JP2000191861A - Soft polypropylene composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft polypropylene composition having a high flexibility, impact resistance, heat-sealing property and transparency. SOLUTION: The titled composition contains (i) a propylene random copolymer which comprises from 90 to 99 mol% propylene structural unit (a), from 0.5 to 9 mol% ethylene structural unit (b) and, if required, from 0 to 9.5 mol% 4-20C α-olefin structural unit (c) and has an intrinsic viscosity [η], measured in decalin at 135 deg.C, of from 0.5 to 6 dl/g, and (ii) a syndiotactic-structured propylene/ethylene copolymer which substantially has a syndiotactic structure and contains from 99 to 50 mol% propylene structural unit and from 1 to 50 mol% ethylene structural unit. Here, the weight ratio of (i) to (ii) is from 90/10 to 10/90.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene composition, and more particularly to a flexible polypropylene composition having excellent flexibility, impact resistance, heat sealability and transparency.

[0002]

Technical Background of the Invention A film comprising a propylene random copolymer obtained by copolymerizing propylene with ethylene and, if necessary, an α-olefin having 4 to 20 carbon atoms is inexpensive, flexible, moisture-resistant, Because of its excellent heat resistance, it is widely used in various packaging materials. However, in order to prevent damage to the contents, when the thickness of the film is increased, the flexibility, heat sealability, and transparency are deteriorated, and when the comonomer content in the propylene-based random copolymer is increased to improve this, The solid component amount became remarkable, and the blocking resistance also became a problem, and it was difficult to produce a thick film material having excellent flexibility, heat sealability, and transparency.

On the other hand, it is known that syndiotactic polypropylene, which is expected to improve physical properties, can be obtained by low-temperature polymerization in the presence of a catalyst comprising a vanadium compound, ether and organoaluminum. However, the polymer obtained by this method has a low syndiotacticity, and it cannot be said that the polymer exhibits the intrinsic syndiotactic property.

On the other hand, in J. A. According to Ewen et al., For the first time, it is possible to obtain a polypropylene having a high tacticity such that the syndiotactic pentad fraction exceeds 0.7 in the presence of a transition metal catalyst having an asymmetric ligand and an aluminoxane catalyst. (J. Am. Chem. Soc., 1988, 110,
6255-6256).

[0005] A. The polymer obtained by the method of Ewen et al. Has a high syndiotacticity and has more elastic properties than isotactic polypropylene. However, this is used as a soft molding material, for example, soft vinyl chloride or polypropylene. When it is intended to use in fields where vulcanized rubber or the like is used, its flexibility, rubber elasticity, and mechanical strength are not sufficient.

In general, attempts have been made to improve the flexibility and impact resistance of a propylene-based polymer by blending it with an ethylene-propylene copolymer rubber or the like in which the stereoregularity of the propylene constituent units is isotactic. It has been done. However, a molded article made of the resin composition obtained by this method is not sufficient, although flexibility and impact resistance are improved to some extent.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a flexible polypropylene composition excellent in flexibility, impact resistance, heat sealability and transparency. It is intended to provide.

[0008]

SUMMARY OF THE INVENTION The flexible polypropylene composition according to the present invention comprises (i) a structural unit derived from propylene (hereinafter referred to as "propylene structural unit") (a) and a structural unit derived from ethylene (hereinafter referred to as "ethylene"). It is called "structural unit.")
A propylene-based random copolymer comprising (b) and, if necessary, a structural unit derived from an α-olefin having 4 to 20 carbon atoms (hereinafter referred to as “α-olefin structural unit”) (c). The propylene structural unit (a) is from 90 to
It contains 99 mol%, 0.5 to 9 mol% of an ethylene structural unit (b), and 0 to 9.5 mol% of an α-olefin structural unit (c) having 4 to 20 carbon atoms. A propylene random copolymer having an intrinsic viscosity [η] in the range of 0.5 to 6 dl / g measured in decalin, and (ii) a propylene structural unit having a substantially syndiotactic structure of 99 to 50. And a propylene-based random copolymer (i) and a propylene-ethylene copolymer (ii) comprising a propylene-ethylene copolymer having a syndiotactic structure containing 1 to 50 mol% of an ethylene structural unit in an amount of 1 to 50 mol%.
Weight ratio {(i) / (ii)} is 90/10 to 10 /
90.

Further, the flexible polypropylene composition according to the present invention comprises (i) a propylene structural unit (a), an ethylene structural unit (b), and if necessary, an α-olefin structural unit having 4 to 20 carbon atoms. (C) a propylene-based random copolymer comprising: a propylene structural unit (a)
90 to 99 mol%, and the ethylene structural unit (b)
Α-olefin having 4 to 20 carbon atoms in an amount of 0 to 9.5 mol%, and having an intrinsic viscosity [η] of 0.5 in decalin at 135 ° C. of 0.5 to 9 mol%. ~ 6dl /
g of a propylene-based random copolymer, and (i
i) 99 to 50 mol% of a propylene structural unit substantially having a syndiotactic structure and 1 of an ethylene structural unit
And a weight ratio of the propylene-based random copolymer (i) to the propylene-ethylene copolymer (ii) ｛(i). / (Ii)｝ is 90/10
It is preferable that the nucleating agent (iii) is contained in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the composition of 10 to 90. In the present invention, the nucleating agent is preferably a sorbitol-based nucleating agent.

In a preferred embodiment of the present invention, the propylene random copolymer (i) has a melting point Tm measured by a differential scanning calorimeter of 70 <T.
m <155-5.5 (100-P) (wherein P is the propylene constituent unit content (mol%) of the copolymer) and the microisotacticity as seen from the triad chain of propylene. Is desirably in the range of 0.8 or more.

[0011] In a preferred embodiment of the present invention,
The propylene-ethylene copolymer (ii) is 135
Intrinsic viscosity [η] measured in decalin at a temperature of 0.01 to
The molecular weight distribution (ratio of weight average molecular weight Mw to number average molecular weight Mn, Mw / Mn) by GPC (gel permeation chromatography) is 4 dl / g.
And a glass transition temperature (Tg) of -15 ° C. or less.

In a preferred embodiment of the present invention,
Presence of a catalyst system wherein the propylene-ethylene copolymer (ii) comprises the following component (A) and at least one compound selected from the group consisting of the following components (B), (C) and (D) (A): a transition metal complex represented by the following formula (I) or (II);

Embedded image [In the above formulas (I) and (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru atoms, Cp ¹ and C
p ² is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or a neutral Lewis base ligand , Y is a ligand containing a nitrogen, oxygen, phosphorus or sulfur atom, and Z is C, O, B, S, G
e, Si or Sn atoms or groups containing these atoms. (B): a compound which reacts with the transition metal M in the component (A) to form an ionic complex; (C): an organoaluminum compound; and (D): an aluminoxane.

The polypropylene composition according to the present invention is excellent in flexibility, impact resistance, heat sealability and transparency in a well-balanced manner.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the flexible polypropylene composition of the present invention will be described in detail. [Soft polypropylene-based composition] The polypropylene-based composition according to the present invention comprises (i) a propylene structural unit (a) and an ethylene structural unit (b) and, if necessary, 4 to 2 carbon atoms.
A propylene-based random copolymer comprising α-olefin structural units (c) of 0 to 90% by mole and 99 to 99% by mole of propylene structural units (a) and 0.5 to 9% by mole of ethylene structural units (b). , Α-olefin structural unit (c) is 0
A propylene-based random copolymer having an intrinsic viscosity [η] in the range of 0.5 to 6 dl / g, as measured in decalin at 135 ° C .; 99 to 50 mol% of a propylene structural unit having a syndiotactic structure and 1 to 50 mol% of an ethylene structural unit
Syndiotactic structure propylene-
And an ethylene copolymer.

First, components (i) and (ii) contained in the polypropylene composition will be described. <(I) Propylene-based random copolymer> The propylene-based random copolymer (i) is composed of a propylene structural unit (a) and an ethylene structural unit (b) and, if necessary, having 4 to 4 carbon atoms.
A propylene random copolymer comprising 20 α-olefin structural units (c), wherein the propylene structural unit (a) is 90 to 99 mol%, preferably 90 to 98 mol%, more preferably 92 to 98 mol%. % Of the ethylene structural unit (b) in an amount of 0.5 to 9 mol%, preferably 0.1 to 9 mol%.
5 to 8 mol%, more preferably 1.5 to 8 mol%, and the α-olefin structural unit (c) is 0 to 9.5 mol%, preferably 0 to 8.5 mol%, and more preferably 0 to 8.5 mol%.
-7% by mole.

The α-olefin having 4 to 20 carbon atoms used as the structural unit (c) in such a propylene-based random copolymer includes 1-butene, 1-pentene,
1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosane and the like. One of these
-Butene is preferred.

The intrinsic viscosity [η] of the propylene random copolymer measured in decalin at 135 ° C.
Is 0.5 to 6 dl / g, preferably 1.0 to 4 dl / g.
g. When the intrinsic viscosity is in this range, good fluidity is exhibited, the propylene-based random copolymer is easily compounded with other components, and a molded article having excellent mechanical strength is obtained from the obtained composition. Tend to be

In the propylene random copolymer, the melting point (Tm) measured by a differential scanning calorimeter is 70 <Tm <155-5.5 (100-
P) (wherein P is the propylene constituent unit content (mol%) of the copolymer), preferably 90 <Tm <155-
It is preferable to satisfy the relation of 5.5 (100-P). When Tm is in such a range, transparency and blocking resistance tend to be excellent.

The microisotacticity of the propylene triad chain is preferably 0.8 or more, more preferably 0.85 or more. When the microisotacticity is in such a range, the crystallization speed is high and the workability is excellent.

Here, the microisotacticity viewed from the triad chain will be described. The triad tacticity of the propylene-based random copolymer (i) was determined by the ¹³ C-NMR spectrum of the copolymer and the following formula, of the three units of the propylene structural unit having a head-to-tail bond: It is determined as the strength (area) ratio of the side chain methyl group.

[0021]

(Equation 1) (Wherein PPP (mm), PPP (mr), and PPP (rr) are each a three-chain portion of the head-to-tail bonded propylene structural unit observed in the shift region in the lower table of the ¹³ C-NMR spectrum,
This is the area of the side-chain methyl group in the second unit. )

[Table 1]

Such PPP (mm), PPP (mr), PP
P (rr) represents a head-to-tail bonded propylene three-unit chain of the following structural formula.

Embedded image

In the methyl carbon region (19 to 23 ppm)
In addition to the side chain methyl group of the propylene structural unit in the head-to-tail bonded propylene three-unit chain as described above, the side chain methyl group peak of the propylene structural unit in other chains as described below is observed. You. When obtaining the mm fraction, the peak area of such a methyl group that is not based on three chains of propylene constituent units is corrected as follows. Hereinafter, E represents an ethylene structural unit.

In the second region, the propylenes are
A peak derived from the side chain methyl group of the second unit (propylene unit) in the tail-linked PPE 3 chain is observed.
The area of the methyl group peak can be determined from the peak area of the methine group (resonating around 30.6 ppm) of the second unit (propylene unit) in the PPE chain.

In the third area, the second in the EPE3 chain
A peak derived from the side chain methyl group of the unit (propylene unit) is observed. The peak area of this methyl group is
The methine group (3) of the second unit (propylene unit) in the chain
(Resonance around 2.9 ppm).

In the second region and the third region, a small amount contained in the propylene-ethylene random copolymer and represented by the following partial structures (i), (ii) and (iii): Peaks derived from the methyl groups CE ′ in the irregular units are observed. In the second region, the methyl group C
A peak, a methyl group D peak and a methyl group D 'peak are observed, and in the third region, a methyl group E peak and a methyl group E' peak are observed.

The methyl group A peak and the methyl group B peak were observed at 17.3 ppm and 17.0 ppm, respectively, in the methyl group in the position irregular units, structures (i) to (iii). Not observed in ~ 3 regions.

[0028]

Embedded image

The peak area of the methyl group C can be determined from the peak area of the adjacent methine group (resonating around 31.3 ppm). The peak area of the methyl group D is represented by the structure (i
1) 1 / of the sum of the peak areas of the peaks (around 34.3 ppm and around 34.5 ppm) based on αβ methylene carbon
2 can be obtained.

The peak area of the methyl group D ′ is determined by the structure (iii)
Of the methine group adjacent to the methyl group E ′ (3
(Around 3.3 ppm). The peak area of the methyl group E was calculated from the adjacent methine carbon (33.7p
pm). The peak area of the methyl group E ′ is determined by the adjacent methine carbon (33.
(Around 3 ppm).

Therefore, by subtracting these peak areas from the total peak areas of the second and third regions, the peak area of the side chain methyl group of the second propylene unit in the three head-to-tail bonded propylene unit chains can be calculated. You can ask. In addition, each carbon peak in the spectrum can be assigned by referring to the literature (Polymer, 30, 1350 (1989)).

In the production of such a propylene-based random copolymer (i), it can be produced using, for example, a known titanium-based catalyst or a known metallocene-based catalyst as a catalyst. Here, the production using a metallocene-based catalyst will be described. As this metallocene catalyst,
For example, [I] reacts with a transition metal compound represented by the following formula (III), [II] [II-a] an organoaluminum oxy compound, and / or [II-b] the transition metal compound [I] to form an ion. A compound forming a pair and optionally [III]
And a catalyst formed from an organic aluminum compound.

[0033]

Embedded image

In the formula (III), M is the periodic table IVa, V
a, a transition metal of group VIa, specifically, titanium, zirconium, hafnium, vanadium, niobium,
Tantalum, chromium, molybdenum, tungsten,
Preferred are titanium, zirconium and hafnium, and particularly preferred is zirconium.

The substituents R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
An oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Also, some of the groups adjacent to each other may be bonded to form a ring together with the carbon atoms to which those groups are bonded. It is to be noted that R ^{1 to} R ⁴ represented by two each indicate that when they are combined to form a ring, they are preferably combined in a combination of the same symbols.

Specifically, the halogen atom includes fluorine,
Chlorine, bromine, iodine and the like, as the hydrocarbon group having 1 to 20 carbon atoms, methyl, ethyl, propyl, butyl,
Alkyl groups such as hexyl, cyclohexyl, octyl, nonyl, dodecyl, aicosyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl And aryl groups such as trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl, etc., and as the halogenated hydrocarbon group, the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms. Groups. The ring formed by the combination of these hydrocarbon groups includes a condensed group such as a benzene ring, a naphthalene ring, an acenaphthene ring and an indene ring, and a group in which a hydrogen atom on these condensed groups is substituted with an alkyl group. Is mentioned.

Further, monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl and dimethylphenylsilyl , Trihydrocarbon-substituted silyls such as methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylphenyl; A hydroxy-containing group, an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, dimethylphenoxy, naph Aryloxy groups such as alkoxy, phenylmethoxy, oxygen-containing substituents such as arylalkoxy group such as phenyl ethoxy;

A sulfur-containing group in which oxygen of the oxygen-containing compound is replaced by sulfur; an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino; Nitrogen-containing groups such as arylamino groups or alkylarylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino; and phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group.

As specific examples, halogen atoms, oxygen-containing groups, hydrocarbon groups having 1 to 20 carbon atoms, and halogenated hydrocarbon groups having 1 to 20 carbon atoms are the same as those described above for R ^{1 to} R ⁴ . Examples of the sulfur-containing group include, in addition to the groups represented by R ^{1 to} R ⁴ , methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, and trimethylbenzene sulfonate. , Triisobutylbenzenesulfonate, p-chlorobenzenesulfonate,
Examples include sulfonate groups such as pentafluorobenzene sulfonate, methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, and pentafluorobenzene sulfinate. Can be

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,-
SO _2- , -NR ^5- , -P (R ⁵ )-, -P (O) (R ⁵ )-,
—BR ⁵ — or —AlR ⁵ — where R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 halogenated hydrocarbon groups], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-
Alkylene groups such as 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, diphenylmethylene, diphenyl-1,2
-1 carbon atoms such as arylalkylene groups such as ethylene
A halogenated hydrocarbon group obtained by halogenating a hydrogen atom of the divalent hydrocarbon group having 1 to 20 carbon atoms, such as a divalent hydrocarbon group having 20 to 20 carbon atoms, chloromethylene, methylsilylene, dimethylsilylene, diethylsilylene, Di (n-propyl)
Alkylsilylene, alkylarylsilylene, arylsilylene groups such as silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene and di (p-chlorophenyl) silylene , Tetramethyl-1,2
Divalent silicon-containing groups such as alkyldisilyl, alkylaryldisilyl, and arylsilyl groups such as -disilyl and tetraphenyl-1,2-disilyl, and divalent silicon obtained by substituting silicon of the above divalent silicon-containing group with germanium R ⁵ is a germanium-containing group, a divalent tin-containing group substituent obtained by substituting silicon in the divalent silicon-containing group with tin, and the like.
The same halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, and halogenated hydrocarbon groups having 1 to 20 carbon atoms as in R ^{1 to} R ⁴ .

Of these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable. Preferred are silylene, alkylarylsilylene, and arylsilylene.

Specific examples of the transition metal compound represented by the above general formula (III) will be given below. rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2,7-dimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7
-Dimethyl-4-i-propylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl) zirconium dichloride, rac-dimethylsilylene-bis} 1- (2,7-dimethyl-4-
sec-butylindenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-n-hexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-trimethylsilylenemethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl- 4-trimethylsiloxymethylindenyl) zirconium dichloride,
rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylenebis {1- (2,7-dimethyl-4-i) -
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylenebis {1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (cyclohexyl) silylene bis {1- (2,7-dimethyl)
-4-i-propylindenyl)｝ zirconium dichloride, rac-methylphenylsilylenebis ｛1- (2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-methylphenylsilylenebis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylenebis ｛1- (2,7-dimethyl-4
-t-butylindenyl) zirconium dichloride, rac
-Diphenylsilylenebis ｛1- (2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-diphenylsilylenebis ｛1- (2,7-dimethyl-4-ethylindenyl)｝ zirconium dichloride , Rac-di (p-tolyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylenebis {1- (2,7-dimethyl) -4-i-propylindenyl) デ zirconium dichloride, rac-dimethylsilylenebis ｛1- (2-methyl-4-i-propyl-7-ethylindenyl)｝ zirconium dibromiderac-dimethylsilylene-bis ｛1 -(2,7-dimethyl-4-i-propyl-1-
Indenyl) zirconium dimethyl, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl) -4-i-propyl-1-indenyl) zirconium-bis-1- (trifluoromethanesulfonato), rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-i-propyl-1-indenyl) Zirconium-bis ｛1- (p-phenylsulfinato), rac-dimethylsilylene-bis ｛1- (2-phenyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride and the like.

Further, rac-dimethylsilylene-bis {1- (4
-Phenyl-1-indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (2-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis ｛1- (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-bromophenyl) Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-tolyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis {1- (2-methyl-4- (o-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1
-(2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis {1- (2-methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium Dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (m-biphenyl) indenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m -Trimethylsilylenephenyl) -1-indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis (2-phenyl-4-phenylindenyl)｝ zirconium dichloride, rac-diethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-di- ( i-Propyl) silylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Dicyclohexylsilylene-bis ｛1
-(2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-
Methyl-4-phenylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac-
Di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-
Chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene- Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstannylene- Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis ｛1
-(2-methyl-4-phenylindenyl)｝ zirconium dimethyl, rac-dimethylsilylene-bis ｛1- (2-methyl-4-
Phenylindenyl) zirconium methyl chloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me, rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} titanium dichloride, rac -Dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} hafnium dichloride and the like.

Further, rac-dimethylsilylene-bis ｛1-
(2-ethyl-4-phenylindenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-
4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(Β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2-
Methyl-1-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-
(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(9-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(O-methylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(M-methylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(P-methylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-)
(2,3-dimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2
-Ethyl-4- (2,5-dimethylphenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-ethyl-4- (2,4,6-trimethylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis} 1- (2-ethyl-4- (2,6-dichlorophenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4 -(2-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (3-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (4-bromophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (4-biphenylyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-ethyl-4- (4-trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4-)
Phenylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4-)
(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-
4- (9-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1 -(2-i
-Propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1 -(2-i-propyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (2-methyl-1-naphthyl) indenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i
-Propyl-4- (5-acenaphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis-1- (2
-i-propyl-4- (9-anthracenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-propyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-s-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2
-s-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s
-Butyl-4- (8-methyl-9-naphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-s-butyl-4- (5-acenaphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-s-butyl-4- (9-anthracenyl) indenyl)｝
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis
-(2-n-pentyl-4- (α-naphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-n-butyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-
4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-
Butyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n
-Butyl-4- (9-anthracenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-n-butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-i-butyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-
4- (2-methyl-1-naphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1- (2-i
-Butyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i
-Butyl-4- (9-anthracenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-i-butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
Neopentyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2
-n-hexyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-hexyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-methylphenylsilylene- Screw ｛1- (2-
Ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-ethyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-ethyl-4- (9-anthracenyl) indenyl) {zirconium dichloride, rac-methylphenylsilylene-bis} 1
-(2-ethyl-4- (9-phenanthryl) indenyl) デ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛ 1- (2-
Ethyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4- (9-anthracenyl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1 -(2
-Ethyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1-
(2-ethyl-4- (4-biferinyl) indenyl)｝ zirconium dichloride, rac-methylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylene-bis ｛1- ( 2-ethyl-4- (α-naphthyl) indenyl) デ zirconium dichloride, rac-ethylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-ethylene-bis ｛1- (2 -Ethyl-4- (α-naphthyl) indenyl) コ zirconium dichloride, rac-ethylene-bis ｛1- (2-n-propyl-4-
(Α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylgermylene-bis ｛1- (2-ethyl -4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermylene-bis ｛1- (2-n-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylstannylene-bis ｛1 -(2-ethyl-4-phenylindenyl) デ zirconium dichloride, rac-dimethylstannylene-bis ｛1- (2-ethyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylstannylene- Bis {1- (2-n-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-n-propyl-4-phenylindenyl)} zil Such as Niumujikurorido.

In the present invention, zirconium metal is replaced with titanium metal, hafnium metal,
Transition metal compounds replaced with vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, and tungsten metal can also be used.

The above transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but it is also possible to use R type or S type. The transition metal compound according to the present invention as described above, Journal of Organometallic
Chem., 288 (1985), pp. 63-67, European Patent Application Publication No. 0,320,762 and its examples can be produced as follows.

The [II-a] organoaluminum oxy compound forming the catalyst used in the production of the propylene random copolymer (i) of the present invention may be a conventionally known aluminoxane. It may be a benzene-insoluble organic aluminum oxy compound as exemplified in Japanese Patent No. 78687.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum. Aluminum, trialkyl aluminum such as tritert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, etc., tricycloalkyl aluminum such as tricyclohexyl aluminum, tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum Chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. Alkylaluminum halides, diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. Further, as an organoaluminum compound used for preparing an aluminoxane, isoprenyl aluminum represented by the following general formula can also be used. (In the above formula, x, y, z are positive numbers, a z ≧ 2x.) (i- C 4 H 9) x Al y (C 5 H 11) z organoaluminum compounds mentioned above are They can be used alone or in combination.

Solvents used for the solution or suspension of aluminoxane include benzene, toluene, xylene,
Aromatic hydrocarbons such as aromatic hydrocarbons such as cumene and cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, and cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane And petroleum fractions such as gasoline, kerosene and light oil, and hydrocarbon solvents such as the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon halides, especially chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

The compound [I] which forms an ion pair by reacting with the above transition metal compound [I] to form a catalyst used in the production of the propylene random copolymer (i) of the present invention.
As Ib], JP-A-1-501950, JP-A-1-50203, JP-A-3-179005, JP-A-3-179006, JP-A-3-207
703, JP-A-3-207704, US-
Examples include Lewis acids, ionic compounds and carborane compounds described in Japanese Patent No. 457718.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorophenyl) _{boron, MgCl 2, Al 2 O 3} , SiO 2 -Al 2
O ₃ can be exemplified.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, Cenium tetra (pentafluorophenyl) borate can be exemplified.

Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, and tri-n-butylammonium (Trideca hydride-7-carboundeca) borate and the like can be exemplified.

Compound [I] forming an ion pair as described above
Ib] can be used in combination of two or more.

The organoaluminum compound [III] optionally used for forming the catalyst used in the production of the propylene random copolymer (i) of the present invention comprises:
For example, it is represented by the following general formula (IV). R ⁹ _n AlX _3-n (IV) (wherein R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms,
X is a halogen atom or a hydrogen atom, and n is a number of 1 to 3. In the general formula (IV), R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group,
Examples include n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Such an organoaluminum compound [II
Specific examples of I] include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminumchloride, diethylaluminumchloride Dialkylaluminum halides such as diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide, alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide Alkyl aluminum dihalides such as um sesquihalide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

The organoaluminum compound [III] is
It may be represented by the following general formula (V). R ⁹ _n AlL _3-n (V) (wherein R ⁹ is the same as in the above formula (IV), and L is -OR
¹⁰ group, -OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR
¹³ ₂ group, an -SiR ¹⁴ ₃ group or -N (R ¹⁵⁾ AlR ¹⁶ ₂ group, n is ^{1~2, R 10, R 11,} R 12 and R ¹⁶ are a methyl group, an ethyl group, an isopropyl Group, isobutyl group,
A cyclohexyl group, a phenyl group or the like; R ¹³ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group or the like; and R ¹⁴ and R ¹⁵ are a methyl group, an ethyl group or the like. ) Among such organoaluminum compounds, R ⁹ _nA
l (OAlR ¹² ₂₎ a compound represented by _3-n, e.g., Et ₂ AlO
AlEt ₂ and (iso-Bu) ₂ AlOAl (iso-Bu) ₂ are preferred.

[0062] Among the above general formula (IV) and an organic aluminum compound represented by (V), the general formula R ⁹ compounds represented by ₃ Al are preferred, especially compounds wherein R ⁹ is an isoalkyl group.

The metallocene catalyst used in the production of the propylene random copolymer (i) of the present invention comprises the above-mentioned component [I], component [II-a] (and / or component [I-a]).
Ib]) and, if necessary, component [III] in an inert hydrocarbon solvent or olefin solvent.

Examples of the inert hydrocarbon solvent used for preparing the catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, cyclopentane, cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof.

In preparing a catalyst from each of the above components, the components can be brought into contact with each other in any order, but the components [I] and [II-a] (and / or component [II-a]) can be used. -
b]) or component [II-a] and component [III] and then component [I] or component [I] and component [II-a] (and / or Contact with component [II-b]) and then mix component [III] or contact component [I] with component [III] and then contact component [II-a] (and / or component [II-b]). [II-b]) is preferably contacted.

When the above components are brought into contact with each other,
The genus compound [I] has about 10^-8-10 ^-1Mol / liter
(Polymerization volume), preferably 10^-7~ 5 × 10^-2Mol / l
Used in the amount of the title.

The component [II-a] is an atomic ratio (Al / transition metal) to the transition metal in the component [I] and is usually from 10 to 100.
00, preferably 20 to 5000. When component [II-b] is used, the molar ratio of component [I] to component [II-b] (component [I] / component [II-b]) is usually 0.01.
-10, preferably 0.1-5.

The component [III] has an atomic ratio (Al _C / Al _B-1 ) between the aluminum atom (Al _C ) in the component [III] and the aluminum atom (Al _B-1 ) in the component [II-a]. ), Usually 0.
An amount of from 02 to 20, preferably from 0.2 to 10, can be used as needed.

The above catalyst components may be mixed and contacted in a polymerization vessel, or may be mixed and contacted in advance and then added to the polymerization vessel. When contacting in advance, usually -50 ~
150 ° C, preferably -20 to 120 ° C, 1 to 100
Contact for 0 minutes, preferably 5 to 600 minutes. At the time of contact, the contact temperature may be changed.

In preparing the metallocene-based catalyst as described above, the components [I], [II] and [II]
At least one of [I] may be supported on a granular or fine particulate carrier to form a solid catalyst.

The carrier is preferably a porous oxide. For example, an inorganic carrier such as SiO ₂ or Al ₂ O ₃ can be used. Further, an organic carrier such as a polymer or a copolymer formed mainly of α-olefin such as ethylene, propylene and 1-butene or styrene can be used.

In the catalyst used in the present invention, olefins such as propylene, ethylene and 1-butene, or these and other olefins may be prepolymerized. The olefin polymerization catalyst used in the present invention,
In addition to the components described above, other components useful for olefin polymerization, such as water as a catalyst component, may be included.

The propylene random copolymer (i) used in the present invention is obtained by copolymerizing propylene and ethylene in the presence of the above-mentioned metallocene catalyst so as to finally have the above-mentioned properties. It can be produced by polymerizing. The polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization or gas phase polymerization methods.

In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the above catalyst preparation can be used, and propylene can be used as the solvent. The polymerization is usually carried out at -50 to 100 when performing the suspension polymerization method.
C., preferably at a temperature of 0 to 90 ° C., and when performing a solution polymerization method, it is usually 0 to 250 ° C.
C., preferably at a temperature of 20 to 200.degree. When carrying out the gas phase polymerization method, it is desirable that the polymerization is usually carried out at a temperature of 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization is usually carried out at normal pressure to 100
kg / cm ² , preferably under normal pressure to 50 kg / cm ² .

The polymerization can be carried out in any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting propylene-based random copolymer is determined by the presence of hydrogen in the polymerization system, or the polymerization temperature,
It can be adjusted by changing the polymerization pressure.

<(Ii) Propylene-ethylene copolymer having a syndiotactic structure> The propylene-ethylene copolymer having a syndiotactic structure is preferably composed of 99 to 50 mol% of propylene structural units having a substantially syndiotactic structure. Is 95 to 55 mol%, particularly preferably 9
0 to 65 mol%, and the ethylene constituent unit is 1 to
It is contained in an amount of 50 mol%, preferably 5 to 45 mol%, particularly preferably 10 to 35 mol%. The syndiotactic propylene-ethylene copolymer (ii) containing the ethylene constitutional unit and the propylene constitutional unit in such an amount has good compatibility with the propylene-based random copolymer, and the resulting polypropylene-based composition Has a tendency to exhibit sufficient flexibility, heat sealability and impact resistance.

The propylene-ethylene copolymer (ii) having the syndiotactic structure has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 10 d.
1 / g, preferably in the range of 0.05 to 10 dl / g. When the intrinsic viscosity [η] of the syndiotactic structure propylene-ethylene copolymer (ii) is within the above range, weather resistance, ozone resistance, heat aging resistance,
It becomes a syndiotactic propylene-ethylene copolymer having excellent properties such as low-temperature properties and dynamic fatigue resistance.

The syndiotactic propylene-ethylene copolymer (ii) has a single glass transition temperature, and the glass transition temperature Tg measured by a differential scanning calorimeter (DSC) is usually -15 ° C. Below, it is desirable to be in the range of preferably below -20C. The syndiotactic propylene-ethylene copolymer (ii)
When the glass transition temperature Tg is within the above range, cold resistance,
Excellent low temperature characteristics.

The molecular weight distribution (M
(w / Mn, in terms of polystyrene) is preferably 4.0 or less. And wherein substantially Shinji Oh tack tick structure, the propylene - In the ethylene copolymer was measured in 1,2,4-trichlorobenzene solution ¹³
The peak intensity observed at about 20.2 ppm in C-NMR is 0.3 or more, preferably 0.5 or more, with respect to the peak intensity 1 attributed to all methyl groups of the propylene unit.
It is more preferably 0.6 or more, and if it is in the range of 0.3 or more, transparency, scratch resistance, and impact resistance are improved, which is preferable.

Note that this syndiotactic structure is
It is measured as follows. That is, sample 0.35
g is dissolved in 2.0 ml of hexachlorobutadiene by heating. After filtering this solution through a glass filter (G2), 0.5 ml of deuterated benzene was added, and the inner diameter was 10 mm.
Into the NMR tube. And JEOL GX-
^13C -NM at 120 ° C using a 500-type NMR measuring apparatus
Perform R measurement. The number of integration is 10,000 or more.

Syndiotactic structure propylene-d
Production of Tylene Copolymer (ii) Such a syndiotactic propylene-ethylene copolymer (ii) is preferably obtained by copolymerization in the presence of a metallocene catalyst shown below.

Examples of such a metallocene catalyst include transition metal complexes (A) represented by the following formulas (I) and (II):

Embedded image [In the above formulas (I) and (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru atoms, Cp ¹ and C
p ² is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or a neutral Lewis base ligand , Y is a ligand containing a nitrogen, oxygen, phosphorus or sulfur atom, and Z is C, O, B, S, G
e, Si or Sn atoms or groups containing these atoms. And at least one compound selected from the group consisting of the following components (B), (C) and (D). (B): a compound that reacts with the transition metal M in the component (A) to form an ionic complex (also referred to as an ionized ionic compound); (C): an organoaluminum compound; and (D): aluminoxane.

First, the transition metal complex (A) represented by the formula (I) used in the present invention will be described.

Transition metal complex (A) In the above formula (I), M is Ti, Zr, Hf, Rn, Nd,
Sm or Ru atom, preferably Ti, Zr or Hf atom, and Cp ¹ and Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, X ¹ and X
² is an anionic ligand or a neutral Lewis base ligand, and Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms, preferably one O , Si or C atom.

In the formula (I), the bonding group Z is preferably C, O,
It is preferably one atom selected from B, S, Ge, Si, and Sn, and this atom may have a substituent such as an alkyl group or an alkoxy group. They may combine to form a ring. Of these, Z is preferably selected from O, Si and C atoms.

Cp ¹ and Cp ² are ligands which coordinate to the transition metal, and include cyclopentadienyl group, indenyl group, 4,5,
A ligand having a cyclopentadienyl skeleton such as a 6,7-tetrahydroindenyl group or a fluorenyl group, and the ligand having a cyclopentadienyl skeleton includes an alkyl group, a cycloalkyl group, and a trialkylsilyl group. And a substituent such as a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, specifically, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfone An acid-containing group (—SO ₃ Ra, where Ra is an alkyl group, an alkyl group in which a hydrogen atom is substituted with a halogen atom, an aryl group, an aryl group in which a hydrogen atom is substituted with a halogen atom, or an aryl substituted with an alkyl group; A), a halogen atom, a hydrogen atom and the like.

The following is an example of a metallocene compound containing one ligand having a cyclopentadienyl skeleton. Diphenylmethylene (cyclopentadienyl) fluorenylhafnium dichloride, diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride,
Isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, or isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride, (t-butylamido) dimethyl (fluorenyl) silanetitanium dimethyl, diphenylmethylene (cyclopentadienyl) Fluorenyl zirconium dichloride and the like.

Further, metallocene compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified.

The metallocene compounds as described above can be used alone or in combination of two or more. The metallocene compound as described above can be used by being supported on a particulate carrier.

Examples of such a particulate carrier include Si
O ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, T
inorganic carriers such as iO ₂ , ZnO, SnO ₂ , BaO, and ThO, polyethylene, polypropylene, poly-1-butene,
Organic carriers such as poly-4-methyl-1-pentene and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

In the present invention, the above-mentioned metallocene catalyst is preferably used as the propylene-ethylene copolymer (ii) polymerization catalyst.

Next, a metallocene catalyst is formed.
(B): a compound that reacts with the transition metal M in the component (A) to form an ionic complex, that is, an ionized ionic compound, (C): an organoaluminum compound, and (D): aluminoxane (aluminum oxy compound) )
Will be described.

(B) Ionized Ionic Compound The ionized ionic compound is a compound that reacts with the transition metal M in the transition metal complex component (A) to form an ionic complex. Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds.

As the Lewis acid, a compound represented by BR ₃ (where R is a fluorine atom, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group or a fluorine atom). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
And tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

As a borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (II
And salts of metal borane anions such as I).

As the carborane compound, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Salts of metal carborane anions such as nickelate (IV) are exemplified.

The ionized ionic compound as described above is
They can be used alone or in combination of two or more.
The organic aluminum oxy compound or the ionized ionic compound can be used by being supported on the above-mentioned particulate carrier.

In forming the catalyst, the following organic aluminum compound (C) may be used together with the organic aluminum oxy compound or the ionized ionic compound.

(C) Organoaluminum Compound As the organoaluminum compound, a compound having at least one Al-carbon bond in a molecule can be used. Examples of such a compound include an organoaluminum compound represented by the following general formula.

(R ¹ ) mAl (O (R ² )) nHpXq (wherein R ¹ and R ² may be the same or different and usually have 1 to 15, preferably 1 to 4 carbon atoms.
X represents a halogen atom, and m represents 0
<M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
A number satisfying q <3, and m + n + p + q = 3
It is. )

(D) Organoaluminum oxy compound (A
( Luminoxane) The organic aluminum oxy compound (D) may be a conventionally known aluminoxane.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-7.

The conventionally known aluminoxane (alumoxane) is specifically represented by the following general formula.

Embedded image

In the above formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, particularly preferably a methyl group. m
Is an integer of 2 or more, preferably an integer of 5 to 40.

Here, the aluminoxane has the formula (OAl
An alkyloxyaluminum unit represented by (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) (where R ¹ and R ² are the same hydrocarbon groups as R; R ¹ and R ² represent different groups.)
May be formed from a mixed alkyloxyaluminum unit consisting of

The organoaluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. In the present invention, as the catalyst (olefin-based catalyst) for producing the propylene-ethylene copolymer (ii), the above-mentioned metallocene-based catalyst is preferably used. In some cases, other than the above-mentioned metallocene-based catalyst, Conventionally known titanium catalysts comprising a solid titanium catalyst component and an organoaluminum compound, and vanadium catalysts comprising a soluble vanadium compound and an organoaluminum compound can also be used.

In the present invention, propylene, ethylene and the like are usually copolymerized in a liquid phase in the presence of the above-mentioned metallocene catalyst. In this case, a hydrocarbon solvent is generally used, but propylene may be used as the solvent. The copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the concentration of the metallocene compound in the polymerization system is usually 0.00005 per liter of polymerization volume.
-1 mmol, preferably 0.0001-0.5 mmol.

The organoaluminum oxy compound has a molar ratio (Al / M) of aluminum atom (Al) to transition metal atom (M) in the metallocene compound of 1 to 1000.
It is used in such an amount that it becomes 0, preferably 10-5000.

The ionized ionic compound has a molar ratio of the ionized ionic compound to the metallocene compound (ionized ionic compound / metallocene compound) of 0.5 to 2
It is used in an amount such that it becomes 0, preferably 1 to 10.

When an organoaluminum compound is used, it is used in an amount of usually about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

In the copolymerization reaction, the temperature is usually -20 to 15
0 ° C, preferably 0 to 120 ° C, more preferably 0 to
In the range of 100 ° C., the pressure exceeds 0 and is ~ 80 kg / cm
² , preferably above 0 and up to 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 10 minutes. 1.5 hours.

The above-mentioned propylene and ethylene monomers for copolymerization are supplied to the polymerization system in such amounts that the syndiotactic propylene-ethylene copolymer (ii) having the specific composition as described above is obtained. At the time of copolymerization, a molecular weight regulator such as hydrogen can be used.

When the monomer for copolymerizing propylene and ethylene is copolymerized as described above, the propylene-ethylene copolymer (ii) having a syndiotactic structure is usually obtained as a polymerization solution containing the copolymer. This polymerization solution is treated by a conventional method to obtain a propylene-ethylene copolymer (ii) having a syndiotactic structure.

The flexible polypropylene composition according to the present invention contains the propylene random copolymer (i) and the syndiotactic propylene-ethylene copolymer (ii). , (Ii) is 90/10 to 10/90, preferably 80/20 to 20/80. Since (i) and (ii) are contained at such a ratio, the resulting polypropylene-based composition tends to be excellent in flexibility, impact resistance, heat sealability, and transparency.

A molded article made of such a soft polypropylene composition has a melt flow rate (according to ASTM D 1238, 230 ° C., load 2.16 kg) of usually 0.0001 to 10
00 g / 10 min, preferably 0.0001 to 900 g /
10 minutes, more preferably 0.0001 to 800 g / 1
0 minutes, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g, more preferably 0.1 to 1 dl / g.
0 dl / g.

The soft polypropylene composition has a melt tension (MT) of usually 0.5 to 10 g, preferably 1 to 10 g, and is excellent in moldability such as film moldability. The melt tension (MT) is taken at a constant speed (10 m / min) by a melt tension tester [manufactured by Toyo Seiki Seisakusho] at a constant speed (10 m / min) at a measurement temperature of 200 ° C. and an extrusion speed of 15 mm / min. In this case, it was determined as the tension applied to the filament.

Further, a preferred soft polypropylene composition according to the present invention comprises the propylene random copolymer (i) and the syndiotactic propylene copolymer.
A ratio of the ethylene copolymer (ii) to the weight ratio of the above (i) and (ii) {(i) / (ii)} of 90/10 to 10/90, preferably 80/20 to 20/80. And a crystal nucleating agent (iii). next,
The nucleating agent (iii) blended in the composition will be described.

<Crystal nucleating agent (iii)> As the crystal nucleating agent (iii), various conventionally known nucleating agents can be used without any particular limitation. Among them, nucleating agents represented by the following formulas can be exemplified as preferred nucleating agents.

[0122]

Embedded image (Wherein, R ¹ is oxygen, sulfur, or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are hydrogen or a carbon group having 1 to 10 carbon atoms.
10 is a hydrocarbon group, R ^2, R ³ may be heterologous be homologous, it may be made R ² together, by bonding R ³ together or R ² and R ³ an annular , M is a metal atom having a valence of 1 to 3, and n is an integer of 1 to 3. )

Specifically, sodium-2,2'-methylene-
Bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene- Screw-
(4,6-di-t-butylphenyl) phosphate, lithium
-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i
-Propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4
-Ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis ( 4-ethyl-6-t-butylphenyl) phosphate]
, Calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4,6-di-t-butylphenyl) Phosphate], magnesium-bis [2,2'-thiobis- (4-t-
Octylphenyl) phosphate], sodium-2,
2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-
Bis (4,6-di-t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2 ,
2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6
-Di-t-butylphenyl) phosphate], sodium
-2,2'-methylene-bis (4-methyl-6-t-butylphenyl)
Phosphate, sodium-2,2'-methylene-bis (4-
Ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4 '-Dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-
6-t-butylphenyl) phosphate, sodium-2,
2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene -Bis (4,6-di-t-butylphenyl) phosphate,
Calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) )
Phosphate], barium-bis [2,2'-ethylidene-
Bis (4,6-di-t-butylphenyl) phosphate],
Aluminum-tris [2,2'-methylene-bis (4,6-di-t-
Butylfel) phosphate] and aluminum-
Tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof can be exemplified.

[0124]

Embedded image (Wherein R ⁴ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a metal atom having 1 to 3 valences, and n is 1 to 3)
It is an integer of 3. )

Specifically, sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-butylphenyl) phosphate
Ethylphenyl) phosphate, sodium-bis (4
-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate, potassium
-Bis (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butyl) Phenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and mixtures of two or more thereof can be exemplified.

[0126]

Embedded image (In the formula, R ⁵ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.)

More specifically, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene Sorbitol, 1,3-p-methylbenzylidene-2,4
-Benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3
-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol 1,3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (2 ', 4' -Dimethylbenzylidene)
Sorbitol, 1,3,2,4-di (p-methoxybenzylidene)
Sorbitol, 1,3,2,4-di (p-ethoxybenzylidene)
Sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-
Benzylidene sorbitol, 1,3-p-chlorobenzylidene
-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1 , 3-p-ethylbenzylidene-2,4-p-
Chlorbenzylidene sorbitol and 1,3,2,4-di (p-
Chlorbenzylidene) sorbitol and mixtures of two or more thereof, especially 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3, 2,4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and the like A mixture of two or more of the above is preferred.

Examples of other nucleating agents include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids.
Examples thereof include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate.

The soft polypropylene-based composition containing the nucleating agent (iii) according to the present invention comprises the above-mentioned propylene-based random copolymer (i) and the above-mentioned syndiotactic propylene-ethylene copolymer (ii). And
The weight ratio {(i) / (ii)} between (i) and (ii) is 90/10 to 10/90, preferably 80/20 to 20.
/ 80 of a composition having a total amount of (i) and (ii) of 10
0.05 to 1 part by weight of the above crystal nucleating agent (iii)
Parts by weight, preferably 0.05 to 0.5 parts by weight. Since the crystal nucleating agent (iii) is further contained in the above amount in addition to the above ratios (i) and (ii), the obtained soft polypropylene-based composition has flexibility, heat sealability, and impact resistance. In addition to excellent transparency, there is a tendency that transparency is particularly excellent.

A molded article made of such a soft polypropylene composition has a melt flow rate (according to ASTM D 1238, 230 ° C., load 2.16 kg) of usually 0.0001 to 10
00 g / 10 min, preferably 0.0001 to 900 g /
10 minutes, more preferably 0.0001 to 800 g / 1
0 minutes, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g, more preferably 0.1 to 1 dl / g.
0 dl / g. The melt tension (MT) of the polypropylene composition is usually 0.5 to 10 g,
It is preferably 1 to 10 g, and is excellent in moldability such as film moldability.

[Production of flexible polypropylene-based composition] The above-mentioned polypropylene-based composition can be prepared by mixing each component with various known methods within the above ranges, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender and the like. Or after mixing, melt kneading with a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, or the like, and then granulating or pulverizing.

The polypropylene-based composition contains a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a pigment, a dye, a rust inhibitor, and other copolymers (elastomer and the like) described in detail below. It can be blended within a range that does not impair the purpose of the present invention.

<Other Copolymers> In the flexible polypropylene composition according to the present invention, if necessary, "other copolymers" (including elastomers and resins for elastomers).
May be included. Examples of such “other copolymers” include an ethylene / α-olefin random copolymer [A], an optionally hydrogenated aromatic hydrocarbon block copolymer [B], and an ethylene / α-olefin. Examples include an olefin block copolymer [C], an ethylene / styrene copolymer [D], an ethylene / diene copolymer [E], and an ethylene / triene copolymer [F]. These copolymers are used alone or in combination of two or more.

These "other copolymers" are used in a total of 100 parts by weight of the propylene random copolymer (i) and the propylene-ethylene copolymer (ii) contained in the polypropylene composition of the present invention. On the other hand, it may be contained usually in an amount of 0 to 40 parts by weight. These “other copolymers” may be contained in the polypropylene composition in a total amount of usually 0 to 30% by weight. When the other copolymer is used in the above-mentioned amount, a composition capable of producing a molded article having an excellent balance of flexibility, hardness, transparency, and impact resistance is obtained.

Ethylene / α-olefin random copolymer
Body [A] The ethylene / α-olefin random copolymer [A] optionally used in the present invention has a density of 0.86.
0 g / cm ³ or more 0.895 g / cm less than ^3, preferably a 0.860~0.890g / cm ^3, a melt flow rate (MFR; ASTM D 1238-compliant, 190 ° C., a load 2.
16 kg) for 0.5 to 30 g / 10 min, preferably 1 to 20
A soft ethylene / α-olefin copolymer having a g / 10 minutes is desirable.

The α-olefin to be copolymerized with ethylene is an α-olefin having 3 to 20 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, -Octene, 1-nonene, 1-decene, 1-
Undecene, 1-dodecene, 1-hexadedecene, 1-octadecene, 1-nonadecene, 1-eicosene, 4-methyl-1-pentene and the like. Among them, α-olefins having 3 to 10 carbon atoms are preferable. These α-olefins are used alone or in combination of two or more.

The ethylene / α-olefin random copolymer [A] contains 60 to 90 mol% of units derived from ethylene and 10 to 40 units of α-olefin having 3 to 20 carbon atoms. Desirably, it is contained in an amount of mol%.

The ethylene / α-olefin random copolymer [A] contains, besides these units, units derived from other polymerizable monomers as long as the object of the present invention is not impaired. Is also good.

Examples of such other polymerizable monomers include:
For example, vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane;
Vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; conjugated dienes such as butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene , 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-
Methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-
Norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3 -Isopropylidene
And non-conjugated polyenes such as -5-norbornene and 2-propenyl-2,2-norbornadiene.

The ethylene / α-olefin random copolymer [A] contains units derived from such other polymerizable monomers in an amount of 10 mol% or less, preferably 5 mol% or less.
More preferably, it may be contained in an amount of 3 mol% or less.

As the ethylene / α-olefin random copolymer [A], specifically, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / propylene / 1-butene random copolymer Polymers include ethylene / propylene / ethylidene norbornene random copolymer, ethylene / 1-hexene random copolymer, ethylene / 1-octene random copolymer and the like. Among these, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer,
Ethylene / 1-hexene random copolymer, ethylene / 1-
Octene random copolymers and the like are particularly preferably used. Two or more of these copolymers may be used in combination.

Further, the ethylene / α-
The olefin random copolymer [A] generally has a crystallinity of 40% or less, preferably 0%, as measured by X-ray diffraction.
To 39%, more preferably 0 to 35%.

The ethylene / α-olefin random copolymer as described above can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst.

The ethylene / α-olefin random copolymer [A] is usually contained in the polypropylene composition in an amount of from 0 to 4%.
It may be present in an amount of 0% by weight, preferably 0-35% by weight. When the ethylene / α-olefin random copolymer [A] is used in the above amount, a composition that can prepare a molded article having an excellent balance of flexibility, hardness, transparency, and impact resistance is obtained.

Aromatic hydrocarbons which may be hydrogenated
Lock copolymer [B] The optionally hydrogenated aromatic hydrocarbon-based block copolymer [B] used as an elastomer in the present invention is a block polymer unit (X) derived from aromatic vinyl. ) And a block polymerized unit (Y) derived from a conjugated diene, and an aromatic vinyl / conjugated diene block copolymer [B1] and a hydrogenated product [B2] thereof.

The form of the aromatic vinyl / conjugated diene block copolymer [B1] having such a structure is, for example, X (Y
X) n or (XY) n [n is an integer of 1 or more]. Among these, a block copolymer in the form of X (YX) n, particularly XYX is preferred, and specifically, in the form of polystyrene-polybutadiene (or polyisoprene or polyisoprene-butadiene) -polystyrene. Styrene block copolymers are preferred.

In such a styrene-based block copolymer, the aromatic vinyl block polymerization unit (X), which is a hard segment, exists as a bridge point of the conjugated diene block polymerization unit (Y) to form a physical crosslink (domain). Has formed. The conjugated diene block polymerization unit (Y) existing between the aromatic vinyl block polymerization units (X) is a soft segment and has rubber elasticity.

Specific examples of the aromatic vinyl forming the block polymerized unit (X) include styrene, α-methylstyrene, 3-methylstyrene, p-methylstyrene, and 4-propylstyrene. And styrene derivatives such as 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, and 4- (phenylbutyl) styrene. Of these, styrene is preferred.

The conjugated diene forming the block polymerized unit (Y) includes butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene and a combination thereof. Of these, butadiene or isoprene or a combination of butadiene and isoprene is preferred.

When the conjugated diene block polymerization unit (Y) is derived from butadiene and isoprene, the unit preferably contains the unit derived from isoprene in an amount of 40 mol% or more.

The conjugated diene block polymerization unit (Y) comprising butadiene / isoprene copolymerization unit
Is a random copolymerized unit of butadiene and isoprene,
It may be either a block copolymer unit or a tapered copolymer unit.

The aromatic vinyl / conjugated diene block copolymer [B1] has an aromatic vinyl block polymerized unit (X) content of 22% by weight or less, preferably 5 to 22% by weight. . The content of the aromatic vinyl polymerized unit can be measured by a conventional method such as infrared spectroscopy and NMR spectroscopy.

The melt flow rate of the aromatic vinyl / conjugated diene block copolymer [B1] (MFR; ASTM
D 1238 standard, 200 ° C, load 2.16kg) is usually 5g / 10
Min., And preferably 5 to 100 g / 10 min.

Various methods can be used for producing the above-mentioned aromatic vinyl / conjugated diene block copolymer [B1]. For example, (1) an alkyllithium compound such as n-butyllithium is used as an initiator. As a method of sequentially polymerizing an aromatic vinyl compound and then a conjugated diene, (2) a method of polymerizing an aromatic vinyl compound and then a conjugated diene, and coupling this with a coupling agent, and (3) using a lithium compound as an initiator. , A conjugated diene, and then a method of sequentially polymerizing an aromatic vinyl compound.

The hydrogenated aromatic vinyl / conjugated diene block copolymer [B2] is obtained by hydrogenating the above aromatic vinyl / conjugated diene block copolymer [B1] by a known method. Can be obtained by Hydrogenated aromatic vinyl / conjugated diene block copolymer [B2]
Usually has a hydrogenation rate of 90% or more.

This hydrogenation ratio is a value when the total amount of carbon-carbon double bonds in the conjugated diene block polymerization unit (Y) is 100%. Specific examples of the hydrogenated product [B2] of the aromatic vinyl / conjugated diene block copolymer include a hydrogenated product of a styrene / isoprene block copolymer (SEP) and a styrene / isoprene / styrene block copolymer. Hydrogenated polymer (SEPS; polystyrene / polyethylene / propylene / polystyrene block copolymer),
Hydrogenated styrene-butadiene block copolymer (SE
BS; polystyrene / polyethylene / butylene / polystyrene block copolymer) and the like. More specifically, HYBRAR [manufactured by Kuraray Co., Ltd.], Clayton [manufactured by Shell Chemical Co., Ltd.], Carifrex TR [shell chemical] Co., Ltd.], Solprene [Philippe Petro Rifum Co., Ltd.], Europrene SOLT [Aniche Co., Ltd.], Tufprene [Asahi Kasei Kogyo Co., Ltd.], Solprene-T [Nihon Elastomer Co., Ltd.], JSR-TR [Nihon Gosei Rubber Co., Ltd.], Electrification STR
And Quintac [manufactured by Zeon Corporation], Clayton G [manufactured by Shell Chemical Co., Ltd.], Tuftec [manufactured by Asahi Chemical Industry Co., Ltd.] (all trade names) and the like.

As the hydrogenated product [B2] of the aromatic vinyl / conjugated diene block copolymer, SEB
S and SEPS are preferably used. The aromatic hydrocarbon-based block copolymer [B] which may be hydrogenated may be contained in the polypropylene composition in an amount of usually 0 to 30% by weight, preferably 0 to 25% by weight. . Aromatic hydrocarbon block copolymer [B] which may be hydrogenated
Is used in an amount as described above, a composition which can prepare a molded article having an excellent balance of flexibility and hardness, transparency and impact resistance is obtained.

Ethylene / α-olefin block copolymer
Body [C] The ethylene / α-olefin block copolymer [C] optionally used as an elastomer in the present invention comprises 0 to 20 mol% of a structural unit derived from an olefin having 3 to 10 carbon atoms, Structural unit 1 derived from ethylene
A crystalline polyethylene portion consisting of 100 to 80 mol%;
It is composed of a low-crystalline copolymer part or an amorphous copolymer part containing two or more kinds of structural units derived from an olefin having 2 to 20 carbon atoms.

In the present invention, the constitutional unit derived from ethylene is contained in an amount of 30 to 95 mol%, and has 3 carbon atoms.
A structural unit derived from an olefin of from 20 to 70 to 5
An ethylene / α-olefin block copolymer contained in an amount of mol% is preferred. In particular, ethylene · α in which the constituent unit derived from ethylene is contained in an amount of 60 to 90 mol% and the constituent unit derived from an olefin having 3 to 20 carbon atoms is contained in an amount of 40 to 10 mol%. −
Olefin block copolymers are preferred.

The olefin having 3 to 20 carbon atoms specifically includes propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 3-methyl-1
-Pentene, 1-octene, 3-methyl-1-butene, 1-decene, 1-dodecene, 1-tetradodecene, 1-hexadecene,
1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a , 5,8,8a-octahydronaphthalene and the like.

The above-mentioned structural unit derived from an olefin having 3 to 20 carbon atoms or ethylene may contain two or more kinds. In addition, the ethylene / α-olefin block copolymer used in the present invention has 4 to 4 carbon atoms.
5 mol% of the structural unit derived from the diene compound of No. 20
It may be contained in the following amounts.

Examples of such a diene compound include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5- Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 6-methyl-1,6-octadiene, 7-
Methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7- Methyl-1,6
-Nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-
1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene,
Examples thereof include 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene.

Such an ethylene / α-olefin block copolymer [C] has a melt flow rate (MF
R; according to ASTM D 1238, 190 ° C, load 2.16 kg).
0001-500 g / 10 min, preferably 0.0001
~ 300 g / 10 min, more preferably 0.0001 ~
The density is in the range of 200 g / 10 min, and the density (according to ASTM D 1505) is 0.85 to 0.90 g / cm ³ , preferably 0.85 to 0.89 g / cm ³ , more preferably 0.1 to 0.89 g / cm ³ .
It is desirably 86 to 0.89 g / cm ³ .

The degree of crystallinity of the boiling heptane-insoluble component in the copolymer [C] measured by X-ray diffraction is usually 0 to 30%, preferably 0 to 28%, more preferably 0 to 25%. .

A boiling heptane-insoluble component of the ethylene / α-olefin block copolymer [C] is prepared as follows. That is, 3 g of a polymer sample, 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500 ml of n-decane were placed in a 1-liter flask equipped with a stirrer, and
Heat and dissolve on a 5 ° C. oil bath. After the polymer sample is dissolved, it is cooled to room temperature over about 8 hours, and then kept on a 23 ° C. water bath for 8 hours. An n-decane suspension containing the precipitated polymer (23 ° C. decane-insoluble component) was added to G-4 (or G-
After filtration and separation through a glass filter of 2) and drying under reduced pressure, 1.5 g of the polymer is subjected to Soxhlet extraction using heptane for 6 hours or more to obtain a boiling heptane-insoluble component.

The crystallinity is measured as follows using the boiling heptane-insoluble component obtained as described above as a sample. That is, a sample was formed into a square plate having a thickness of 1 mm by a pressure molding machine at 180 ° C., and immediately thereafter, measured using a press sheet obtained by cooling with water using a Rotaflex RU300 measuring device manufactured by Rigaku Corporation. (Output 50 kV, 250 mA). As a measuring method at this time, a transmission method is used, and the measurement is performed while rotating the sample.

The density of the boiling heptane-insoluble component of the ethylene / α-olefin block copolymer [C] used in the present invention is usually 0.86 g / cm ³ or more, preferably 0.1 g / cm ³ or more.
It is 87 g / cm ³ or more.

The ethylene / α-olefin block copolymer [C] had a n-decane soluble component at 23 ° C. of 0.1%.
To 99%, preferably 0.5 to 99%, more preferably 1 to 99%.

In the present invention, the amount of n-decane-soluble components at 23 ° C. of the ethylene / α-olefin block copolymer is measured as follows. That is, 3 g of the polymer sample and 2,6-di-tert-butyl-4 were placed in a 1-liter flask equipped with a stirrer.
-20 mg of methylphenol and 500 ml of n-decane are added and dissolved by heating on an oil bath at 145 ° C. After the polymer sample was dissolved, it was cooled to room temperature over about 8 hours, followed by 2 hours.
Hold on water bath at 3 ° C. for 8 hours. The precipitated polymer and an n-decane solution containing the dissolved polymer were subjected to G-4 (or G-
Filter and separate with the glass filter of 2). The solution thus obtained was heated under the conditions of 10 mmHg and 150 ° C., and dried until the polymer dissolved in the n-decane solution was quantified. .Alpha.-olefin block copolymer 23
The n-decane-soluble component at ° C is calculated as a percentage based on the weight of the polymer sample.

The ethylene used in the present invention is
The α-olefin block copolymer [C] can be prepared by a conventionally known method. The ethylene / α-olefin block copolymer [C] may be contained in the polypropylene composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight. When the ethylene / α-olefin block copolymer [C] is used in the above amount, a composition that can prepare a molded article having an excellent balance of flexibility, hardness, transparency, and impact resistance is obtained.

Ethylene / styrene-based copolymer [D] The ethylene-styrene-based copolymer [D] used as an elastomer as required in the present invention is a random copolymer of ethylene and styrene or a derivative thereof. .

Examples of the styrene or its derivative copolymerized with ethylene include, in addition to styrene, α
-Methylstyrene, 3-methylstyrene, p-methylstyrene, 4-propylstyrene, 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene,
Styrene derivatives such as 4- (phenylbutyl) styrene are exemplified. In the present invention, styrene is preferred.

The ethylene / styrene copolymer [D] is
It is desirable to contain units derived from ethylene in an amount of 5 to 99 mol% and units derived from styrene and / or styrene derivatives in an amount of 1 to 95 mol%.
The ethylene / styrene copolymer [D] may have one or more units derived from styrene or a derivative thereof.

The ethylene / styrene copolymer [D] is
The density is 0.85 to 1.02 g / cm ³ , preferably 0.1 to 1.0 g / cm ³ .
86 to 1.02 g / cm ³ , and a melt flow rate (MFR; according to ASTM D1238, 190 ° C., load 2.16 kg) of 0.001 to 500 g / 10 min, preferably 0.001
It is desirably 300 g / 10 min.

The crystallinity of the ethylene / styrene copolymer [D] measured by an X-ray diffraction method is usually 80% or less, preferably 0 to 75%, more preferably 0 to 70%. .

The ethylene / styrene copolymer [D] as described above can be prepared by a conventionally known method. The ethylene / styrene copolymer [D] may be contained in the polypropylene composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight. ethylene·
When the styrene-based copolymer [D] is used in the amount described above, a composition that can prepare a molded article having an excellent balance of flexibility, hardness, transparency, and impact resistance is obtained.

Ethylene / diene copolymer [E] The ethylene / diene copolymer [E] used as the elastomer in the present invention is a random copolymer of ethylene and diene.

As the diene to be copolymerized with ethylene,
Specific examples include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene; and conjugated dienes such as butadiene and isoprene. Of these, butadiene and isoprene are preferred. These dienes can be used alone or in combination of two or more.

In the ethylene-diene copolymer [E] used in the present invention, the content of the structural unit derived from diene is usually 0.1 to 30 mol%, preferably 0.1 to 30 mol%.
-20 mol%, more preferably 0.5-15 mol%. The iodine value is usually 1-1.
50, preferably 1 to 100, more preferably 1 to 5
Desirably, it is 0. The intrinsic viscosity [η] of the ethylene / diene copolymer [E] measured in decalin at 135 ° C. is 0.01 to 10 dl / g, preferably 0.0 to 10 dl / g.
5 to 10 dl / g, more preferably 0.1 to 10 dl
/ G is desirable. Such an ethylene / diene copolymer [E] can be prepared by a conventionally known method.

The ethylene / diene copolymer [E] may be contained in the polypropylene composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight. When the ethylene-diene copolymer [E] is used in the above amount, a composition that can prepare a molded article having an excellent balance of flexibility, hardness, transparency, and impact resistance is obtained.

Ethylene / triene copolymer [F] The ethylene / triene copolymer [F] used as the elastomer in the present invention is a random copolymer of ethylene and triene.

Specific examples of the triene to be copolymerized with ethylene include 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, -Dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1 , 5,9-Undecatriene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-
Octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND), 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7 -
Dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-
1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadiene, 8- Methyl
-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-
A non-conjugated triene such as undecadiene; a conjugated triene such as 1,3,5-hexatriene; These trienes can be used alone or in combination of two or more.

The above-mentioned triene is, for example, EP0
It can be prepared by a conventionally known method as described in JP 691354A1 and WO96 / 20150.

In the ethylene / triene copolymer [F] used in the present invention, the content of the structural unit derived from triene is usually 0.1 to 30 mol%, preferably 0.1 to 20 mol%, and more preferably 0.1 to 20 mol%. Preferably, it is in the range of 0.5 to 15 mol%. It is desirable that the iodine value is usually 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

The ethylene / triene copolymer [F]
The intrinsic viscosity [η] measured in decalin at 135 ° C. is
0.01 to 10 dl / g, preferably 0.05 to 10 d
1 / g, more preferably in the range of 0.1 to 10 dl / g.

The ethylene / triene copolymer [F] as described above can be prepared by a conventionally known method. The ethylene / triene copolymer [F] is contained in the polypropylene composition in an amount of usually 0 to 40% by weight, preferably 0 to 40% by weight.
May be present in amounts of up to 35% by weight. When the ethylene / triene copolymer [F] is used in the above amount, a composition that can prepare a molded article having an excellent balance of flexibility, hardness, transparency, and impact resistance is obtained.

<Molded Article> The above-mentioned polypropylene-based composition according to the present invention can be widely used for conventionally known polyolefin applications. In particular, the polyolefin composition can be used, for example, in the form of a sheet, unstretched or stretched film, filament, It can be used after being molded into molded articles of other various shapes.

Specific examples of the molded article include known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. And a molded article obtained by the above method. The molded product will be described below with reference to several examples.

When the molded article according to the present invention is, for example, an extruded molded article, its shape and product type are not particularly limited, but for example, sheets, films (unstretched), pipes,
Examples include hoses, wire coatings, and filaments, and particularly preferred are sheets, films, and filaments.

When extruding the soft composition, a conventionally known extruder and molding conditions can be employed. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like can be used. The molten syndiotactic polypropylene composition can be extruded from a T-die or the like to form a sheet or film (unstretched).

The stretched film is prepared by subjecting the extruded sheet or the extruded film (unstretched) as described above to a known stretching method such as a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method and a uniaxial stretching method. It can be obtained by stretching.

The stretching ratio when stretching a sheet or an unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 μm by stretching. In addition, an inflation film can be produced as a film-shaped molded product. Drawdown hardly occurs during inflation molding.

The above-mentioned sheet and film formed from the polypropylene composition according to the present invention are hardly charged, and have flexibility, heat resistance, heat sealability, impact resistance, aging resistance, transparency and transparency. It has excellent properties, gloss, moisture-proof properties and gas barrier properties, and can be widely used as a packaging film. Especially because it has excellent moisture resistance,
It is suitably used for a press through pack used for packaging tablets, capsules and the like of chemicals.

The filament molded article can be produced, for example, by extruding a molten polypropylene composition through a spinneret. The filament thus obtained may be further drawn. This stretching may be carried out so that at least the uniaxial direction of the filament is molecularly oriented, and is usually desirably performed at a magnification of about 5 to 10 times. The filament made of the polypropylene composition according to the present invention is hardly charged, and is excellent in transparency, heat resistance and impact resistance.

An injection molded article can be produced by injection molding a polypropylene composition into various shapes using a conventionally known injection molding apparatus under known conditions. The injection molded article comprising the polypropylene composition according to the present invention is hardly charged, and has flexibility, heat resistance, impact resistance, surface gloss,
It is excellent in chemical resistance, abrasion resistance and the like, and can be widely used in trim materials for automobile interiors, exterior materials for automobiles, housings and containers of home electric appliances and the like.

The blow molded article can be produced by blow molding a polypropylene composition using a conventionally known blow molding apparatus under known conditions.

For example, in extrusion blow molding, the above-mentioned polypropylene composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is held in a mold having a desired shape. Afterward, air is blown into the mold at a resin temperature of 130 ° C to 300 ° C, whereby a hollow molded body can be manufactured.
The stretching (blow) magnification is desirably about 1.5 to 5 times in the lateral direction.

In the injection blow molding, the above-mentioned polypropylene-based composition is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison. Is blown into the mold at a resin temperature of 120 ° C. to 300 ° C. to produce a hollow molded body. The stretching (blow) magnification is 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.2 in the lateral direction.
Preferably, it is 5 times.

The blow-molded article made of the flexible polypropylene composition according to the present invention is excellent in transparency, flexibility, heat resistance and impact resistance, and also excellent in moisture resistance.

Examples of the press-molded body include a mold stamping-molded body. For example, the base material and the skin material are simultaneously press-formed and the base material of the present invention is subjected to composite integrated molding (mold stamping molding) according to the present invention. It can be formed of a polypropylene-based composition.

Specific examples of such a mold stamping molded body include automotive interior materials such as door trim, rear package trim, seat back garnish, and instrument panel.

The flexible polypropylene-based composition according to the present invention exhibits high rigidity, for example, shows a sufficiently high rigidity even if it contains an elastomer component, and can be used for various high rigidity applications. For example, automotive interior and exterior materials,
It can be suitably used for applications such as housing of home appliances and various containers.

The press-formed product made of the soft polypropylene composition according to the present invention is hardly charged, and has flexibility, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, and abrasion resistance. And so on.

The flexible polypropylene composition of the present invention comprises:
It can be used mainly for the following applications. Film: Multilayer stretched film, multilayer unstretched film, laminate film, shrink film, stretch film, wrap film, protect film, retort film, porous film, barrier film, metallized film, agricultural film; sheet and sheet molded product: Wallpaper, foam sheet, electric wire covering, blister packaging, tray, stationery, food containers, toys,
Cosmetic containers, medical instruments, washing containers, flooring, cushion floors, decorative sheets, shoe soles; Blow products: Bottles; Extruded products: Tubes, wire coatings, cable coatings, pipes, gaskets; Fibers: Fibers, flat yarns; Non-woven fabric products: Non-woven fabrics, filters; Injection products: Automotive interior skin materials, automotive exterior materials, daily necessities, home appliances, caps, containers, pallets; Modifiers: adhesives, adhesives, lubricant additives, hot melts Adhesives, toner release agents, pigments, dispersants, asphalt modifiers; others: sealants, vacuum formed bodies, powder slush bodies.

[0205]

According to the present invention, there can be obtained a polypropylene composition capable of obtaining a molded article excellent in flexibility, impact resistance, heat sealability, transparency, heat resistance, scratch resistance and the like in a well-balanced manner. .

[0206]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The physical property test conditions are described below. 1. Tensile modulus According to JIS K6301, a JIS No. 3 dumbbell was used to measure at 23 ° C. at a span interval of 30 mm and a tensile speed of 30 mm / min. 2. Heat sealability <Heat seal strength (HST) (g /
15mm width)> Using a cast film molding machine, cylinder temperature 23
0 ° C, chill roll temperature 20 ° C, screw rotation speed 80rp
A test film having a width of 250 mm and a thickness of 50 μm was prepared under the conditions of m, and measured at a heat seal pressure of 2 kg / cm ² , a heat seal temperature of 120 ° C., a heat seal time of 1 sec, and a pulling speed of 300 mm / min. did. 3. Film impact strength (J / m) Cylinder temperature 23
0 ° C, chill roll temperature 20 ° C, screw rotation speed 80rp
Under a condition of m, a test film having a width of 250 mm and a thickness of 50 μm was prepared, and the film impact strength at 0 ° C. was measured according to ASTM D3420. 4. Haze (%) Using a cast film molding machine, cylinder temperature 23
0 ° C, chill roll temperature 20 ° C, screw rotation speed 80rp
Under the condition of m, a test film having a width of 250 mm and a thickness of 50 μm was prepared, and a digital turbidimeter “ND” manufactured by Nippon Denshoku Industries Co., Ltd.
H-20D ". (Based on ASTM D1003)

5. Melting point (Tm), glass transition temperature (T
g) and crystallinity Using a DSC (differential scanning calorimeter), the sample was packed in an aluminum pan, and heated to 200 ° C at 100 ° C / min.
, And the temperature was lowered to -150 ° C at 10 ° C / min., And then an endothermic curve when the temperature was raised at 10 ° C / min was determined. The temperature at the maximum peak position was defined as Tm. In addition, when the baseline inflected, the intersection of the initial baseline and the inflection point was defined as Tg. The heat of fusion per unit weight is determined from the endothermic peak at the time of DSC measurement, and this is divided by the heat of fusion of crystal of polyethylene 70 cal / g to obtain the degree of crystallinity (%).
I asked. 6. Intrinsic viscosity [η] Measured in decalin at 135 ° C. 7. Measurement was performed at 140 ° C. using an Mw / Mn GPC (gel permeation chromatography) in an orthodichlorobenzene solvent.

(Synthesis Example 1) <Synthesis of Propylene-based Random Copolymer (i)> In a 200-liter polymerization vessel equipped with stirring fins sufficiently purged with nitrogen, 80 liters of hexane and 80 mmol of triisobutylaluminum were added. After charging 0.25 liters of hydrogen, 9 kg of ethylene and 0.3 kg of propylene, and heating to 70 ° C., 18 mmol of methylaluminoxane, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride Was converted to Zr atoms and 0.06 mmol was added, and propylene and ethylene were fed at 13.7 kg and 0.5 kg, respectively. After polymerization,
Degas and recover the polymer in a large amount of methanol, 80
It dried under reduced pressure at 10 degreeC for 10 hours.

The obtained polymer was 7.0 kg, and the polymerization activity was 117 kg · polymer / mmol Zr · hr. This polymer has a molecular weight distribution Mw / Mn of 2.
0, ethylene constituent unit is 4.7 mol%, intrinsic viscosity [η]
Is 2.7 dl / g, melting point is 123 ° C, propylene tri
The value of microisotacticity observed in ad chain 0.9
It was 7.

(Synthesis Example 2) <Synthesis of Syndiotactic Propylene-Ethylene Copolymer (iia)>
In a 5 liter autoclave, add 75 heptane at room temperature.
Then, a 1.0 mmol / ml-toluene solution of triisobutylaluminum (hereinafter abbreviated as TIBA) in toluene was converted to an aluminum atom to have an amount of 0.3 ml.
0.3 ml was added so as to obtain a mmol, and 50.7 liter (25 ° C., 1 atm) of propylene was inserted with stirring, and the temperature was raised to 30 ° C. Thereafter, the system was pressurized with ethylene to 5.5 kg / cm ² G, and a diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride heptane solution (0.0002 mM / ml) synthesized by a known method. 3.75 ml of a toluene solution of triphenylcarbenium tetra (pentafluorophenyl) borate (0.002 mM / ml)
Was added to initiate copolymerization of propylene and ethylene. The catalyst concentration at this time was 0.001 mmol / liter of diphenylmethylene (cyclopentadienyl) fluorenyl zirconium dichloride with respect to the whole system.
Triphenylcarbenium tetra (pentafluorophenyl) borate was 0.004 mmol / l.

During polymerization, the internal pressure was maintained at 5.5 kg / cm ² G by continuously supplying ethylene. Thirty minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out, and the polymer solution was washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1. Transferred to the aqueous phase. After the catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the polymerization liquid phase separated from the oil and water was brought into contact with three times the volume of acetone under vigorous stirring to precipitate a polymer, which was then sufficiently washed with acetone, and a solid part (copolymer) was collected by filtration. 130 ° C, 350mmH under nitrogen flow
g for 12 hours. The yield of the propylene / ethylene copolymer obtained as described above was 50 g,
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 2.4 dl.
/ G, the glass transition temperature Tg was -28 ° C, the ethylene constitutional unit was 24.0 mol%, and the molecular weight distribution (Mw / Mn) measured by GPC was 2.9.
Further, under the above-mentioned DSC measurement conditions, a melting peak was not substantially observed.

(Synthesis Example 3) <Synthesis of Syndiotactic Propylene-Ethylene Copolymer (iib)>
° C, ethylene pressure 7 kg / cm ² G, polymerization time 15
The same operation as in Synthesis Example 2 was performed except that the amount was changed. The yield of the obtained propylene / ethylene copolymer was 33 g.
And the intrinsic viscosity [η] measured in 135 ° C. decalin
Is 2.0 dl / g, and the glass transition temperature Tg is −5.
4 ° C., ethylene content 45 mol%, GP
The molecular weight distribution by C was 2.9. In addition, the aforementioned D
Under the SC measurement conditions, substantially no melting peak was observed.

Example 1 70 parts by weight of the propylene random copolymer obtained in Synthesis Example 1 and 30 parts by weight of the syndiotactic propylene / ethylene copolymer obtained in Synthesis Example 2 were kneaded. Thus, a soft polypropylene composition was obtained. Table 2 shows the measurement results of the physical properties of this composition.

(Example 2) In Example 1, Synthesis Example 2
A soft polypropylene-based composition was prepared in the same manner as in Example 1 except that the syndiotactic propylene / ethylene copolymer obtained in the above was replaced with the syndiotactic propylene / ethylene copolymer obtained in Synthesis Example 3. Obtained. Table 2 shows the measurement results of the physical properties of this composition.

(Comparative Example 1) Synthesis Example 2 in Example 1
The syndiotactic propylene / ethylene copolymer obtained in the above was used as an isotactic propylene / ethylene copolymer (iv) (intrinsic viscosity [η]: 2.0 dl / g, melting point Tm: 76 ° C., glass transition temperature Tg). : -32 ° C, ethylene constituent unit: 23 mol%, molecular weight distribution M by GPC
A soft polypropylene-based composition was obtained in the same manner as in Example 1 except that w / Mn: 2.1) was used. Table 2 shows the measurement results of the physical properties of this composition.

Example 3 Total amount of 70 parts by weight of the propylene random copolymer obtained in Synthesis Example 1 and 30 parts by weight of the syndiotactic propylene / ethylene copolymer obtained in Synthesis Example 2 Was added and melt-kneaded to obtain a soft polypropylene-based composition. Table 2 shows the measurement results of the physical properties of this composition.

Example 4 Synthesis Example 2 in Example 3
A soft polypropylene-based composition was prepared in the same manner as in Example 1 except that the syndiotactic propylene / ethylene copolymer obtained in the above was replaced with the syndiotactic propylene / ethylene copolymer obtained in Synthesis Example 3. Obtained. Table 2 shows the measurement results of the physical properties of this composition.

[0219]

[Table 2]

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Claims (6)

[Claims] (I) a structural unit (a) derived from propylene, a structural unit (b) derived from ethylene, and, if necessary, a structural unit (c) derived from an α-olefin having 4 to 20 carbon atoms; ), Wherein the structural unit (a) derived from propylene is 9
0 to 99 mol%, 0.5 to 9 mol% of a structural unit (b) derived from ethylene, and 0 to 9.5 mol% of a structural unit (c) derived from an α-olefin having 4 to 20 carbon atoms. A propylene-based random copolymer having an intrinsic viscosity [η] in the range of 0.5 to 6 dl / g as measured in decalin at 135 ° C., and (ii) having a substantially syndiotactic structure. And a syndiotactic propylene-ethylene copolymer containing 99 to 50 mol% of a structural unit derived from propylene and 1 to 50 mol% of a structural unit derived from ethylene. Weight ratio of coalesced (i) to propylene-ethylene copolymer (ii) {(i) / (ii)}
Is 90/10 to 10/90. (I) a structural unit (a) derived from propylene, a structural unit (b) derived from ethylene, and, if necessary, a structural unit (c) derived from an α-olefin having 4 to 20 carbon atoms; ), Wherein the structural unit (a) derived from propylene is 9
0 to 99 mol%, 0.5 to 9 mol% of a structural unit (b) derived from ethylene, and 0 to 9.5 mol% of a structural unit (c) derived from an α-olefin having 4 to 20 carbon atoms. A propylene-based random copolymer having an intrinsic viscosity [η] in the range of 0.5 to 6 dl / g as measured in decalin at 135 ° C., and (ii) having a substantially syndiotactic structure. And a syndiotactic propylene-ethylene copolymer containing 99-50 mol% of a structural unit derived from propylene and 1-50 mol% of a structural unit derived from ethylene, and a propylene-based random copolymer. Weight ratio of (i) to propylene-ethylene copolymer (ii) {(i) / (ii)}
Is a soft polypropylene-based composition characterized by comprising 0.05 to 1 part by weight of a crystal nucleating agent (iii) based on 100 parts by weight of a composition of 90/10 to 10/90. 3. The flexible polypropylene-based composition according to claim 2, wherein the nucleating agent is a sorbitol-based nucleating agent. 4. In the propylene random copolymer (i), the melting point (Tm) measured by a differential scanning calorimeter is 70 <Tm <155-5.5 (100-P). P is the content of propylene-derived constituent units (mol%) in the copolymer) and the value of microisotacticity in the propylene triad chain is in the range of 0.8 or more. The flexible polypropylene-based composition according to any one of claims 1 to 3, characterized in that: 5. The propylene-ethylene copolymer (i)
i) shows that the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g, and GPC
The molecular weight distribution (the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, Mw / Mn) is 4 or less and the glass transition temperature (Tg) is -15 ° C or less. 5. The soft polypropylene-based composition according to any one of items 4 to 4. 6. The propylene-ethylene copolymer (i)
i) is obtained in the presence of a catalyst comprising the following component (A) and at least one compound selected from the group consisting of the following components (B), (C) and (D): A flexible polypropylene-based composition according to any one of claims 1 to 5, characterized in that: (A): a transition metal complex represented by the following formula (I) or (II): [In the above formulas (I) and (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru atoms, Cp ¹ and C
p ² is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or a neutral Lewis base ligand , Y is a ligand containing a nitrogen, oxygen, phosphorus or sulfur atom, and Z is C, O, B, S, G
e, Si or Sn atoms or groups containing these atoms. (B): a compound which reacts with the transition metal M in the component (A) to form an ionic complex, (C): an organoaluminum compound, and (D): an aluminoxane.