) to (5).
It is preferable to satisfy the following. (8) The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is 4 or less. (9) Melt flow rate (MF) measured under the conditions of 230 ° C. and 21.18 N load.
R) is 0.01 to 1000 g / 10 min. Mw / Mn
Is more preferably 3.5 or less, particularly preferably 3 or less.
If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur on the film or sheet.

The above Mw / Mn is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn in terms of polyethylene measured by gel permeation chromatography (GPC) using the following apparatus and conditions. GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / milliliter Injection amount: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)

The melt flow rate (MFR) measured at 230 ° C. and a load of 21.18 N is 0.1 to 500 g /
10 minutes is more preferable, and particularly preferably 1 to 200 g /
10 minutes. If the MFR is less than 0.01 g / 10 minutes, the resin may not easily flow during injection molding.
If the FR exceeds 1000 g / 10 minutes, the sticky component may increase. The MFR is JIS K7
It is a value measured according to No. 210. The propylene homopolymer [I] includes a differential scanning calorimeter (DS) described later.
Those which do not show the melting point (Tm) in the measurement by C) are preferable in terms of excellent softness.

Furthermore, in addition to the above requirements, the propylene homopolymer [I] of the present invention is preferably excellent in flexibility when the melting endothermic amount ΔH measured by DSC is 20 J / mol or less. ΔH is an index indicating whether the material is soft or not, and when this value is large, it means that the elastic modulus is high and the softness is low. Note that Tm and ΔH are determined by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), 10 mg of a sample is melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then the temperature is lowered to 0 ° C. at 10 ° C./min. Further, after holding at 0 ° C. for 3 minutes, the peak end of the maximum peak of the melting endothermic curve obtained by increasing the temperature at 10 ° C./min is the melting point: Tm, and the melting endotherm in this case is ΔH. .

In general, during the polymerization of propylene, the carbon atom on the methylene side of the propylene monomer is bonded to the active site of the catalyst, and the propylene monomer is coordinated and polymerized in the same manner in the order of 1,2. Polymerization of insertion is usually performed, but rarely 2, 1 insertion or 1, 3 insertion (also referred to as abnormal insertion). The homopolymer [I] in the present invention preferably has a small amount of the 2,1 or 1,3 insertion. Further, the ratio of these insertions is expressed by the following relational expression (1) [(m−2,1) 10 (r−2,1) 10 (1,3)] ≦ 5.0 (%) (1) [Wherein (m-2,1) is the meso-2,1 insertion content (%) measured by ¹³ C-NMR, and (r-2,1) is ¹³ C-N
Racemic-2,1 insertion content (%) measured by MR,
(1,3) indicates the 1,3 insertion content (%) measured by ¹³ C-NMR. Is preferable, and the relational expression (2) [(m−2,1) 10 (r−2,1) 10 (1,3)] ≦ 1.0 (%) (2) Satisfaction is more preferable. In particular, the one that satisfies the relational expression (3) [(m−2,1) 10 (r−2,1) 10 (1,3)] ≦ 0.1 (%) (3) is most preferable. This relational expression (1)
If not, the crystallinity may be reduced more than expected, which may cause stickiness.

(M-2,1), (r-2,1) and (1,3) are reported by Grassi et al. (Macromolucule).
s, 21, p. 617 (1988)) and a report by Busico et al. (Macromolucules, 27, p. 7538 (1994)).
It is each insertion content determined from the integral intensity of each peak after the assignment of the peak of the ¹³ C-NMR spectrum was determined. That is, (m−2,1) is Pα, γthreo appearing around 17.2 ppm with respect to the integrated intensity in the entire methyl carbon region.
Calculated from the ratio of the integrated intensities of the peaks belonging to
2,1 insertion content (%). (R-2,1) is 15.0 ppm based on the integrated intensity in the entire methyl carbon region.
Racemic-2,1 insertion content (%) calculated from the ratio of the integrated intensities of peaks belonging to Pα and γthreo appearing in the vicinity
It is. (1,3) is the 1,3 insertion content (%) calculated from the ratio of the integrated intensity of the peak belonging to Tβ, γ10 appearing around 31.0 ppm to the integrated intensity in the entire methine carbon region.

Further, the propylene homopolymer [I] of the present invention was measured by ¹³ C-NMR spectrum.
It is more preferable that the peak attributable to the end of the molecular chain (n-butyl group) derived from the 2,1 insertion is not substantially observed. Regarding the molecular chain terminal derived from this 2,1 insertion,
Jungling et al. (J. Polym. Sci .: Part
A: Po1ym. Chem., 33, p1305 (1995))
The assignment of peaks in the ¹³ C-NMR spectrum is determined, and each insertion content is calculated from the integrated intensity of each peak. In the case of isotactic polypropylene, a peak appearing at about 18.9 ppm is assigned to the unsubstituted methyl group carbon of the n-butyl group. Also, regarding abnormal insertion or molecular chain end measurement
The measurement of ¹³ C-NMR may be performed with the above-described apparatus and conditions.

The propylene homopolymer [I] according to the present invention
Is a method of homopolymerizing propylene using a catalyst system called a metallocene catalyst.
Examples of metallocene catalysts include JP-A-58-19309, JP-A-61-130314, and JP-A-3-130.
JP-A-63088, JP-A-4-300887, JP-A-4-21694, and JP-T-1-502036
Cyclopentadienyl group as described in
A transition metal compound having one or two ligands such as a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group;
And a catalyst obtained by combining a co-catalyst with a transition metal compound in which the ligand is geometrically controlled.

In the present invention, among the metallocene catalysts, it is preferable that the ligand comprises a transition metal compound forming a crosslinked structure via a crosslinking group.
More preferred is a method in which propylene is homopolymerized using a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure via two crosslinking groups with a cocatalyst. Specifically, (A) the general formula (I)

[0019]

Embedded image

[Wherein, M is a member of Groups 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Coordination selected from groups, hydrocarbon groups and silicon-containing groups
A child¹And A^TwoTo form a crosslinked structure through
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Ys are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, containing silicon
Group, germanium-containing group, tin-containing group, -O-, -CO
-, -S-, -SO_Two-, -Se-, -NR¹-, -P
R¹-, -P (O) R¹-, -BR¹-Or-AlR¹
-Indicates R¹Represents a hydrogen atom, a halogen atom, and a carbon number of 1 to
20 hydrocarbon groups or halogen-containing carbons having 1 to 20 carbon atoms
Represent hydride groups, which may be the same or different
You may. q is an integer of 1 to 5 [(valency of M) -2]
And r represents an integer of 0 to 3. Transition gold
Genus compound, and (B) (B-1) transition gold of the component (A)
Reacts with genus compounds or their derivatives to form ionic complexes
Selected from compounds that can be formed and (B-2) aluminoxane
Propylene in the presence of a polymerization catalyst containing
A method of performing homopolymerization is exemplified.

In the above general formula (I), M is the periodic table
A metal element of group 3 to 10 or a lanthanoid series,
Specific examples include titanium, zirconium, hafnium,
Thorium, vanadium, chromium, manganese, nickel
Metal, cobalt, palladium and lanthanoid metals
Among them, olefin polymerization active among these
Titanium, zirconium and hafnium are preferred
It is. E¹And E¹Is a substituted cyclopentadi
Enyl group, indenyl group, substituted indenyl group, heterocy
Clopentadienyl group, substituted heterocyclopentadienyl
Amide group (-N <), phosphine group (-P <),
Hydrocarbon group [> CR-,> C <] and silicon-containing group [>
SiR-,> Si <] (where R is hydrogen or carbon atom 1)
~ 20 hydrocarbon or heteroatom-containing groups)
A represents a ligand selected from ¹And A^TwoThrough
A crosslinked structure is formed. Also, E¹And E^TwoLong
May be the same or different. This E¹And E^Twoage
Are substituted cyclopentadienyl groups, indenyl groups and
Substituted indenyl groups are preferred.

X represents a σ-binding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different and are cross-linked to other X, E ¹ , E ² or Y. You may.
Specific examples of X include a halogen atom and a carbon atom having 1 to 20 carbon atoms.
Hydrocarbon group, C1-C20 alkoxy group, C6-C20 aryloxy group, C1-C20 amide group, C1-C20 silicon-containing group, C1-C20 phosphide Group, a sulfide group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, and the like. On the other hand, Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked to another Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include:
Examples include amines, ethers, phosphines, and thioethers.

Next, A ¹ and A ² are divalent bridging groups for bonding the two ligands, and are a hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group containing 1 to 20 carbon atoms. , Silicon-containing group, germanium-containing group, tin-containing group, -O-,-
CO -, - S -, - SO 2 -, - Se -, - NR 1 -,
-PR ^1- , -P (O) R ^1- , -BR ¹ -or -Al
R ¹ - indicates, R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, they may be the same with or different from each other . At least one of such crosslinking groups is preferably a crosslinking group comprising a hydrocarbon group having 1 or more carbon atoms. As such a crosslinking group, for example, a general formula

[0024]

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(E represents a carbon atom, a germanium atom or a tin atom. R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, And e may be an integer of 1 to 4), and specific examples thereof include a methylene group, an ethylene group, and an ethylidene group. , Propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ ＣC =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethyl Examples include a stannylene group, a tetramethyldisilylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred. q is an integer of 1 to 5 [(valence of M)-
2], and r represents an integer of 0 to 3.

In the transition metal compound represented by the general formula (I), when E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group,
The bond of the crosslinking group of ¹ and A ² is (1,2 ′) (2,1 ′
) Double cross-linking is preferred. Among such transition metal compounds represented by general formula (I), general formula (II)

[0027]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferred. In the general formula (II), M, X, Y, A ¹ , A
² , q and r are the same as above. R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a heteroatom-containing group. One needs to be not a hydrogen atom. Also, R ⁴ ~
R ⁹ may be the same or different, and adjacent groups may be bonded to each other to form a ring.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably has a (1,2 ') (2,1') double-bridged ligand. Specific examples of the transition metal compound represented by the general formula (I) include:
(1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene)
Methylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′- Ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium Dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-
Ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,
2′-ethylene) (2,1′-ethylene) -bis (4
7-diisopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)-
Bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)-
Bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′
-Ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2
1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1 '
-Ethylene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 ' -Dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-i-propylindenyl) Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene ) Screw (3
-Phenylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1'-dimethylsilylene) bis (4-isopropylpropenyl) zirconium dichloride, (1,2'-
Dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di -I-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4
-Phenylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Dimethylsilylene) bis (5
6-benzoindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-methyl Indenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2 ′
-Dimethylsilylene) (2,1'-isopropylidene)
-Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-
(Isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1'-isopropylidene)-
Bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1′-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethyl) Silylene) (2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-i
-Propylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-
(Trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (indenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene)- Bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2
1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2 '
-Diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene)
(2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3
-Methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2 ′
-Dimethylsilylene) (2,1'-isopropylidene)
(3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-ethylene) (3
-Methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2 ′
-Ethylene) (2,1'-methylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene)
(2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl)
Zirconium dichloride, (1,2'-methylene)
(2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-
Isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2
1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1'-isopropylidene)
(3,4-dimethylcyclopentadienyl) (3 ′,
4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 '
-Ethylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2
1'-methylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-
Methylene) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2 ′
-Methylene) (2,1'-isopropylidene) (3,4
-Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,
(1,2′-isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3′−
Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1′-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3 ′ −
Methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl)
(3′-methyl-5′-ethylcyclopentadienyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 ′ −
Ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-
Dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,
1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopendienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Methylene) (3-methyl-
5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2'-Ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5 '-I-propylcyclopentadienyl) zirconium dichloride, (1,
2′-methylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1 , 2'-methylene) (2,
1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i
-Propylcyclopentadienyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these. Also,
It may be a similar compound of a metal element of another group or a lanthanoid series.

Next, as the component (B-1) of the component (B), any compound which can react with the transition metal compound of the above component (A) to form an ionic complex can be used. The following general formulas (III), (IV) ([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b ... (III) ([L ² ] ^{k +} ) _a ([Z] ^-) _b ··· (IV) (provided that, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R
A ¹⁴ M ^3. In the formulas (III) and (IV), L ¹ is a Lewis base, and [Z] ⁻ is
Non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 G 1 G 2 ··· G} f ] ^- ( Here, M ¹ is an element belonging to Groups 5 to 15 of the periodic table, preferably ^{13 to 1} of the periodic table.
Shows Group 5 elements. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 2 to 4 carbon atoms.
0 dialkylamino group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C7-C40 alkylaryl group, C7-C40 Arylalkyl group, 1 to 1 carbon atoms
A halogen-substituted hydrocarbon group of 20; an acyloxy group of 1 to 20 carbon atoms; an organic metalloid group; or a heteroatom-containing hydrocarbon group of 2 to 20 carbon atoms. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(center metal M
Represents an integer of ¹ valence) +1]. ), [Z ² ] ^-
A conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base of an acid generally defined as a super strong acid is shown. Further, a Lewis base may be coordinated. Further, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, R ¹¹ and R ¹²
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is an ionic valence of [L ¹ -R ¹⁰ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² contains an element of Groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents an element of Groups 7 to 12 of the periodic table. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, a p-methoxyphenyl group and the like, and specific examples of R ¹⁴ include a tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ¹ G ¹ G
² ... G ^f ], B and A are specific examples of M ^1.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, hydrocarbon groups such as phenoxy
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group, as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , a fluorosulfonic acid anion (FS
O ₃ ) ^- , chlorosulfonic acid anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅₎ ^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the compound of the component (B-1) include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n-butyl) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) , Triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
(1,1'-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, manganese tetrakis (pentafluorophenyl) borate, porphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

As the component (B-1), a compound which can react with the transition metal compound of the component (A) to form an ionic complex may be used alone or in combination of two or more. You may. On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

[0037]

Embedded image

(Wherein R ¹⁵ represents an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each R ¹⁵ may be the same or different. Aluminoxane represented by the general formula (VI):

[0039]

Embedded image

(Wherein, R ¹⁵ and w are the same as those in the above formula (V)). Specific examples of aluminoxanes include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and t-butylaluminoxane. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. ,
There are a method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. The aluminoxane may be toluene-insoluble.

These aluminoxanes may be used alone or in combination of two or more. When the (B-1) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component to the (B) catalyst component is preferably from 10: 1 to 1: 100, Preferably 2: 1
If the ratio deviates from the above range, the catalyst cost per unit weight polymer increases,
Not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1,000,000,
More preferably, the range is from 1:10 to 1: 10000. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical. Further, as the catalyst component (B), (B-1) and (B-2) can be used alone or in combination of two or more.

The propylene homopolymer [I] according to the present invention
As the polymerization catalyst in the production method of (1), an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of the component (C), a compound represented by the general formula (VII) R ¹⁶ _v AlJ _3-v (VII) wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, and J is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
And v is an integer of 1 to 3].

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. In the method for producing the propylene homopolymer [I], preliminary contact can also be performed using the above-mentioned components (A), (B) and (C). The preliminary contact can be performed by bringing the component (A) into contact with the component (B), for example, but the method is not particularly limited, and a known method can be used. These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the cocatalyst (B) used. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be seen together with the above-mentioned effect. The pre-contact temperature is usually -20C to 200C, preferably -10C to 1C.
The temperature is 50 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons.

The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 1000 in molar ratio.
0, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1: 1000.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least one of the catalyst components can be used by being supported on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier,
Any other inorganic and organic carriers can be used, but inorganic oxide carriers or other inorganic carriers are particularly preferred. As the inorganic oxide carrier, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO
₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO,
ThO ₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like can be mentioned. Among them, SiO ₂ and Al ₂ O ₃ are particularly preferable. In addition, the inorganic oxide carrier contains a small amount of carbonate,
It may contain nitrates, sulfates and the like.

On the other hand, as a carrier other than the above, MgC
l_Two, Mg (OC_TwoH_Five)_TwoMagnesium compounds such as
General formula MgR represented by¹⁷ _xX¹ _yMagne represented by
Examples of the compound include a calcium compound and a complex salt thereof. This
Where R¹⁷Is an alkyl group having 1 to 20 carbon atoms,
20 alkoxy groups or aryl groups having 6 to 20 carbon atoms,
X ¹Represents a halogen atom or an alkyl group having 1 to 20 carbon atoms.
X is 0-2, y is 0-2, and x + y = 2
It is. Each R¹⁷And each X¹May be the same,
They may be different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, and polyarylate, starch, and carbon. The carrier used in the present invention is MgC
l ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ ,
SiO ₂ and Al ₂ O ₃ are preferred. The shape of the carrier varies depending on the type and production method, but the average particle size is usually 1 to 300 µm, preferably 10 to 200 µm, more preferably 20 to 100 µm.

When the particle size is small, fine powder in the polymer increases,
If the particle size is large, coarse particles in the polymer increase, causing a decrease in bulk density and clogging of a hopper. The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 1000 m ² / g.
500 m ² / g, pore volume is usually 0.1-5 cm ³ / g,
Preferably it is 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume are
For example, it can be determined from the volume of nitrogen gas adsorbed according to the BET method.

Further, when the carrier is an inorganic substance, it is usually at 150 to 1000 ° C., preferably at 200 to 80 ° C.
It is desirable to use it after firing at 0 ° C. When at least one of the catalyst components is supported on the carrier, it is desirable that at least one of the catalyst component (A) and the catalyst component (B), and preferably both the catalyst component (A) and the catalyst component (B) be supported. .

The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the component (A) and the component (B) is mixed with the carrier. Method, a method of treating a carrier with an organoaluminum compound or a halogen-containing silicon compound, and then mixing the carrier with at least one of the component (A) and the component (B) in an inert solvent.
Or a method of reacting the component (B) with an organoaluminum compound or a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing the component (B) or the component (A). And a method of mixing the contact reactant of the components (A) and (B) with the carrier, and a method of coexisting the carrier during the contact reaction between the components (A) and (B).

In the above and the above reactions,
An organoaluminum compound as the component (C) can be added. In the present invention, the above (A), (B),
When contacting (C), an elastic wave may be irradiated to prepare the catalyst. Examples of the elastic wave include a sound wave, particularly preferably an ultrasonic wave. Specifically, the frequency is 1 to 1
000 kHz ultrasonic wave, preferably 10-500 kHz
Ultrasound.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at normal pressure to 2 MPa to give -20.
A method in which preliminary polymerization is performed at a temperature of about 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the weight ratio of the component (B-1) to the carrier is preferably 1: 5 to 1:10.
000, more preferably 1:10 to 1: 500, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000 by weight, more preferably It is desirable to set it as 1: 1 to 1:50. When two or more components (B) are used as a mixture, it is desirable that the ratio of each component (B) to the carrier be within the above range in terms of weight ratio. Further, the use ratio of the component (A) and the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 by weight.

Component (B) [Component (B-1) or (B-
If the usage ratio of [2) component] and the carrier or the usage ratio of component (A) and the carrier deviates from the above range, the activity may be reduced. The polymerization catalyst of the present invention thus prepared has an average particle size of usually 2 to 200 μm, preferably 1 to 200 μm.
It is 0 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. If the average particle size is less than 2 μm, the fine powder in the polymer may increase,
If it exceeds 0 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of the transition metal in 100 g of the carrier is usually 0.05 to 1%.
It is preferably 0 g, especially 0.1 to 2 g. If the amount of the transition metal is out of the above range, the activity may be low.

By supporting on a carrier in this way,
Polymerization with industrially advantageous high bulk density and excellent particle size distribution
You can get the body. Propylene alone used in the present invention
The polymer [I] was prepared using the polymerization catalyst described above.
It is produced by homopolymerizing ren. This place
In this case, the polymerization method is not particularly limited.
Polymerization, bulk polymerization, solution polymerization, suspension polymerization, etc.
Slip polymerization, gas phase polymerization,
Legitization is particularly preferred. Regarding the polymerization conditions, the polymerization temperature is
Usually -100 to 250C, preferably -50 to 200
° C, more preferably 0 to 130 ° C. Also, the reaction source
The usage ratio of the catalyst to the raw material is as follows:
Component (A) (molar ratio) is preferably 1 to 10 ⁸, Especially 1
00-10^FivePreferably, In addition, polymerization time
Is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 2 hours.
0 MPaG, particularly preferably normal pressure to 10 MPaG.
You.

Methods for controlling the molecular weight of the polymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane And halogenated hydrocarbons such as chloroform and dichloromethane. These solvents may be used alone or in a combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the polymerization, preliminary polymerization can be carried out using the polymerization catalyst. The prepolymerization can be carried out by, for example, bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and may be the same as those exemplified above, for example, ethylene, α- having 3 to 20 carbon atoms.
Olefins or mixtures thereof can be mentioned, but it is advantageous to use propylene used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0 ° C.
８０80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product was 0.1.
The amount of the prepolymerized product is at least 2 deciliters / g, especially at least 0.5 deciliters / g, and the amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is from 1 to 10,000 g, especially from 10 to 10 g.
It is desirable to adjust the conditions so that the weight becomes 00 g.

The propylene-ethylene block copolymer [II] blended in the propylene-based resin composition of the present invention comprises:
It is necessary to satisfy the following (6) and (7). (6)
The melt flow rate (MFR) measured under the conditions of 230 ° C. and a load of 21.18 N is 0.01 to 1000 g / 10 min. (7) The soluble component in normal temperature (25 ° C.) xylene is 3 to 60% by mass. The MFR of the propylene-ethylene block copolymer [II] is preferably from 0.1 to 500 g / 10 minutes, more preferably from 1 to 200 g / 10 minutes.
When the MFR is less than 0.01 g / 10 minutes, the resin does not easily flow during injection molding, and when the MFR exceeds 1000 g / 10 minutes, the amount of sticky components increases. The MFR is JI
It is a value measured according to SK7210. Room temperature (2
5 ° C.) The xylene-soluble component is preferably from 10 to 60% by mass, more preferably from 20 to 50% by mass. If this xylene-soluble component is less than 3% by mass, impact resistance is not sufficient, and if it exceeds 60% by mass, rigidity, surface hardness, and heat resistance are poor, and physical properties are insufficient. . The xylene-soluble component at normal temperature (25 ° C.) was obtained as follows. A sample was precisely weighed in an amount of 5 ± 0.05 g and placed in an eggplant-shaped flask having an internal volume of 1000 ml.
After adding 5 g, the rotor and para-xylene 700 ±
Add 10 ml. Next, a condenser is attached to the eggplant-shaped flask, and the flask is heated in an oil bath at 140 ± 5 ° C. for 120 ± 30 minutes while the rotor is operated to dissolve the sample in para-xylene. Next, after pouring the content of the flask into a beaker having an internal volume of 1000 ml, the solution in the beaker was allowed to cool to room temperature (25 ° C.) (8 hours or more) while stirring with a stirrer, and then the precipitate was deposited. With a wire mesh. The filtrate was further filtered through filter paper, and the filtrate was poured into 2000 ± 100 ml of methanol in a 3000 ml beaker, and the beaker was stirred with a stirrer at room temperature (25 ° C.). Leave for more than an hour. Next, the precipitate is collected by filtration with a wire mesh, and then air-dried for 5 hours or more, and then dried at 100 ± 5 ° C. for 240 to 270 minutes using a vacuum drier to recover a xylene-soluble component at normal temperature (25 ° C.). I do. The content (w) of the soluble component with respect to normal temperature (25 ° C.) xylene is as follows: when the sample weight is A grams and the weight of the soluble component recovered above is C grams, w (% by mass) = 100 × It is represented by C / A.

The propylene-ethylene block copolymer [II] can be produced by the following method. The polymerization catalyst used in the production of the propylene-ethylene block copolymer [II] is a solid catalyst component obtained by contacting and reacting a titanium compound, a magnesium compound and an electron-donating compound with a solid catalyst of the general formula (VIII) SiR ²¹ _m (OR ²² ) _4-m (VIII) (wherein, R ²¹ is a branched chain hydrocarbon group having 1 to 20 carbon atoms;
R ²² represents a straight-chain hydrocarbon group or a cyclic hydrocarbon group, and R ²² represents a straight-chain hydrocarbon group or a branched-chain hydrocarbon group having 1 to 4 carbon atoms. R ²¹ and R ²² may be the same or different. m shows the integer of 0-3. It is preferable to use a catalyst system comprising an organosilicon compound and an organoaluminum compound represented by the formula (1).

In the organosilicon compound represented by the general formula (VIII), R ²¹ is preferably a branched hydrocarbon group having 1 to 20 carbon atoms and a saturated cyclic hydrocarbon group. As R ²¹ , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group,
And a vinyl group and an aryl group.
A tertiary alkyl group of 0 and a cycloalkyl group are preferred. R
^Examples of ²² include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. As the organosilicon compound represented by the general formula (VIII), specifically, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, t- Butyltrimethoxysilane, texyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane,
Isobutyltriethoxysilane, t-butyltriethoxysilane, texyltriethoxysilane, propyltripropoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di- t-butyldimethoxysilane, ethylmethyldimethoxysilane, t
Alkylalkoxysilanes such as -butylmethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane, triisopropylmethoxysilane, tributylmethoxysilane, di-t-butyldiethoxysilane, etc .; cyclopentyltrimethoxysilane, cyclopentyltrisilane Cycloalkylalkoxysilanes such as ethoxysilane, cyclohexyltrimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, and the like; phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and the like Phenylalkylalkoxysilane; cyclopentylmethyldimethoxysila , Cyclohexylmethyl dimethoxysilane, cyclopentyl lutein cyclohexyl dimethoxysilane,
Cyclohexyl texyl dimethoxy silane, t-butyl cyclopentyl dimethoxy silane, t-butyl cyclohexyl dimethoxy silane, cyclohexyl cyclopentyl dimethoxy silane, t-butyl cyclopentyl diethoxy silane, t-butyl cyclohexyl diethoxy silane, cyclopentyl texyl diethoxy silane, cyclohexyl texyl silane Ethoxysilane, cyclohexylcyclopentyldiethoxysilane and the like can be mentioned. These organic silicon compounds may be used alone or in combination of two or more. Among these, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, di-t-butyldimethoxysilane, t-butylcyclopentyldimethoxysilane, t-butylcyclohexyldimethoxysilane, cyclopentyltexyldimethoxysilane, cyclohexyltexyldimethoxysilane, cyclohexylcyclopentyl Dimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, di-t-butyldiethoxysilane, t-butylcyclopentyldiethoxysilane, t-butylcyclohexyldiethoxysilane, cyclopentyltexyldiethoxysilane, cyclohexyltexyldiethoxysilane And cyclohexylcyclopentyldiethoxysilane are preferred.

As the titanium compound, general formula (IX) TiX ¹ _p (OR ²³ ) _4-p (IX) In the above general formula (IX), X ¹ represents a halogen atom, and among them, a chlorine atom And a bromine atom are preferred, and a chlorine atom is particularly preferred. R ²³ is a hydrocarbon group, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group; , Oxygen, silicon, phosphorus and the like. Preferably 1 to 1 carbon atoms
Zero hydrocarbon groups, particularly alkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, and the like are preferable, and linear or branched alkyl groups are particularly preferable. When a plurality of —OR ²³ are present, they may be the same or different from each other. Specific examples of R ²³ include methyl group, ethyl group, n- propyl group, an isopropyl group, n-
Butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl Group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. p shows the integer of 0-4.

Specific examples of the titanium compound represented by the above general formula (IX) include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium and tetraisotitanium. Tetraalkoxy titanium such as butoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium; titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride, and propoxytitanium trichloride Trihalogenated alkoxytitanium such as chloride, n-butoxytitanium trichloride and ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-titanium
dialkoxytitanium dihalides such as n-propoxytitanium dichloride and diethoxytitanium dibromide; trimethoxytitanium chloride, triethoxytitanium chloride,
Monohalogenated trialkoxytitaniums such as triisopropoxytitanium chloride, tri-n-propoxytitanium chloride and tri-n-butoxytitanium chloride can be mentioned. Among these, a titanium compound having a high halogen content, particularly titanium tetrachloride, is preferred from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.

As the magnesium compound, a magnesium compound represented by the general formula (X) MgR ²⁴ R ²⁵ ... (X) can be used.
In the general formula (X), R ²⁴ and R ²⁵ represent a hydrocarbon group, an OR ²⁶ group (R ²⁶ is a hydrocarbon group) or a halogen atom. Here, as the hydrocarbon group of R ²⁴ and R ²⁵ , an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group and the like, and as the OR ²⁶ group, R ²⁶ has 1 to 12 carbon atoms Twelve alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups and the like, and halogen atoms include chlorine, bromine, iodine, fluorine and the like. R ²⁴ and R ²⁵ may be the same or different.

Specific examples of the magnesium compound represented by the above general formula (X) include dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, diphenylmagnesium and dicyclohexylmagnesium. Alkylmagnesium, arylmagnesium; alkoxymagnesium such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium, dicyclohexyloxymagnesium, etc .; Chloride, butylmagnesium chloride, hex Le chloride, isopropyl magnesium chloride, isobutyl magnesium chloride, t- butyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride,
Alkyl magnesium halides such as ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium chloride, and butyl magnesium iodide, aryl magnesium halides; butoxymagnesium chloride, cyclohexyloxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, ethoxymagnesiumiodide Examples thereof include alkoxymagnesium halides such as dyed and aryloxymagnesium halides; and magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide.

The above-mentioned magnesium compound can be prepared from metallic magnesium or a compound containing magnesium. The magnesium compound may be in contact with a halide. The halogenated compounds include SiCl ₄ , SiBr ₄ , SnCl ₄ , S
Examples include nBr ₄ and HCl. Among these, SiCl ₄ is particularly preferred. Further, the magnesium compound may be supported on a support such as silica or alumina. The above magnesium compounds may be used alone or in combination of two or more. Further, it may contain halogen such as iodine, other elements such as silicon and aluminum, and may contain an electron donating compound such as alcohol, ether and ester.

Typical examples of the electron donating compound used for the solid catalyst component in the production of the propylene-ethylene block copolymer [II] are carboxylic acid ester derivatives, preferably aromatic carboxylic acid ester derivatives. And more preferably an ester derivative of an aromatic dicarboxylic acid. Further, the organic group of the ester portion is a straight chain,
It is preferably a branched or cyclic aliphatic hydrocarbon group. Among these, a phthalic acid diester derivative or a malonic acid diester derivative is preferable, and a linear or branched aliphatic hydrocarbon group having 4 or more carbon atoms is particularly preferable as the organic group in the ester portion. Specifically, di-n-butyl phthalate, di-iso-butyl phthalate, di-n-butyl malonate, di-iso-butyl malonate and the like are preferable. These aromatic dicarboxylic acid ester compounds may be used alone or in combination of two or more. The solid catalyst component may be brought into contact with the magnesium compound, the titanium compound, the halogen atom, the ester compound and, if necessary, the silicon compound by a usual method except for the temperature, and the contacting procedure is not particularly limited. For example, the components may be brought into contact in the presence of an inert solvent such as a hydrocarbon, or the components may be diluted with an inert solvent such as a hydrocarbon in advance and brought into contact. Examples of the inert solvent include aliphatic hydrocarbons such as n-octane and n-decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof. Can be mentioned. Here, the titanium compound is usually 0.5 to 100 with respect to 1 mol of magnesium of the magnesium compound.
Mol, preferably 1 to 50 mol. If the molar ratio is outside the above range, the catalytic activity may be insufficient. The electron donor is used in an amount of usually 0.01 to 10 mol, preferably 0.05 to 1.0 mol, per 1 mol of magnesium of the magnesium compound. If the molar ratio deviates from the above range, catalytic activity and stereoregularity may be insufficient. Further, when a silicon compound is used, it is usually 0.001 to 100 mol, preferably 0.005 mol, per 1 mol of magnesium of the above magnesium compound.
Use up to 5.0 moles. If the molar ratio deviates from the above range, the effect of improving catalytic activity and stereoregularity may not be sufficiently exhibited, and the amount of fine powder in the produced polymer may increase.

The above magnesium compound, titanium compound,
The contact of the halogen atom, the ester compound, and the silicon compound to be used if necessary, is performed after adding these components.
It is carried out in a temperature range of 20 to 150 ° C, preferably 125 to 140 ° C. When the contact temperature is in the above range, the effect of improving the catalytic activity and stereoregularity may not be sufficiently exhibited. The contact is usually performed for 1 minute to 24 hours, preferably 10 minutes to 6 hours. The pressure at this time varies depending on the type of solvent, the contact temperature, and the like when a solvent is used.
This is performed in the range of 1 MPaG. In addition, during the contact operation, it is preferable to perform stirring in view of uniformity of contact and contact efficiency. Further, it is preferable that the titanium compound is contacted twice or more to sufficiently support the magnesium compound serving as a catalyst carrier. When a catalyst is used in the contacting operation, it is usually 5,000 ml or less, preferably 10 to 10 mol per 1 mol of the titanium compound.
Use 1,000 ml of solvent. If this ratio deviates from the above range, contact uniformity and contact efficiency may deteriorate.

The solid catalyst component obtained by the above contacting is washed with an inert solvent at a temperature of 100 to 150 ° C., preferably 120 to 140 ° C. If the washing temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity may not be sufficiently exhibited. As the inert solvent,
For example, aliphatic hydrocarbons such as n-octane and n-decane; alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenation such as tetrachloroethane and chlorofluorocarbons. Hydrocarbons or mixtures thereof can be mentioned. Of these, aliphatic hydrocarbons are preferably used. The washing method is not particularly limited,
Methods such as decantation and filtration are preferred. There are no particular restrictions on the amount of the inert solvent used, the washing time, and the number of washings.
00-100,000 ml, preferably 1,000
~ 50,000 ml of solvent, usually 1 minute ~
The reaction is performed for 24 hours, preferably for 10 minutes to 6 hours. 0 moles,
Preferably, 0.005 to 5.0 mol is used. If the molar ratio deviates from the above range, the washing may be incomplete.
The pressure at this time depends on the type of solvent, washing temperature, etc.
The range varies, but is usually in the range of 0 to 5 MPaG, preferably 0 to 1 MPaG. During the washing operation, it is preferable to perform stirring from the viewpoint of uniformity of washing and washing efficiency. The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as a hydrocarbon.

The organoaluminum used in the production of the propylene-ethylene block copolymer [II] includes trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum and trioctylaluminum; dimethylaluminum chloride, Dialkylaluminum chlorides such as diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dioctylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride and ethylaluminum dichloride; dialkylaluminum fluorides such as dimethylaluminum fluoride; diisobutylaluminum hydride and diethylachloride , And the like alkylaluminum sesquihalide such as ethylaluminum sesquichloride; dialkylaluminum hydrides such as Miniumuhidorido. These organic aluminum compounds may be used alone or in combination of two or more.

The propylene-ethylene block copolymer [II] is prepared by producing a propylene homopolymer in the first polymerization step, and then copolymerizing propylene and ethylene in the second polymerization step in the presence of the propylene homopolymer. It can be manufactured by the following. As the polymerization method, any of a gas phase polymerization method, a liquid phase polymerization method, a slurry polymerization method, a bulk polymerization method and the like can be applied. In addition, the propylene homopolymerization in the first stage, and the copolymerization of propylene and ethylene in the second stage,
Each of these steps may be performed in two or more steps, or may be performed by different polymerization methods. In particular, in the latter stage of copolymerization of propylene and ethylene, a gas phase polymerization method, in which the copolymerization component is incorporated into the propylene block copolymer without elution, has a high yield with respect to the consumed olefin, and is industrially advantageous, is preferable. Furthermore, the catalyst at the time of polymerization is
A preliminarily polymerized α-olefin such as ethylene, propylene, 1-butene, or 1-hexene may be used.

The polymerization conditions differ depending on the polymerization method. The case of the gas phase polymerization method will be described. When a propylene polymer is produced in the former polymerization step, the polymerization temperature is 20 to 120 ° C., preferably 50 to 10 ° C. using the polymerization catalyst.
The polymerization can be carried out at a temperature of 0 ° C. and a polymerization pressure of 0.1 to 10 MPaG, preferably 0.1 to 5 MPaG while introducing propylene. Further, a molecular weight regulator such as hydrogen may be added to regulate the molecular weight. Further, as the catalyst at the time of polymerization, a catalyst which has been preliminarily polymerized with an α-olefin such as ethylene, propylene, 1-butene, or 1-hexene may be used. In the latter copolymerization step, propylene and ethylene are copolymerized in the presence of the propylene polymer obtained in the previous step. This copolymer is usually carried out subsequent to the preceding propylene polymerization. The polymerization temperature is preferably from 50 to 100 ° C, more preferably from 60 to 100 ° C.
90 ° C. range. When the polymerization temperature is lower than 50 ° C.,
Propylene-ethylene block copolymer produced [I
I] may have reduced transparency. Polymerization pressure is 0.1
The range is from 10 to 10 MPaG, preferably from 0.1 to 5 MPaG, and the polymerization can be carried out while introducing a mixed gas of propylene and ethylene. Further, a molecular weight regulator such as hydrogen may be added to regulate the molecular weight of the propylene-ethylene block copolymer [II]. Propylene-
The ethylene content in the ethylene block copolymer [II] is adjusted by the ratio of propylene to ethylene in the supplied mixed gas. Further, the copolymerization ratio of the propylene-ethylene block copolymer [II] is adjusted by the polymerization time and the polymerization pressure.

The propylene resin composition of the present invention can be obtained by dry blending the propylene homopolymer [I] and the propylene-ethylene block copolymer [II] using a Henschel mixer or the like, or Alternatively, it can be obtained by melt-kneading using a twin-screw extruder, a Banbury mixer or the like. The mixing ratio of the propylene homopolymer [I] is 1 to 99% by weight, preferably 1% by weight.
0-90% by weight, particularly preferably 20-80% by weight. If the propylene homopolymer [I] is less than 1% by weight, a composition having flexibility cannot be obtained.

The propylene resin composition of the present invention has a tensile modulus (E) of 100 MPa or more,
Melting point (Tm) measured by differential scanning calorimeter (DSC)
(° C.)) and the tensile modulus (E (MPa)) satisfy the following relationship: Tm> 0.06 × E + 76.6, and when the tensile modulus (E) is less than 100 MPa, Tm> 82. 6 and the Izod impact strength measured at −5 ° C.
It is preferable that the molded product of 2.0 kJ / m ² or more and having a thickness of 3 mm made of the propylene-based resin composition has a total light transmittance of 50% or more. When the propylene-based resin composition has a tensile modulus (E) of 100 MPa or more, Tm
> 0.06 × E + 80, more preferably Tm>
0.06 × E + 100 is more preferable, and Tm
It is particularly preferred that> 0.06 × E + 115. When the tensile modulus (E) of the propylene-based resin composition is less than 100 MPa, Tm> 86 is more preferable, Tm> 106 is more preferable, and Tm> 121 is preferable. Particularly preferred. Tm is 8
If it is less than 2.6, the heat resistance, especially the heat resistance against boiling water, will decrease.

Various additives may be added to the propylene resin composition of the present invention as desired. Various additives used as desired include antioxidants, neutralizing agents, slip agents, antiblocking agents, antifogging agents, and antistatic agents. These additives may be used alone or in a combination of two or more.
For example, examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

Specific examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, tris (2,4-di-
t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-
t-butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphonite,
ADK STAB 1178 (manufactured by Asahi Denka Co., Ltd.), SUMILIZER TNP (manufactured by Sumitomo Chemical Co., Ltd.), JP-135 (manufactured by Johoku Chemical Co., Ltd.), ADK STAB 2112 (manufactured by Asahi Denka Co., Ltd.)
Manufactured), JPP-2000 (manufactured by Johoku Chemical Co., Ltd.), Wes
ton 618 (manufactured by GE), ADK STAB PEP-2
4G (made by Asahi Denka Co., Ltd.), Adekastab PEP-36
(Made by Asahi Denka Co., Ltd.), ADK STAB HP-10 (made by Asahi Denka Co., Ltd.), Sandstab P-EPQ (made by Sando Co., Ltd.), Phosphite 168 (made by Ciba Specialty Chemicals Co., Ltd.) and the like. It is.

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol,
n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 4,4'-butylidenebis- (3-
Methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-
Bis {2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy] -1,1-
Dimethylethyl｝ -2,4,8,10-tetraoxaspiro [5,5] undecane, Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox BHT (Yoshitomi Pharmaceutical Co., Ltd.)
), Antage BHT (Kawaguchi Chemical Co., Ltd.), Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.), Irganox 1010 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-6
0 (made by Asahi Denka Co., Ltd.), Sumilizer BP-101 (made by Sumitomo Chemical Co., Ltd.), Tominox TT (Yoshitomi Pharmaceutical Co., Ltd.)
Manufactured), TTHP (manufactured by Toray Industries, Inc.), Irganox 31
14 (manufactured by Ciba Specialty Chemicals Co., Ltd.),
Adekastab AO-20 (made by Asahi Denka Co., Ltd.), Adekastab AO-40 (made by Asahi Denka Co., Ltd.), Sumilizer BB
MS (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox BB (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Antage W-300 (manufactured by Kawaguchi Chemical Co., Ltd.), Irganox 245 (manufactured by Ciba Specialty Chemicals Co., Ltd.) , ADK STAB AO-70
(Manufactured by Asahi Denka Co., Ltd.), Tominox 917 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), ADK STAB AO-80 (Asahi Denka Co., Ltd.)
Manufactured by Sumitomo Chemical Co., Ltd.) and Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.).

Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate. Pentaerythritol tetrakis (3-laurylthiopropionate),
Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox L
(Nippon Oil & Fats Co., Ltd.), Sumilizer TPM (Sumitomo Chemical Co., Ltd.), Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.)
Antiox M (Nippon Yushi Co., Ltd.), Sumilizer TPS (Sumitomo Chemical Co., Ltd.), Yoshinox DS
TP (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Antiox S (manufactured by NOF Corporation), ADK STAB AO-412S (manufactured by Asahi Denka Co., Ltd.), SEENOX 412S (manufactured by Cipro Kasei Co., Ltd.), Sumilizer TDP (Sumitomo) Chemical Co., Ltd.)
And the like.

When the propylene-based resin composition of the present invention is used for film and sheet applications, examples of the antioxidant include Irganox 1010: substance name: pentaerythrityl-tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] Irgafos 168: substance name: tris (2,4-di-t)
-Butylphenyl) phosphite Irganox 1076: Substance: Octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate Irganox 1330: Substance: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-
4-Hydroxybenzyl) benzene Irganox 3114: Substance: Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate P-EPQ: Substance: Tetrakis (2,4-di-t-) Butylphenyl) 4,4′-biphenylene-diphosphite is particularly preferred.

When an antioxidant is used in the present invention, the antioxidant may be added in an amount of about 0.001 to 1 part by weight based on 100 parts by weight of the propylene resin composition.
This is preferable because yellowing and the like can be prevented. Specific examples of use of the above antioxidants include: Example 1 Irganox 1010 1000 ppm PEP-Q 1000 ppm Example 2 Irganox 1076 1200 ppm PEP-Q 600 ppm Irgafos 168 800 ppm Example 3 Irganox 1010 400 to 1000 ppm Irgafos 168 750 to 750 1500 ppm and the like.

As the neutralizing agent for film and sheet applications,
Calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (DHT-4
A): Composition formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5
H ₂ O and the like are particularly preferred. As the antiblocking agent for use in films and sheets, “Sylysia”: a synthetic silica type manufactured by Fuji Silysia Ltd., and “Mizukasil”: a synthetic silica type manufactured by Mizusawa Chemical Industry Co., Ltd. are particularly preferable.

Examples of slip agents for use in films and sheets include erucamide, oleamide, stearamide, behenic amide, ethylenebisstearic amide, ethylenebisoleic amide, stearyl erucamide, and oleyl palmitamide. Particularly preferred.
When using a nucleating agent in the present invention, the amount of the nucleating agent is usually 10 ppm based on the propylene-based resin composition.
And more preferably in the range of 10 to 10000 ppm, more preferably in the range of 10 to 5000 ppm, and still more preferably in the range of 10 to 2500 ppm.
If it is less than 10 ppm, no improvement in low-temperature heat-sealing properties is observed, while if it exceeds 10,000 ppm, not only does the preferred effect not increase, but it also causes poor appearance.

[0084]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of catalyst and polymerization of propylene homopolymer [I] Synthesis of complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) Synthesis of zirconium dichloride (1,2′-dimethylsilylene) (2,2)
3.0 g (6.97 mmol) of lithium salt of 1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to -78 ° C. 2.1 mL (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise, and the mixture was stirred at room temperature for 12 hours. The solvent is distilled off, 50 ml of ether is added, and the mixture is washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried and the solvent was removed, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was added. ) Was obtained (yield 84).
%). Next, the (1,2′-dimethylsilylene) (2,1′-) obtained above was placed in a Schlenk bottle under a nitrogen stream.
3.04 g (5.88 mmol) of dimethylsilylene) -bis (3-trimethylsilylmethylindene) and 50 ml of ether were charged. Cool to -78 ° C and n-Bu
Li (1.54M in hexane) was added to 7.6 ml (1
(1.7 mmol), and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of a lithium salt as an ether adduct (yield 73%).
The result of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) is: δ 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.
10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2-7.7
(M, 8H, Ar-H). The lithium salt obtained above was dissolved in 50 ml of toluene under a nitrogen stream. The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride in toluene (20 ml) previously cooled to -78 ° C was added dropwise. After the addition, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off.
The obtained residue was recrystallized from dichloromethane to give 0.9 g of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride. 33
Mmol) (yield 26%). ¹ H-NMR (90 M
Hz, CDCl ₃ ) gives: δ 0.0
(S, 18H, trimethylsilyl), 1.02, 1.12
(S, 12H, dimethylsilylene), 2.51 (dd, 4
H, methylene), 7.1-7.6 (m, 8H, Ar-H).

Polymerization of Propylene 37.4 L / h of n-heptane / triisobutylaluminum (manufactured by Nippon Alkali Aluminum Co., Ltd.) was placed in a stainless steel autoclave having an internal volume of 250 L with a stirrer.
9 mmol / h, 13.6 mmol / h of methylaluminoxane (manufactured by Albemarle), further obtained as described above (1,
2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl)
Zirconium dichloride at 13.6 micromol / h,
It was supplied continuously. While the temperature was raised to 60 ° C., the volume ratio of hydrogen / propylene was 0.09, and the total pressure in the reactor was 0.8 M.
Propylene and hydrogen were continuously supplied so as to maintain PaG.
Polymerization was performed at a polymerization temperature of 60 ° C. for 120 minutes. Post-treatment The solvent of the obtained polymerization solution was distilled off under reduced pressure, and the following addition was prescribed thereto.
35-20) to obtain pellets.

(Additive formulation) Phenolic antioxidant: Ciba Specialty Chemicals, Irganox 1010; 500 ppm Phosphorus antioxidant: Ciba Specialty Chemicals, Irgafos 168; 1,000 ppm

(2) Preparation of Catalyst and Polymerization of Propylene-Ethylene Block Copolymer [II] Preparation of Solid Catalyst Component 16 g of diethoxymagnesium was placed in a 500 ml stainless steel three-necked flask purged with nitrogen.
(0.14 mol) and dehydrated heptane was added to 60
Milliliter was added. This was heated to 40 ° C., and 2.45 ml (22.5 mmol) of silicon tetrachloride was added.
After stirring for 0 minutes, 12.7 mmol of di-n-butyl phthalate was added. The temperature of the solution was raised to 80 ° C., and then 77 ml (0.70 mol) of titanium tetrachloride was added dropwise using a dropping funnel. As a second loading operation, the mixture was stirred for 2 hours at an internal temperature of 110 ° C. Thereafter, washing was sufficiently performed using dehydrated heptane to obtain a solid catalyst component. Polymerization of Propylene-Ethylene Block Copolymer 30 g of polypropylene powder was charged into a stainless steel autoclave with a stirrer and having a capacity of 5 liters, and the system was sufficiently purged with nitrogen gas. Dimethoxysilane
0.5 mmol and 0.01 mmol of the solid catalyst component obtained above in terms of titanium atoms were charged, and hydrogen and propylene were converted to 0.5 MPaG hydrogen, 2.3 MPaG propylene, and the total pressure in the reactor to 2.8 MPaG. The solution was continuously supplied so as to maintain the temperature, and polymerization was performed at a polymerization temperature of 70 ° C. for 45 minutes. Subsequently, after purging the reaction gas in the system, hydrogen, propylene and ethylene were purged with hydrogen at 0.3 MPaG, a volume ratio of propylene and ethylene of 7/3 (propylene / ethylene), and the total pressure in the reactor was reduced.
Supply continuously to keep at 1.5 MPaG, polymerization temperature 70 ° C
For 15 minutes. Post-treatment The solvent of the obtained polymerization solution was distilled off under reduced pressure, and the same addition as above was prescribed.
LC 35-20) to obtain pellets.

(3) Production of propylene-based resin composition 25 parts by weight of the pellets produced in the above (1) as propylene homopolymer [I] and propylene-ethylene block copolymer [II] in the above (2) 75 parts by weight of the produced pellets are charged into a blender and mixed well, and then a single screw extruder (manufactured by Tsukada Juki Seisakusho: TLC 35-2)
0) to obtain pellets of the propylene-based resin composition. (4) Injection molding The pellets of the propylene-based resin composition obtained as described above are injection-molded at a resin temperature of 240 ° C. and a mold temperature of 45 ° C. using an injection molding machine (manufactured by Toshiba Machine Co., IS100FIII). Was.

(5) Evaluation of Resin Properties and Physical Properties The propylene homopolymer [I], the propylene-ethylene block copolymer [II] and the resin composition were evaluated by the following methods. The results are shown in Tables 1 to 3. Measurement of melt flow rate (MFR) 230 ° C, load 21.1 according to JIS K7210
Measured at 8N. Measurement of Pentad Fraction It was measured by the method described in the text of the specification. Molecular weight distribution (Mw / Mn) It was measured by the method described in the specification text. Melting Endotherm (ΔH) Measured by the method described in the text of the specification. Amount of components eluted at 25 ° C. or lower in temperature rising chromatography (W25) It was measured by the method described in the specification. Xylene soluble fraction Measured by the method described in the text of the specification. Melting point (Tm) It was measured by the method described in the text of the specification. Tensile modulus (E) Based on JIS K7162, it was measured under the following conditions by a tensile test using a tensile test piece (No. 2 dumbbell, 3 mm in thickness). Crosshead speed: 50.0 mm / min Measurement direction: machine direction (MD direction) Izod impact strength According to JIS K-7110, an injection molded product of a propylene-based resin composition (63 mm × 12 mm × 3) was used as a test piece.
mm), the notched Izod impact strength was measured at an ambient temperature of 23 ° C. and −5 ° C. ■ Total light transmittance According to JIS K-7105, an injection molded product of a propylene-based resin composition (63 mm × 12 mm × 3
mm). (2) Moldability When the injection molded article was taken out of the mold during injection molding, 場合 indicates that the molded article did not adhere to the mold, and x indicates that the molded article could not be removed because it adhered to the mold.

Example 2 In Example 1, (3), the propylene homopolymer [I] was used.
Of 50 parts by weight and 50 parts by weight of the propylene-ethylene block copolymer [II] were subjected to granulation, injection molding and physical property evaluation in the same manner as in Example 1. Table 3 shows the results. Comparative Example 1 Injection molding was performed using only the propylene homopolymer [I].
Physical properties were evaluated. Table 3 shows the results.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

The propylene resin composition of the present invention is excellent in transparency, heat resistance, softness and low-temperature impact resistance.

Continued on the front page F term (reference) 4F071 AA15X AA20 AA20X AA75 AA81 AA84 AA88 AF20 AF20Y AF23 AF23Y AF30 AF30Y AF45 BA01 BB05 BC07 4J002 BB12W BP02X FD070 FD170 4J100 AA03P CA01 CA11 DA04 DA43

Claims (4)

[Claims] 1. The following (1) to (5) (1) a mesopentad fraction (mmmm) is 20 to 60 mol%, and (2) a racemic pentad fraction (rrrr).
And (1-mmmm) satisfy [rrrr / (1-mmmm)] ≦ 0.1, (3) a pentad fraction (rmrm) exceeds 2.5 mol%, and (4) a mesotriad fraction (mm). , Racemic triad fraction (rr), triad fraction (mr)
Satisfies the following relationship (mm) × (rr) / (mr) ² ≦ 2.0.
Propylene homopolymer [I] 1 to 99 that satisfies that the amount of the component (W25) eluted at a temperature of not more than 20 ° C is 20 to 100% by mass.
Mass%, and the following (6) and (7) (6) 230 ° C,
The melt flow rate (MFR) measured under the condition of a load of 21.18 N is 0.01 to 1000 g / 10 min.
(7) The soluble component in normal temperature (25 ° C.) xylene is 3 to
A propylene-based resin composition comprising 99 to 1% by mass of a propylene-ethylene block copolymer [II] satisfying 60% by mass. 2. The propylene homopolymer [I] has a molecular weight distribution (Mw / Mn) of 4 or less as measured by the following (8) and (9) (8) gel permeation chromatography (GPC). (9) The melt flow rate (MF) measured under the conditions of 230 ° C. and a load of 21.18 N.
The propylene resin composition according to claim 1, wherein R) satisfies 0.01 to 1000 g / 10 min. 3. When the propylene-based resin composition has a tensile modulus (E) of 100 MPa or more, a melting point (Tm (° C.)) and a tensile modulus (Tm) measured by a differential scanning calorimeter (DSC) are used. E (MPa)), the following relationship Tm> 0.06 × E + 76.6 is satisfied, and when the tensile modulus (E) is less than 100 MPa, Tm> 82.6, and measured at −5 ° C. Izod impact strength
2.0 kJ / m ² or more, and a molded article of the propylene resin composition having a thickness of 3 mm having a total light transmittance of 50
% Of the propylene-based resin composition according to claim 1. 4. A molded article comprising the propylene-based resin composition according to claim 1.