JPH11293062A - Polypropylene resin composition and non-stretched film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for films excellent in transparency and low temperature heat sealing properties by mixing a polypropylene resin, an ethylene/α-olefin random copolymer and a propylene/ethylene/1-butene random copolymer, each in a specific amount. SOLUTION: There is provided a resin composition comprising 50-95 pts.wt. of at least one polypropylene resin selected from a propylene homopolymer, a propylene/α-olefin random copolymer containing not more than 10 mole % of other α-olefin units and a propylene/α-olefin block copolymer having an n-decane extract content of not more than 10 wt.%; 3-40 pts.wt. of an ethylene/α- olefin random copolymer comprising 60-95 mole % of ethylene units and having a density of not more than 0.900 g/cm<3> and an MFR of 0.1-50 g/10 min; and 2-20 pts.wt. of a propylene/ethylene/1-butene random copolymer comprising 50-88 mole % of propylene units, 2-30 mole % of ethylene units and 10-40 mole % of 1-butene units and having an MFR of 0.1-50 g/10 min, the three ingredients making up to 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition and a non-stretched film comprising the composition, and more particularly, to a polypropylene resin, a specific ethylene / α-olefin random copolymer, and a specific The present invention relates to a polypropylene resin composition containing an ethylene / 1-butene random copolymer, and a non-stretched film comprising the composition.

[0002]

2. Description of the Related Art Polypropylene resin films are excellent in mechanical properties such as tensile strength and rigidity, optical properties such as gloss and transparency, and are also excellent in food hygiene in terms of non-toxicity and odorlessness. Widely used in the field of food packaging. In this case, a film made of only a polypropylene resin is inferior in impact resistance and has a high heat sealing temperature, so that a rubber-like substance such as an ethylene-propylene copolymer or an ethylene-butene copolymer is added. .

[0003] The addition of a rubber-like substance improves the impact resistance of a polypropylene resin film and lowers the heat sealing temperature, but has the disadvantage of lowering the transparency and heat seal strength of the polypropylene resin film.

[0004]

An object of the present invention is to provide a polypropylene resin composition for an unstretched film capable of providing an unstretched film having excellent transparency, impact resistance, low-temperature heat sealability, and heat seal strength. To provide. Another object of the present invention is to provide a non-stretched film excellent in transparency, impact resistance, low-temperature heat sealability, and heat seal strength.

[0005]

The present invention provides the following polypropylene resin composition for an unstretched film, and an unstretched film. (1) (A) 50 to 95 parts by weight of a polypropylene resin,
(B) an ethylene unit content of 60 to 95 mol%, a density of 0.900 g / cm ³ or less, and an MFR
(ASTM D-1238, 190 ° C, 2.16 kg load) is 0.1 to 50 g / 10 min, and the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3 or less. 3 to 40 parts by weight of an ethylene / α-olefin random copolymer (here, the α-olefin has 3 or more carbon atoms) and (C) propylene / ethylene / 1 satisfying the following conditions 1) to 3) -2 to 20 parts by weight of a butene random copolymer (where the total amount of (A), (B) and (C) is 10
0 parts by weight) for a non-stretched film. Conditions for propylene / ethylene / 1-butene random copolymer (C): 1) 50 to 88 mol% of propylene units, 2 of ethylene units
３０30 mol%, and 10-40 mol% of 1-butene unit
And the content of 1-butene units is greater than the content of ethylene units. 2) MFR (ASTM D-1238, 230 ° C, 2.
16 kg load) is 0.1 to 50 g / 10 min. 3) Gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 3 or less. (2) The polypropylene resin (A) has a propylene homopolymer and an α-olefin unit content other than propylene of 1
At least one selected from the group consisting of a propylene / α-olefin random copolymer having 0 mol% or less and a propylene / α-olefin block copolymer having n-decane extraction amount of 10% by weight or less. The polypropylene resin composition for an unstretched film according to (1). (3) The ethylene / α-olefin random copolymer (B) has an ethylene unit content of 60 to 95 mol%,
Ethylene having a 1-butene unit content of 5 to 40 mol%
The above (1) or (2), which is a butene random copolymer
A polypropylene resin composition for an unstretched film as described in the above. (4) A non-stretched film comprising the polypropylene resin composition according to any one of the above (1) to (3).

The polypropylene resin composition for an unstretched film and the unstretched film of the present invention will be described in detail below. The polypropylene resin composition for an unstretched film of the present invention comprises a polypropylene resin (A), ethylene
It is a composition containing an α-olefin random copolymer (B) and a propylene / ethylene / 1-butene random copolymer (C). And the non-stretched film of this invention consists of the said polypropylene resin composition.

First, the polypropylene resin (A) constituting the polypropylene resin composition will be described. In the present invention, a conventionally known polypropylene resin can be appropriately selected and used as the polypropylene resin (A). Examples of such a polypropylene resin (A) include a propylene homopolymer, a propylene / α-olefin random copolymer of propylene and another α-olefin other than propylene, and a propylene / α-olefin block copolymer. be able to. Further, the polypropylene resin (A) may be modified with a polar group-containing monomer such as maleic anhydride.

Preferred polypropylene resins (A) are propylene homopolymer, propylene / α-olefin random copolymer containing 10 mol% or less, preferably 8 mol% or less of other α-olefin units, and n-olefin.
At least one selected from the group consisting of propylene / α-olefin block copolymers having an extraction amount of decane of 10% by weight or less, particularly 8% by weight or less is exemplified. In the present invention, "α-olefin unit"
Represents a structural unit derived from an α-olefin and constituting a polymer. Ethylene unit, propylene unit, 1
The same applies to butene units and the like. In the present invention, ethylene is included in the α-olefin.

As the other α-olefin forming the propylene / α-olefin random copolymer or the propylene block copolymer, an α-olefin having 2 to 20 carbon atoms other than propylene is preferably exemplified. Is ethylene, 1-butene, 1-pentene, 1-hexene,
Examples thereof include 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1-pentene. These α-olefins can be used alone or in combination of two or more.

The polypropylene resin (A) used in the present invention can be produced by a method known per se using a solid titanium catalyst or a metallocene catalyst known per se.

The crystallinity of the polypropylene resin (A) by the X-ray method is preferably at least 40%, particularly preferably at least 50%, and the melting point (Tm) by the DSC method is 100 to 16%.
Preferably it is 5 ° C. Further, it is preferable to use a polypropylene resin (A) having a melting point higher than the melting points of the ethylene / α-olefin random copolymer (B) and the propylene / ethylene / 1-butene random copolymer (C).

The polypropylene resin (A) is made of AS
The melt flow rate (MFR: 230 ° C., under a load of 2.16 kg) measured according to TM D-1238 is
Usually 0.1 to 300 g / 10 min, preferably 1 to 300 g / 10 min.
50 g / 10 min. The polypropylene resin (A)
One type may be used alone, or two or more types may be used in combination.

Next, the ethylene / α-olefin random copolymer (B) will be described. The ethylene / α-olefin random copolymer (B) used in the present invention comprises: 1) an ethylene unit content of 60 to 95 mol%, preferably 70 to 90 mol%, and 2) a density of 0.900 g / cm ³ or less, preferably 0.1 cm ³ .
850-0.880 g / cm ³ ) 3) MFR (melt flow rate, ASTM D-12
38, 190 ° C., 2.16 kg load) 0.1 to 50 g
/ 10 min, preferably 0.2 to 30 g / 10 min, particularly preferably 0.5 to 10 g / 10 min, and 4) gel permeation chromatography (GP
C), the molecular weight distribution (Mw / M) was determined as a polystyrene conversion value using ortho-dichlorobenzene as an elution solvent and monodisperse polystyrene as a standard substance.
n) is 3 or less.

The α-olefin of the ethylene / α-olefin random copolymer (B) has 3 or more carbon atoms, preferably 3 to 20, and particularly preferably 3 to 8 carbon atoms. α-
Specific examples of olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene,
-Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl -1
-Dodecene, 12-ethyl-1-tetradecene and the like. These can be used alone or in combination of two or more.

By blending such an ethylene / α-olefin random copolymer (B) with a propylene / ethylene / 1-butene random copolymer (C) in a polypropylene resin (A), a low-temperature impact resistance can be obtained. A resin composition having excellent heat resistance, low-temperature heat sealability, and excellent transparency can be obtained.

The ethylene / α-olefin random copolymer (B) preferably has a crystallinity of less than 40%, more preferably 30% or less, as measured by X-ray diffraction. When the ethylene / α-olefin random copolymer (B) having a crystallinity of less than 40% is used, a film excellent in low-temperature heat sealability and impact resistance (film impact strength characteristics) can be obtained.

Further, the ethylene / α-olefin random copolymer (B) is a parameter showing the randomness of the copolymer monomer chain distribution obtained by ¹³ C-NMR method.
(B value) is preferably in the range of 1.0 to 1.4. The B value is an index indicating the composition distribution state of the structural unit in the copolymer chain, and can be calculated by the following formula [I].

B = POE / (2PO.PE) [I] (wherein, PE and PO are the mole fraction of ethylene component and α-contained in the ethylene / α-olefin random copolymer, respectively) (The mole fraction of the olefin component, and POE is the ratio of the number of ethylene / α-olefin alternating chains to the total number of dyads.)
Such PE, PO and POE values are specifically:
It can be calculated as follows.

In a 10 mmφ test tube, about 200 mg of the ethylene / α-olefin random copolymer (B)
A sample is prepared by uniformly dissolving in 1 l of hexachlorobutadiene, and the ¹³ C-NMR spectrum of this sample is measured under the following conditions. [Measurement conditions] Measurement temperature: 120 ° C. Measurement frequency: 20.05 MHz Spectral width: 1500 Hz Filter width: 1500 Hz Pulse repetition time: 4.2 sec Pulse width: 7 μsec Number of times of integration: 2000 to 5000 times

The PE, PO and POE values were obtained from the ¹³ C-NMR spectrum measured as described above.
J. Ray (Macromolecules, 10, 773 (1977)), JC R
andall (Macro-molecules, 15, 353 (1982)), K. Kimu
ra (Polymer, 25, 4418 (1984)).

The B value obtained from the above formula is 2 when the ethylene / α-olefin random copolymer (B) is alternately distributed, and both values are completely separated. In the case of a polymerized complete block copolymer, the value is 0.

When the ethylene / α-olefin random copolymer (B) having a B value in the range of 1.0 to 1.4 is used, a polypropylene resin composition having excellent heat resistance can be obtained.

The ethylene / α-olefin random copolymer (B) has an intrinsic viscosity [η] of 0.5 to 5.0 at 135 ° C. measured in decalin (decahydronaphthalene).
It is preferably in the range of dl / g.

Further, the ethylene / α-olefin random copolymer (B) has a gη ^* value (JP-B-3-14045) defined by the following formula [II] of 0.2 to 0.2.
A long-chain branched ethylene / α-olefin random copolymer (B) in the range of 0.95, or gη ^* value of 0.9;
More than 5 linear ethylene / α-olefin random copolymers (B) are preferred. gη ^* = [η] / [η] blank ... [II]

In the above formula [II], [η] is 135
C is the intrinsic viscosity of the ethylene / α-olefin random copolymer (B) measured in decalin. Also, [η] bl
ank is the limiting viscosity of the control linear ethylene / propylene random copolymer, and is the same weight average molecular weight (light scattering method) as the ethylene / α-olefin random copolymer (B) in which the above [η] was measured. Is the intrinsic viscosity of a linear ethylene / propylene copolymer having an ethylene content of 70 mol%.

The long-chain branched ethylene / α-olefin random copolymer (B) having a gη ^* value of 0.2 to 0.95 is
A copolymer produced using a metallocene-based catalyst containing a metallocene compound represented by the following formula (2) is preferable.
The Jiita ^* value linear ethylene exceeding 0.95 alpha-
Olefin random copolymer (B) is a metallocene catalyst or a metallocene compound represented by the formula (2), comprising a metallocene compound represented by the formula (1) described below, each other R ⁴¹ to R ⁴⁴ A copolymer produced using a metallocene-based catalyst in which a part of adjacent groups is bonded to form a ring while those groups are bonded is preferable.

Ethylene α-having the above-mentioned properties
When the olefin random copolymer (B) is used, a polypropylene resin composition having excellent mechanical strength, weather resistance, ozone resistance, low-temperature flexibility and heat resistance can be obtained. In particular, gη
^{* When} a long-chain branched ethylene / α-olefin random copolymer (B) having a value of 0.2 to 0.95 is used, a polypropylene resin composition particularly excellent in moldability is obtained, and gη ^* Linear ethylene α- value exceeding 0.95
When the olefin random copolymer (B) is used, a polypropylene resin composition which is particularly excellent in terms of film impact can be obtained. The α-olefin has 6 to 6 carbon atoms.
When the ethylene / α-olefin random copolymer (B) is used, a polypropylene resin composition having excellent mechanical strength, low-temperature flexibility and heat resistance can be obtained.

The ethylene / α-olefin random copolymer (B) can be produced with a vanadium-based catalyst or a titanium-based catalyst. However, ethylene and α-olefin are copolymerized in the presence of a metallocene-based catalyst described later. An ethylene / α-olefin random copolymer obtained by polymerization is preferred.

The vanadium-based catalyst used for producing the ethylene / α-olefin random copolymer (B) is preferably a vanadium-based catalyst comprising a soluble vanadium compound and an alkylaluminum halide compound. Specific examples of the soluble vanadium compound of the vanadium-based catalyst include vanadium tetrachloride, vanadium oxytrichloride, vanadium monoethoxy dichloride, vanadium triacetylacetonate, and oxyvanadium triacetylacetonate.

Specific examples of the alkylaluminum halide compound of the vanadium catalyst include ethylaluminum dichloride, diethylaluminum monochloride, ethylaluminum sesquichloride, diethylaluminum monobromide, diisobutylaluminum monochloride, isobutylaluminum dichloride, isobutylaluminum. Sesquichloride and the like.

The titanium-based catalyst used in the production of the ethylene / α-olefin random copolymer (B) is formed from a solid titanium catalyst component, an organometallic compound catalyst component and, if necessary, an electron donor. The olefin polymerization catalyst used is preferred.

The solid titanium catalyst component of the catalyst for olefin polymerization is, for example, a solid titanium catalyst component in which titanium trichloride or a titanium trichloride composition is supported on a carrier, for example, a carrier having a specific surface area of 100 m ² / g or more. Or magnesium, halogen, electron donor (preferably aromatic carboxylic acid ester or alkyl group-containing ether)
And titanium as an essential component, and a solid titanium catalyst component in which these essential components are supported on a carrier, for example, a carrier having a specific surface area of 100 m ² / g or more. Among these, the latter solid titanium catalyst component is preferred.

The organometallic compound catalyst component of the olefin polymerization catalyst is preferably an organic aluminum compound, and specific examples thereof include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide. The organoaluminum compound can be appropriately selected according to the type of the solid titanium catalyst component used.

As the electron donor of the olefin polymerization catalyst, an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom or the like can be used, and an ester compound having the above atom is preferable. And ether compounds. Such an olefin polymerization catalyst may be activated by a method such as co-milling, or the olefin may be prepolymerized.

Next, the propylene / ethylene / 1-butene random copolymer (C) will be described. The propylene / ethylene / 1-butene random copolymer (C) used in the present invention satisfies the conditions 1) to 3) as described above. These conditions will be described sequentially.

The condition 1) is that propylene / ethylene / ethylene
The composition of the 1-butene random copolymer (C) is specified. That is, the propylene / ethylene / 1-butene random copolymer (C) contains 50 to 50 propylene units.
88 mol%, 2-30 mol% of ethylene units, and 1
-10 to 40 mol% of butene units, preferably 60 to 85 mol% of propylene units, 3 to 20 mol% of ethylene units, 10 to 30 mol% of 1-butene units, particularly preferably 60 to 85 mol% of propylene units, Ethylene unit 3 to 2
0 mol%, 1-butene unit 12 to 30 mol%.
And the content of 1-butene units is greater than the content of ethylene units.

When the propylene / ethylene / 1-butene random copolymer (C) has the above composition, the copolymer has elastomeric properties, compatibility with the polypropylene resin (A), and ethylene / α- This results in a well-balanced compatibility with the olefin random copolymer (B). The propylene / ethylene / 1-butene random copolymer (C) is in a range not impairing the above advantages.
Α-Olefin units other than propylene units, 1-butene units and ethylene units may be contained in small amounts, for example, 10 mol% or less.

The above conditions 2) and 3) satisfy the conditions of propylene / ethylene / 1-butene random copolymer (C), respectively.
The melt flow rate (MFR) and the molecular weight distribution (Mw / Mn), which are a measure of the molecular weight of the polymer, are specified. MFR of propylene / ethylene / 1-butene random copolymer (C) (ASTM D-1238, 230 ° C, 2.16
kg load) is 0.1 to 50 g / 10 min, preferably 0.1 g.
2 to 30 g / 10 min, particularly preferably 0.1 to 10 g / min
Minutes.

The Mw / Mn of the propylene / ethylene / 1-butene random copolymer (C) is 3 or less.
Mw / Mn is a value in terms of polystyrene measured by gel permeation chromatography (GPC) using orthodichlorobenzene as an elution solvent and monodisperse polystyrene as a standard substance.

The molecular weight distribution (Mw / Mn) can be measured, for example, by using GPC-150C manufactured by Water Corporation according to the following method. That is, as a separation column, TSK GNH TH (column size is 7.8 m in diameter)
m, length 600 mm, manufactured by Tosoh Corporation, trademark)
The column temperature was 140 ° C., the mobile phase was o-dichlorobenzene and BHT was 0.025% by weight as an antioxidant.
And moved at 1.0 ml / min, and the sample concentration was 0.1
% By weight, the sample injection amount is 500 μl, and a differential refractometer can be used as a detector. As separation columns, TSK GEL GMH-HT, TSK GEL
GMH-HTL (trademark, manufactured by Tosoh Corporation) or the like can also be used. Standard polystyrene manufactured by Tosoh Corporation can be used.

When the MFR and molecular weight distribution of the propylene / ethylene / 1-butene random copolymer (C) are within the above ranges, the compatibility with the polypropylene resin (A) is excellent, and the obtained composition is molded. The molded product obtained is excellent in processability and excellent in transparency, and the surface is less sticky.

The propylene / ethylene / 1 used in the present invention
-The butene random copolymer (C) preferably has a specific microstructure. That is, the propylene / ethylene / 1-butene random copolymer (C) is (i) head-
It preferably contains a three-chain structure consisting of only tail-bonded propylene units, or (ii) a three-chain structure consisting of head-tail bonded propylene units and 1-butene units.
Further, regarding the side chain methyl group of the propylene unit of the second unit of the three-chain structure of (i) or (ii), ¹³ C—N
When measured by MR (hexachlorobutadiene solution, based on tetramethylsilane), 19.7 to 21.7 ppm
Is 100% of the total area of the peaks appearing in
It is desirable that the area of the peak appearing at 21.7 ppm is 90% or more, preferably 92% or more.

The propylene / ethylene / 1-butene random copolymer (C) has a proportion of regio-irregular units based on 2,1-insertion of propylene monomer in all propylene units measured by ¹³ C-NMR. Is 0.05% or more, preferably 0.05 to 0.4%, more preferably 0.05%
It is desirable that it is about 0.3%.

The propylene / ethylene / 1-butene random copolymer (C) is a propylene monomer of 1,
3- 0.05% of irregular position unit based on insertion
The following is preferred. At the time of polymerization, the propylene monomer is 1,2-inserted (the methylene side binds to a catalyst described later), but may be rarely 2,1-inserted or 1,3-inserted. The 2,1-inserted or 1,3-inserted monomers form regio-irregular units in the polymer.

The ratio of 2,1-insertion of the propylene monomer in all propylene units was determined by using ¹³ C-NMR.
lymer, 30 (1989) 1350, and can be determined from the following formula [III].

[0046]

## EQU1 ## Ratio of regio-irregular units based on 2,1-insertion = ([0.25Iαβ [structure (i)] + 0.5Iαβ [structure (ii)]] × 100) / (Iαα + Iαβ [structure (ii )] + 0.5 [Iαγ + Iαβ [Structure (i)] + Iαδ]) ... [III]

Here, the peaks are named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). Iαβ and the like indicate peak areas such as αβ peaks. When it is difficult to determine the area such as Iαβ directly from the spectrum due to overlapping peaks, a carbon peak having a corresponding area can be used instead.

The three-chain amount based on the 1,3-insertion of propylene is obtained by dividing one half of the area of the βγ peak (resonating around 27.4 ppm) by the sum of half of the total methyl group peak and half of the βγ peak. By multiplying by 100, the ratio can be calculated in%.

The propylene / ethylene / 1 used in the present invention
The butene random copolymer (C) is preferably a copolymer produced using a metallocene catalyst.

The above-mentioned metallocene catalyst is represented by the following formula (1)

Embedded image [In the formula (1), M is a transition metal atom of Groups IV to VIB of the periodic table, and R ¹ , R ² , R ³ , and R ⁴ are the same or different and 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,
A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group, and a part of groups adjacent to each other is bonded to form a ring with the carbon atom to which those groups are bonded. Is also good. X ¹ and X ² are the same or different and 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,
It is an oxygen-containing group or a sulfur-containing group. Y is carbon number 1
To 20 divalent hydrocarbon groups, divalent halogenated hydrocarbon groups having 1 to 20 carbon atoms, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-, -S- , -SO
_{-, - SO 2 -, -} NR 5 -, - P (R 5) -, - P (= O)
^{(R 5) -, - BR} 5 -, or -AlR ⁵ - a. Here, R ⁵ is a hydrogen atom, a halogen atom, a carbon number of 1 to 20.
Or a halogenated hydrocarbon group having 1 to 20 carbon atoms. And a compound capable of activating this transition metal compound (a), and an organoaluminum compound (b) ),
At least one selected from the group of compounds (b) to (d) consisting of an organoaluminum oxy compound (c) and (d) an ionized ionic compound which forms an ion pair by reacting with the transition metal compound (a). And a metallocene-based catalyst containing

In the above formula (1), M is the periodic table Nos. IV to VIB
Group transition metals, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
Chromium, molybdenum, tungsten, and the like, preferably titanium, zirconium, and hafnium, and particularly preferably zirconium.

In the above formula (1), R ¹ , R ² , R ³ and R ⁴
Are the same or different, and each has 1 carbon atom which may be substituted with a hydrogen atom, a halogen atom, or halogen.
To 20 hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, and some of the groups adjacent to each other are bonded to form a carbon atom to which those groups are bonded. It may form a ring. Incidentally, R ¹ to R ⁴ present two each in the formula indicates that it is preferable to bind a combination between the same symbols in forming these bonded to ring, for example, a R ¹ R ¹
Indicate that it is preferable to combine with and to form a ring.

In the above formula (1), examples of the halogen atom represented by R ^{1 to} R ⁴ include fluorine, chlorine, bromine and iodine. In the above formula (1), R ¹ to
As the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ ,
For example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, n-
Alkyl groups such as pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, And aryl groups such as biphenylyl.

The ring formed by combining these hydrocarbon groups includes a condensed ring such as a benzene ring, a naphthalene ring, an acenaphthene ring and an indene ring, and a condensed ring such as a benzene ring, a naphthalene ring, an acenaphthene ring and an indene ring. Examples thereof include a group in which a hydrogen atom on the group is substituted with an alkyl group such as methyl, ethyl, propyl, and butyl. Further, these hydrocarbon groups may be substituted with halogen.

In the above formula (1), the silicon-containing groups represented by R ^{1 to} R ⁴ include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; Trihydroyl-substituted silyls such as triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; A silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylphenyl;

In the formula (1), the oxygen-containing group represented by R ^{1 to} R ⁴ includes an alkoxy group such as a hydroxy group, methoxy, ethoxy, propoxy and butoxy; an allyloxy such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy. Groups; arylalkoxy groups such as phenylmethoxy and phenylethoxy;

In the formula (1), the sulfur-containing group represented by R ^{1 to} R ⁴ includes a substituent in which oxygen of the oxygen-containing compound is replaced by sulfur; methyl sulfonate, trifluoromethane sulfonate, phenyl sulfone Phonate,
Benzylsulfonate, p-toluenesulfonate,
Sulfonate groups such as trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluene Examples thereof include sulfinate groups such as sulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate.

In the above formula (1), the nitrogen-containing group represented by R ^{1 to} R ⁴ includes an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; Examples thereof include an arylamino group such as amino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino, or an alkylarylamino group.

In the formula (1), examples of the phosphorus-containing group represented by R ^{1 to} R ⁴ include dimethylphosphino, diphenylphosphino and the like.

In the above formula (1), X ¹ and X ² may be the same or different from each other and represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen, It is an oxygen-containing group or a sulfur-containing group. Specific examples of these atoms or groups include those similar to the atoms or groups represented by R ^{1 to} R ⁴ .

In the above formula (1), Y is substituted by halogen.
A divalent hydrocarbon group having 1 to 20 carbon atoms which may be
Divalent silicon-containing group, divalent germanium-containing group, -O
-, -CO-, -S-, -SO-, -SO_Two-, -NR^Five
-, -P (R^Five)-, -P (O) (R ^Five)-, -BR^Five-Or
-AlR^Five-. Where R^FiveIs a hydrogen atom, as above
Halogen atoms and charcoals optionally substituted with halogen
It is a hydrocarbon group having a prime number of 1 to 20.

The divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen represented by Y in the above formula (1) includes methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1 , 2-ethylene, 1,3-trimethylene,
Examples include alkylene groups such as 1,4-tetramethylene, 1,2-cyclohexylene, and 1,4-cyclohexylene; and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene. Further, a halogenated hydrocarbon group obtained by halogenating the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene can be exemplified.

Examples of the divalent silicon-containing group represented by Y in the above formula (1) include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene,
Di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene,
Alkylsilylenes such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene; alkylarylsilylenes, arylsilylene groups, and alkyldisilyls such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl , An alkylaryldisilyl group or an aryldisilyl group.

Examples of the divalent germanium-containing group represented by Y in the above formula (1) include compounds in which the silicon of the above-mentioned divalent silicon-containing group is replaced with germanium.

Specific examples of the bridge type transition metal compound (a) represented by the above formula (1) will be described below. Bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride,
Bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (neopentylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (1-cyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- ( 3-methylcyclopentadienyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,4-dimethylcyclopentadienyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,5-trimethylcyclopentadienyl)} zirconium dichloride and the like.

In the present invention, among the transition metal compounds (a) represented by the above formula (1), bridge type transition metal compounds represented by the following formula (2) are preferably used.

Embedded image (In the formula (2), M, R ¹ , R ³ , X ¹ , X ² and Y are the same as the definition of the formula (1). R ^{21 to} R ²⁴ and R ⁴¹ to R ²¹ )
R ⁴⁴ is a hydrogen atom, a halogen atom, an alkyl group or an aryl group, wherein the alkyl group or the aryl group is
It may be substituted with a halogen or an organic silyl group.
R ^{41 to} R ⁴⁴ may form a ring together with a carbon atom to which a part of the groups adjacent to each other is bonded. )

Specific examples of the bridge type transition metal compound represented by the above formula (2) are described below. rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-ethylene-bis (1-indenyl) zirconium dichloride, r
ac-ethylene-bis (1-indenyl) zirconium dibromide, rac-ethylene-bis (1-indenyl) dimethyl zirconium, rac-ethylene-bis (1-indenyl) diphenyl zirconium, rac-ethylene-bis (1-indenyl) Methyl zirconium monochloride, rac-ethylene-
Bis (1-indenyl) zirconium bis (methanesulfonato), rac-ethylene-bis (1-indenyl) zirconium bis (p-toluenesulfonate), rac-ethylene-bis (1-indenyl) zirconium bis (trifluoromethanesulfonate) Nato), rac-ethylene-bis ｛1- (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride,
rac-isopropylidene-bis (1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis ｛1- (2-methyl-
4-i-propylindenyl) zirconium dichloride,

Rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-)
n-propylindenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-sec-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis
-(2,7-dimethyl-4-n-pentylindenyl)｝ 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-chloromethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis
(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
(2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (cyclohexyl) silylenebis ｛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-diphenylsilylene bis ｛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) zirconium dichloride, rac-dimethylsilylene bis 1- (2-methyl
-4-i-propyl-7-ethylindenyl) zirconium dibromide, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dimethyl, rac-dimethyl Silylene-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, rac-dimethylsilylene-bis (1,2-dihydroacenaphtho [4,5-b] cyclopentadienyl) zirconium dichloride, rac-dimethyl Silylene-bis (benzo [e] indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (4-phenylindenyl)} zirconium dichloride, rac-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) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-
Tolyl) indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis ｛1- (2-methyl-4- (o-tolyl)
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, ra
c-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) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-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
-(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)｝ zirconium monochloride mono (trifluoromethanesulfonate),

Rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfonate), rac-dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium di (p-toluenesulfonate), rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium Di (methylsulfonate), rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfinate), rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium di (trifluoroacetate), rac-dimethylsilylene-bis ｛1-
(2-methyl-4-phenylindenyl) zirconium monochloride (n-butoxide), rac-dimethylsilylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium di (n-butoxide), rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride (phenoxide) ), Rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-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-dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} 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-dimethylsilyl -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
-(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)｝ 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, ra
c-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 ｛1- (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-dimethylsilylene-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
(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-bis ｛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) デ zirconium dichloride, rac-methylphenylsilylene-
Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} 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.

Further, there may be mentioned transition metal compounds in which zirconium in the above transition metal compounds is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten.

The transition metal compound (a) is usually used as a catalyst component for olefin polymerization in the form of a racemate, but R-type or S-type can also be used. In the present invention, two or more transition metal compounds (a) as described above may be used in combination.

The activating compound capable of activating the transition metal compound (a) is at least one selected from the group consisting of an organic aluminum compound (b), an organic aluminum oxy compound (c), and an ionic compound (d). One compound is used.

The organoaluminum compound (b) is represented, for example, by the following formula (3). R ¹ _n AlX _3-n (3) (in the formula (3), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3)
3. )

In the above formula (3), R ¹ has 1 to ¹ carbon atoms.
12 hydrocarbon groups, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, A cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group and the like.

Such an organoaluminum compound (b)
As, specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum,
Trialkylaluminums such as triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dialkylaluminums such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide Halides; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum Examples thereof include alkylaluminum dihalides such as mudichloride and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

As the organoaluminum compound (b), a compound represented by the following formula (4) can also be used. During ^{_{R 1 n AlY 3-n ...}} (4) ( formula (4), R ¹ is the same as R ¹ of formula (3), Y is -OR ² group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂
Group, -SiR ⁶ ₃ group or -N (R ⁷⁾ is AlR ⁸ ₂ group, n
Is 1-2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group,
R ⁵ is a hydrogen atom, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R ⁶ and R ⁷ are methyl. And an ethyl group. )

Specifically, the following compounds can be mentioned. _{^{(1) R 1 n Al (}} OR 2) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (2) R 1 n Al}} (OSiR 3 3) 3 a compound represented by _-n ,
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc. (3) R ¹ _n Al
Compound represented by (OAlR ⁴ ₂ ) _3-n , for example, Et ₂ AlO
(4) such as AlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _{2
^{R 1 n Al (NR 5 2}} ) a compound represented by _3-n, e.g., Me ₂ A
l NEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ A
lN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) _2, etc.
_{^{(5) R 1 n Al (}} SiR 6 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} , (6) R 1 n Al (N (R 7)
AlR ⁸ ₂₎ a compound represented by _3-n, e.g., Et ₂ AlN (M
e) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like. In the above, Me is a methyl group, Et is an ethyl group,
Bu represents a butyl group.

[0087] Of these, the formula ^{_{R 1 3 Al, R 1 n}} Al
(OR ²⁾ _3-n, preferably compounds represented by ^{_{R 1 n Al (OAlR 4 2}} ) 3-n, in particular R is an isoalkyl radical, n is 2
Are preferred. These can be used in combination.

The above-mentioned organoaluminum oxy compound (c)
May be a conventionally known benzene-soluble aluminoxane, or may be a benzene-insoluble organic aluminum oxy compound as disclosed in JP-A-2-276807.

The aluminoxane as described above 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 aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing the aluminoxane include the same compounds as those described above as the organoaluminum compound (b). Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred. Organoaluminum compounds can be used in combination.

Solvents used in the production of aluminoxane include benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene; pentane, hexane, heptane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane; cyclopentane,
Alicyclic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated products And hydrocarbon solvents such as bromides. Others
Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound (c) used in the present invention has an Al component soluble in benzene at 60 ° C. of 10% or less in terms of Al atoms.
Preferably 5% or less, particularly preferably 2% or less;
Insoluble or poorly soluble in benzene.

The solubility of such an organoaluminum oxy compound (c) in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligram atoms of Al in 100 ml of benzene and stirring at 60 ° C. for 6 hours. After mixing, hot filtration was performed at 60 ° C. using a G-5 glass filter equipped with a jacket, and the solid part separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and the total filtrate was washed. Is determined by measuring the abundance (X mmol) of Al atoms present in
%).

The ionized ionic compound (d) is a compound which reacts with the transition metal compound (a) represented by the formula (1) to form an ion pair. Examples of such an ionized ionic compound (d) include JP-A-1-50195.
No. 0, Japanese Patent Application Laid-Open No. Hei.
JP 179005, JP-A-3-179006,
JP-A-3-207703, JP-A-3-20770
No. 4, US Pat. No. 5,321,106, Lewis acids, ionic compounds, carborane compounds and the like can be used.

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 and the} like can be mentioned.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocarbon. Cenium tetra (pentafluorophenyl) borate and the like can be mentioned.

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.

The ionized ionic compound (d) can be used in combination of two or more kinds. Further, as the activating compound capable of activating the transition metal compound (a), the above-mentioned components (b), (c) and (d) can be used in combination.

The metallocene catalyst is prepared by mixing the above transition metal compound (a) and at least one activating compound selected from the group consisting of (b) to (d) in an inert hydrocarbon solvent or olefin solvent. Can be prepared.

As the inert hydrocarbon solvent used for preparing the metallocene catalyst, for example, propane, butane,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and hexadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; petroleum fractions such as gasoline, kerosene, and light oil; mixtures thereof;

Preparation of metallocene catalyst from each of these components
In doing so, the transition metal compound (a) usually contains about 10^-8
-10^-1mol / liter (polymerization volume), preferably
10 ^-7~ 5 × 10^-2Use at a concentration of mol / liter
It is desirable.

As the activating compound, component (b) and / or
Alternatively, when the component (c) is used, the atomic ratio of aluminum to the transition metal of the transition metal compound (a) (A
1 / transition metal), usually in an amount of from 10 to 10,000, preferably from 20 to 5,000, as component (b) and / or (c).
It is preferred to use components. When the organoaluminum compound (b) and the organoaluminum oxy compound (c) are used in combination, the aluminum atom (Al-
The atomic ratio (Al-1 / Al-2) of the aluminum atoms (Al-2) in the components (1) and (c) is 0.02 to 3, preferably 0.05.
It is desirable to use it in an amount of about 1.5.

When the ionized ionic compound (d) is used, the molar ratio of the transition metal compound (a) to the component (d) ((a) / (d)) is usually 0.01 to 10%. , Preferably in amounts of 0.1 to 5.

The above catalyst components may be mixed in a polymerization vessel, or a premixed one may be added to the polymerization vessel.
When mixing these components in advance, usually -50 to +15
0 ° C., preferably at a temperature of −20 to + 120 ° C., for 1 minute to
The contact can be carried out for 50 hours, preferably 5 minutes to 25 hours. Further, the mixing temperature may be changed during the mixing contact.

The metallocene catalysts described in the above (a) to (d)
A solid catalyst in which all or any of the components are supported on a granular or particulate solid (carrier) may be used.
This carrier may be an inorganic carrier or an organic carrier. As the inorganic carrier, a porous oxide such as SiO ₂ and Al ₂ O ₃ is preferably used. As the organic carrier, for example, ethylene, propylene, 1-butene,
(Co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as 4-methyl-1-pentene or polymers or copolymers mainly composed of vinylcyclohexane or styrene. Can be used.

The metallocene catalyst may be used after preliminarily polymerizing an olefin with each of the above catalyst components to form a prepolymerized catalyst. As the olefin used for the prepolymerization, propylene, ethylene, α such as 1-butene
-Although olefins are used, these can be used in combination with other olefins.

In forming the metallocene catalyst, other components useful for olefin polymerization, such as water as a catalyst component, can be used in addition to the above components.

The ethylene / α-olefin random copolymer (B) and the propylene / ethylene / 1-butene random copolymer (C) used in the present invention are prepared by reacting ethylene with ethylene in the presence of the above-mentioned metallocene catalyst. It can be produced by copolymerizing α-olefin or propylene, 1-butene and ethylene.

The polymerization can be carried out by any of liquid phase polymerization such as suspension polymerization and solution polymerization or gas phase polymerization. In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the above catalyst preparation can be used, and an α-olefin such as propylene can be used as the solvent.

When the polymerization is carried out by a suspension polymerization method, -5
It is desirable to carry out the reaction at a temperature of 0 to + 100 ° C, preferably 0 to 90 ° C, and when performing the solution polymerization method, at a temperature of 0 to 250 ° C, preferably 20 to 200 ° C. When the polymerization is carried out by a gas phase polymerization method, at a temperature of 0 to 120 ° C, preferably 20 to 100 ° C, at normal pressure to 9.8 MPa (normal pressure to 9.8 MPa).
100 kgf / cm ² , gauge pressure), preferably normal pressure
4.9 MPa (normal pressure to 50 kgf / cm ² , gauge pressure)
It is desirable to carry out under a pressure of.

The polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the obtained copolymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

The polypropylene resin composition of the present invention comprises 50 to 95 parts by weight of the above polypropylene resin (A) and 3 to 3 parts of the ethylene / α-olefin random copolymer (B).
40 parts by weight, 2 to 20 parts by weight of the propylene / ethylene / 1-butene random copolymer (C), preferably 60 to 92 parts by weight of the polypropylene resin (A), and the ethylene / α-olefin random copolymer ( B) 5-30
3 to 10 parts by weight of a propylene / ethylene / 1-butene random copolymer (C). here,
The total amount of the components (A), (B) and (C) is 100 parts by weight.

The above polypropylene resin composition, together with polypropylene (A), ethylene / α-olefin random copolymer (B), and propylene / ethylene / 1-butene random copolymer (C), together with the composition of the present invention Other components such as other additives and other polymers may be contained within a range not to impair the advantage of the above. As the above additives,
Weathering stabilizer, heat stabilizer, anti-fogging agent, anti-blocking agent,
Slip agents, lubricants, antistatic agents, flame retardants, pigments, dyes,
Fillers and the like can be mentioned.

The polypropylene resin composition of the present invention is prepared by a general method known as a method for preparing a polypropylene resin composition. For example, a polypropylene resin (A), an ethylene / α-olefin random copolymer (B ), And the propylene / ethylene / 1-butene random copolymer (C), and further other components optionally blended can be prepared by melt-kneading. For example, the polypropylene resin composition of the present invention may be prepared by simultaneously or sequentially charging the above components into a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, and the like, and then mixing them. It can be obtained by melt-kneading with a machine, kneader, Banbury mixer or the like.

MF of polypropylene resin composition of the present invention
R (ASTM D-1238, 230 ° C, 2.16 kg
Load) is 1 to 100 g / 10 min, especially 1 to 50 g / 1
Preferably, it is 0 minutes. The melting point (DSC method) of the polypropylene resin composition of the present invention is 100 to 167 ° C,
Particularly, the temperature is preferably from 120 to 167 ° C.

From the polypropylene resin composition of the present invention,
A non-stretched film can be formed by a known extrusion molding method. The unstretched film obtained by the extrusion molding method has excellent transparency, impact resistance, low-temperature heat sealability, and heat seal strength, and is suitable for use as a single-layer unstretched film.

The non-stretched film of the present invention is a non-stretched film obtained by molding the polypropylene resin composition of the present invention by an extrusion method. The thickness of the unstretched film of the present invention varies depending on the application, but is usually 10 to 1
00 μm, preferably 20 to 80 μm.

Since the unstretched film of the present invention is excellent in the above-mentioned various properties, it can be used in various packaging fields, for example, fresh foods such as vegetables and fish meat; snacks, dried foods of noodles, soups,
Various food packaging fields such as pickles and other water foods; tablets,
It can be used in a wide range of packaging fields, such as fields for packaging medical-related products used for various forms of medical products such as powders and liquids, and peripheral materials for medical devices; and fields for packaging various electric devices such as cassette tapes and electric components. .

The molding method for molding the unstretched film of the present invention can be carried out by appropriately employing the equipment and conditions conventionally used for extrusion molding a known polypropylene resin or a polypropylene resin composition.

[0121]

As described above, the polypropylene resin composition for an unstretched film of the present invention comprises a polypropylene resin,
Because it contains a specific amount of a specific ethylene / α-olefin random copolymer and a specific propylene / ethylene / 1-butene random copolymer, it has excellent transparency, impact resistance, low-temperature heat sealability, and heat seal strength. An excellent unstretched film can be formed, and the formed unstretched film is excellent in the above-mentioned various properties.

[0122]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the examples. The evaluation method in each case is
It is as follows.

[Evaluation method] (1) Heat seal strength Heat seal strength (peel strength) was measured under the following conditions in accordance with JIS Z1707. Sealing pressure: 0.2 MPa Sealing time: 1 second Peeling speed: 300 mm / min (2) Impact resistance The film impact strength, which is an index of impact resistance, is measured by JI.
It measured according to SP8134. The capacity of the tester was 30 kg / cm · cm, and the impact head was 1/2 inch φ. (3) Transparency The haze (cloudiness) as an index of transparency is determined according to ASTM D100.
3 was measured. (4) Gloss (gloss) Gloss was measured in accordance with ASTM D523.

Production Example 1 (Production of random copolymer of ethylene / 1-butene (B)) A random copolymer of ethylene / 1-butene was produced using a metallocene catalyst. That is, 950 m of hexane was placed in a 2-liter autoclave sufficiently purged with nitrogen.
l, 1-butene (50 g) was added, triisobutylaluminum (1 mmol) was added thereto, and the temperature was raised to 70 ° C.
² , gauge pressure), 0.30 mmol of methylaluminoxane, rac-dimethylsilylene-bis {1- (2-n-propyl)
4- (9-phenanthryl) indenyl) zirconium dichloride was added in an amount of 0.001 mmol in terms of Zr atom, and ethylene was continuously supplied to adjust the total pressure to 0.1%.
The polymerization was carried out for 30 minutes while maintaining the pressure at 7 MPa (7 kgf / cm ² , gauge pressure). After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The resulting polymer (a long-chain branched ethylene / 1-
Butene random copolymer (B-1)) was 28.0 g, and the polymerization activity was 56 kg · polymer / mmol Zr · h.
r.

The composition and physical properties of this polymer are as follows. (1) Composition Ethylene unit content: 89.0 mol% 1-butene unit content: 11.0 mol% (2) MFR (ASTM D-1238, 190 ° C,
2.16 kg load): 3.6 g / 10 min. (3) Molecular weight distribution by GPC (Mw / Mn): 2.0 (4) Density: 0.885 g / cm ³ (5) B value: 1.1 (6 ) Intrinsic viscosity [η]: 1.48 dl / g (7) gη ^* : 0.89

Production Example 2 In Production Example 1, rac-dimethylsilylene-bis {1- (2-
n-propyl-4- (9-phenanthryl) indenyl) zirconium dichloride was replaced by linear ethylene -1-butene random copolymer (B-2) was obtained.

The composition and physical properties of this polymer are as follows. (1) Composition Ethylene unit content: 89.2 mol% 1-butene unit content: 10.8 mol% (2) MFR (ASTM D-1238, 190 ° C,
2.16 kg load): 3.4 g / 10 min (3) Molecular weight distribution (Mw / Mn) by GPC: 2.0 (4) Density: 0.884 g / cm ³ (5) B value: 1.0 (6) ) Intrinsic viscosity [η]: 1.49 dl / g (7) gη ^* : 1.00

Production Example 3 (Production of propylene / ethylene / 1-butene random copolymer (C)) Propylene / ethylene / 1-
A butene random copolymer was produced. That is, 950 ml of hexane and 75 g of 1-butene were charged into a 2-liter autoclave sufficiently purged with nitrogen, 1 mmol of triisobutylaluminum was added thereto, and the temperature was raised to 70 ° C. Pressure 0.7
MPa (7 kgf / cm ² , gauge pressure), methylaluminoxane 0.30 mmol, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride is converted to Zr atom 0.001 mmol, continuously supplied so that the molar ratio (propylene / ethylene) between the propylene supply amount and the ethylene supply amount was 95/5, and the total pressure was 0.7 MPa (7 kgf). / Cm ² , gauge pressure) for 30 minutes. After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (propylene / 1-butene / ethylene copolymer) was 28.0 g, and the polymerization activity was 56 kg · polymer / mmol Zr · hr.

The composition and physical properties of this polymer are as follows:
It is on the street. 1) Composition Propylene unit content: 68.5 mol% Ethylene unit content: 10.2 mol% 1-butene unit content: 21.3 mol% 2) MFR (ASTM D-1238, 230 ° C, 2.
16 kg load): 4.4 g / 10 min 3) Molecular weight distribution (Mw / Mn) by GPC: 2.3  4) Three-chain structure consisting of head-to-tail bonded propylene units
Structure: exists 5) Head-to-tail bonded propylene unit and 1-butene unit
3 chains in which a propylene unit is present in the second unit
Structure: exists

Example 1 A propylene unit content of 96.8 mol%, an ethylene unit content of 3.2 mol%, an MFR (ASTM D-1238,
Propylene / ethylene random copolymer resin (A) at 6.9 g / 10 min (230 ° C., 2.16 kg load) and the long-chain branched ethylene / 1-butene random copolymer (elastomer obtained in Production Example 1) ) (B-1) and the propylene / ethylene / 1-butene random copolymer (C) obtained in Production Example 3 were blended at the blending ratio shown in Table 1, and mixed with a mixer. The polypropylene resin composition melt-kneaded at a temperature of ° C. and extruded into strands was cut in water to produce pellets of the composition.
From the pellets, an extruder equipped with a slit die (40 mmφ uniaxial, L / D = 26, cylinder temperature 21
0 ° C.) to prepare a single-layer unstretched film having a thickness of 50 μm. Table 1 shows the evaluation results of the obtained single-layer unstretched film.

Examples 2 and 3 The same procedures as in Example 1 were carried out except that the compositions shown in Table 1 were changed.
Table 1 shows the results.

[0132]

[Table 1] * 1 Propylene / ethylene random copolymer resin (A) * 2 Production example 1 long-chain branched ethylene / 1-butene random copolymer (B-1) * 3 Linear ethylene / 1- production example 2 Butene random copolymer (B-2) * 4 Propylene / ethylene / 1-butene random copolymer of Production Example 3 (C)

Example 4 In Example 1, the long-chain branched ethylene / 1-butene random copolymer (B-1) obtained in Production Example 1 was replaced with the linear ethylene obtained in Production Example 2. -A single-layer unstretched film was produced in the same manner as in Example 1 except that the 1-butene random copolymer (B-2) was used. Table 2 shows the evaluation results of the obtained unstretched films.

Comparative Example 1 In Example 1, the propylene / ethylene / 1-butene random copolymer (C) was not used, and the ethylene / 1-butene random copolymer was used.
Except that the blending amount of the butene random copolymer (B-1) was changed to 20 parts by weight, the same procedure was performed as in Example 1 to obtain a thickness of 50%.
A μm single-layer unstretched film was prepared. Table 2 shows the evaluation results of the obtained single-layer unstretched film.

[0135]

[Table 2] * 1 Propylene / ethylene random copolymer resin (A) * 2 Production example 1 long-chain branched ethylene / 1-butene random copolymer (B-1) * 3 Linear ethylene / 1- production example 2 Butene random copolymer (B-2) * 4 Propylene / ethylene / 1-butene random copolymer of Production Example 3 (C)

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁶ identifications FI C08L 23:14)

Claims (4)

[Claims] (A) 50 to 95 parts by weight of a polypropylene resin, (B) a content of ethylene units of 60 to 95 mol%, a density of 0.900 g / cm ³ or less, and MFR
(ASTM D-1238, 190 ° C, 2.16 kg load) is 0.1 to 50 g / 10 min, and the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3 or less. 3 to 40 parts by weight of ethylene / α-olefin random copolymer (here, α-olefin has 3 or more carbon atoms) and (C) propylene / ethylene / 1 satisfying the following conditions 1) to 3) -A polypropylene resin composition for a non-stretched film, comprising 2 to 20 parts by weight of a butene random copolymer (here, the total amount of (A), (B) and (C) is 100 parts by weight). Conditions for propylene / ethylene / 1-butene random copolymer (C): 1) 50 to 88 mol% of propylene units, 2 of ethylene units
３０30 mol%, and 10-40 mol% of 1-butene unit
And the content of 1-butene units is greater than the content of ethylene units. 2) MFR (ASTM D-1238, 230 ° C, 2.
16 kg load) is 0.1 to 50 g / 10 min. 3) Gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 3 or less. 2. The polypropylene resin (A) is a propylene homopolymer, a propylene / α-olefin random copolymer having an α-olefin unit content other than propylene of 10 mol% or less, and an extractable amount of n-decane. The polypropylene resin composition for an unstretched film according to claim 1, which is at least one selected from the group consisting of 10% by weight or less of a propylene / α-olefin block copolymer. 3. An ethylene / α-olefin random copolymer (B) having an ethylene unit content of 60 to 95 mol% and a 1-butene unit content of 5 to 40 mol%. 3. The polypropylene resin composition for an unstretched film according to claim 1, which is a polymer. 4. A non-stretched film comprising the polypropylene resin composition according to claim 1.