JP2795482B2 - Polypropylene stretched film - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a 3-methyl-1-butene polymer unit containing 3-methyl-1-butene polymer units which are densely blended in propylene polymer units. The present invention relates to a stretched polypropylene film produced from the composition.

Technical Background of the Invention There have already been many proposals for a method for producing a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor as essential components, and such a solid titanium catalyst component having 3 or more carbon atoms has been proposed. It is also known that a polymer having high stereoregularity can be produced in a high yield by using it in the polymerization of α-olefin, particularly propylene.

Further, when producing a propylene-based polymer using an olefin polymerization catalyst component comprising the solid titanium catalyst component and the organoaluminum compound catalyst component as described above,
Using the olefin polymerization catalyst component, 3-methyl-1-
It is known that propylene-based polymers having excellent properties can be obtained by prepolymerizing butene.

The present inventors have further intensively studied based on the above-mentioned findings, and by forming the resin composition obtained as described above into a film form, it was impossible to achieve the conventional polypropylene. It has been found that a film having excellent transparency can be obtained, and that the crystallization speed is increased by using such a composition, and the present invention has been achieved.

OBJECT OF THE INVENTION The present invention has been made in view of the above prior art, and has as its object to provide a stretched polypropylene film having particularly excellent transparency.

SUMMARY OF THE INVENTION The stretched polypropylene film according to the present invention comprises: [A] a liquid magnesium compound having no reducing property;
A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components obtained by reacting a liquid titanium compound in the presence of an electron donor [B] An organoaluminum compound catalyst component and a necessary component 3-methyl-1-butene is prepolymerized in the presence of an olefin polymerization catalyst [I] formed from [C] an electron donor, and then a linear α-olefin having 2 to 5 carbon atoms. Is polymerized using the prepolymerized catalyst formed by prepolymerizing the above and, if necessary, the above [B] organoaluminum compound catalyst component and [C] an electron donor, or Having 2 to 2 carbon atoms in the presence of the catalyst [I]
5 is prepolymerized, and then 3-
Propylene is polymerized using a prepolymerization catalyst component [I] formed by prepolymerizing methyl-1-butene, and if necessary, the above [B] organoaluminum compound catalyst component and [C] an electron donor. 3-methyl-1-butene polymer unit obtained by
It contains an olefin polymer unit and a propylene polymer unit, and has a 3-methyl-1-butene polymer unit content of 10
It is characterized by being formed from a composition containing a 3-methyl-1-butene polymer unit in the range of 10000 ppm by weight.

The stretched polypropylene film according to the present invention comprises a composition in which a specific amount of a 3-methyl-1-butene polymer unit and a propylene polymer unit are densely blended (in the present invention, such a composition To "3-methyl-1-
Butene polymer unit-containing composition ")
, It is particularly excellent in transparency.

DETAILED DESCRIPTION OF THE INVENTION The stretched polypropylene film according to the present invention will be specifically described below.

The stretched polypropylene film according to the present invention is formed from a composition containing a 3-methyl-1-butene polymer unit.

The 3-methyl-1-butene polymer unit-containing composition in which the 3-methyl-1-butene polymer unit and the propylene polymer unit are densely blended is, for example, as described below. 3-methyl-1-butene and a linear α having 2 to 5 carbon atoms using an olefin polymerization catalyst.
-A composition produced by polymerizing propylene using the prepolymerized catalyst [I] obtained by performing prepolymerization of an olefin can be exemplified.
The composition containing a 3-methyl-butene polymer unit used in the present invention is an α-olefin formed from a 3-methyl-1-butene polymer unit and a linear α-olefin having 2 to 5 carbon atoms.
This is a composition in which an olefin polymer unit and a propylene polymer unit are densely blended in the same manner as described above. Such densely blended 3-methyl-1-
In some cases, the composition containing butene polymer units contains poly-3-methyl-1-butene and linear poly α having 2 to 5 carbon atoms.
-Sometimes referred to as a block copolymer of olefin and polypropylene.

Next, a method for producing the 3-methyl-1-butene polymer unit-containing composition used for forming the stretched polypropylene film according to the present invention will be specifically described.

The 3-methyl-1-butene polymer unit-containing composition can be produced, for example, using the following olefin polymerization catalyst.

The olefin polymerization catalyst used in the present invention is formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and, if necessary, an electron donor [C].

FIG. 1 shows an example of a flowchart of a method for producing a 3-methyl-1-butene-containing composition using the olefin polymerization catalyst as described above.

The solid titanium catalyst component [A] used in the present invention includes:
It is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such a solid titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below.

In the present invention, as the titanium compound used for adjusting the solid titanium catalyst component [A], for example, Ti (OR)
_g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be exemplified.

More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC _{2 H 5) 2 Cl 2, Ti} (On-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) Giro halogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC _{2 H 5) 3 Cl, Ti} (On-C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H 5 _{) 4, Ti (On-C} 4 H 9) 4 Ti (Oiso-C 4 H 9) 4 Ti (O2- _ethylhexyl), and the like tetraalkoxytitanium such as _4.

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a reducing magnesium compound and a non-reducing magnesium compound.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond.

Specific examples of the magnesium compound having such a reducing property include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, dioctylmagnesium, didecylmagnesium, decylbutylmagnesium, and ethylbutyl. Dialkyl magnesium such as magnesium; alkyl magnesium halides such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, and butyl magnesium halide; and alkyl alkoxy magnesium such as butyl ethoxy magnesium. . These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid. Further, the alkyl group in the magnesium compound described above may be branched or linear.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium and the like Magnesium magnesium; magnesium laurate, magnesium stearate, etc. Or the like can be mentioned Bonn salt.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

In the present invention, the magnesium compound is, in addition to the magnesium compound having a reducing property and the magnesium compound having no reducing property, a complex compound of the magnesium compound and another metal, a double compound or another metal compound. May be used. Also, magnesium metal can be used as a starting material. further,
It may be a mixture of two or more of the above compounds.

In the present invention, any magnesium compound other than those described above can be used. In any case, some or all of them must be finally halogenated. Among these magnesium compounds, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable.
Among them, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferably used.

In the present invention, as the electron donor used for preparing the solid titanium catalyst component [A], preferably a polyvalent carboxylic acid ester is used, and specifically, a compound having a skeleton represented by the following formula is used. Can be

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , R ⁶ is a hydrogen atom, a substituted or unsubstituted hydrocarbon group, R ³ , R ⁴ is a hydrogen atom, It is a substituted or unsubstituted hydrocarbon group. Preferably, at least one of R ³ and R ⁴ is a substituted or unsubstituted hydrocarbon group.
R ³ and R ⁴ may be connected to each other to form a cyclic structure. Here, as the substituted hydrocarbon group, N,
O, there are mentioned hydrocarbon group substituted containing a hetero atom such as S, for example, -C-O-C -, - COOR, -COOH, -OH, -SO 3 H, -C
-N-C -, - and hydrocarbon group substituted with a structure such as NH _2.

Among these, a diester in which at least one of R ¹ and R ² is derived from a dicarboxylic acid having an alkyl group having 2 or more carbon atoms is preferable.

Specific examples of the polyvalent carboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, butyl Diethyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyldiisobutylmalonate, diethyldinormalbutylmalonate, dimethyl maleate, monooctyl maleate,
Diisooctyl maleate, diisobutyl maleate,
Diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methyl gludalate, diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarbamcarbonates such as diethyl itaconate, diisobutyl itaconate, diisooctyl citrate, dimethyl citrate; diethyl 2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Aliphatic polycarboxylic acid esters such as monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono n-butyl phthalate, n-butyl ethyl phthalate; Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate,
Diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, trimellitic acid Aromatic polycarboxylic acid esters such as dibutyl; and esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid.

Other examples of polycarboxylic acid esters include long adducts such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. Esters derived from chain dicarboxylic acids can be mentioned.

Among these polycarboxylic acid esters, compounds having a skeleton represented by the above-mentioned general formula are preferred, and more preferably phthalic acid, maleic acid, substituted malonic acid and the like, and alcohols having 2 or more carbon atoms are derived. Esters, phthalic anhydride and phthalic chloride are preferred, and diesters, phthalic anhydride and phthalic chloride obtained by reacting phthalic acid with an alcohol having 2 or more carbon atoms are particularly preferred.

As these polyvalent carboxylic esters, it is not always necessary to use the above-mentioned polyvalent carboxylic esters as starting materials, and for example, carboxylic acids and acid halides corresponding to the above-described esters, such as acid anhydrides, In the process of preparing the solid titanium catalyst component [A], using a compound capable of deriving these polycarboxylic acid esters,
A polyvalent carboxylic acid ester may be generated at the stage of preparing the solid titanium catalyst component [A].

In the present invention, when preparing the solid titanium catalyst component [A], an electron donor other than the polyvalent carboxylic acid ester can be used, and an electron other than the polyvalent carboxylic acid that can be used in the present invention can be used. As the donor, as described below, alcohols, amines, amides, ethers,
Ketones, nitriles, phosphines, stippines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, etc. And amides and salts of metals belonging to Groups I to IV of the Periodic Table.

In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium) into contact with an electron donor and a titanium compound. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum.

The method for producing the solid titanium catalyst component [A] will be briefly described below with several examples.

(1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. When reacting as described above, the solid compound may be pulverized.
Furthermore, when reacting as described above, each component may be pretreated with an electron donor and / or a reaction assistant such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once.

(2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium complex.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A solid obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. In this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

(9) magnesium compound and alkoxytitanium and / or
Or a method in which a catalyst component in a hydrocarbon solution containing at least an electron donor such as alcohol or ethanol is reacted with a halogen-containing compound such as a titanium compound and / or a halogen-containing silicon compound. A method in which an electron donor represented by diethyl phthalate as described above coexists.

Among the methods for preparing the solid titanium catalyst component [A] described in the above (1) to (9), a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a method using a titanium compound When used, a method using a halogenated hydrocarbon is preferred.

The amount of each of the above components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. In an amount of 5 moles, preferably 0.05-2 moles, the titanium compound is about 0.01-500
It is preferably used in an amount of 0.05 to 300 moles.

The solid titanium catalyst component [A] thus obtained
Contains magnesium, titanium, halogen and an electron donor as essential components.

In this solid titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 1
00 and the electron donor / titanium (molar ratio) is about 0.1
-10, preferably about 0.2 to about 6, magnesium /
It is desirable that titanium (atomic ratio) is about 1-100, preferably about 2-50.

This solid titanium catalyst component [A] contains magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 30 m ² / g.
Or more, preferably about 60~1000m ² / g, more preferably about 10
It is 0 to 800 m ² / g.

Such a solid titanium catalyst component [A] can be used alone, but also includes, for example, a silicon compound,
It can be used after being diluted with an inorganic compound or an organic compound such as an aluminum compound or polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity.

For a method of preparing such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-126590.
No. 51-20297, No. 51-28189, No. 51
No. 64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52-100596, No. 52-1
No. 47688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-43
No. 094, No. 55-135102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-119
No. 08, No. 56-18606, No. 58-83006,
JP-A-58-138705, JP-A-58-138706, JP-A-58-138707
JP-A-58-138708, JP-A-58-138709,
Nos. 58-138710, 58-138715, 60-23404
No. 61-21109, No. 61-37802, No. 61
And -37803.

As the organoaluminum compound catalyst component [B], a compound having at least one Al-carbon bond in the molecule can be used. Examples of such a compound include: (i) a compound represented by the general formula R ¹ _m Al (OR ² ) _{n Hp} X _q (wherein R ¹ and R ² each usually have 1 to 15 carbon atoms, preferably 1 to X is a hydrocarbon group containing four, and may be the same or different from each other, and X represents a halogen atom;
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0
.Ltoreq.q <3, and m + n + p + q =). An organoaluminum compound, (ii) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is a Li, Na, K, R ¹ is as defined above) alkylated complex of Group 1 metal and aluminum represented by And the like.

As the organoaluminum compound belonging to the above (i), the following compounds can be exemplified.

General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.
A general formula R ¹ _m AlX _3-m (where R ¹ is the same as above; X is a halogen, and m is preferably 0 <m <3); R ¹ _m AlH _3-m (wherein R ¹ is the same as above. M is preferably 2 ≦ m <3
In a), the general formula _{^{R 1 m Al (OR 2)}} n X q ( wherein, R ¹ and R ² are the same .X said halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
And the like.

Specific examples of the aluminum compound belonging to (i) include: trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; ; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide formula R ¹ _2.5 Al (OR ²⁾ partially alkoxylated alkyl aluminum having an average composition represented _0.5 like; diethylaluminum chloride, Dialkylaluminum halides such as dibutylaluminum chloride and diethylaluminum bromide; Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; Alkyl aluminum halides such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum Dialkylaluminum hydrides such as hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride and alkylaluminum dihydride such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethyl Partial access to aluminum ethoxy bromide Kokishi reduction and halogenated alkylaluminum can be exemplified.

Examples of the compound similar to (i) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, Methyl aluminoxane and the like can be mentioned.

Examples of the compound belonging to (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more kinds of aluminum compounds described above are bonded.

In the present invention, the electron donor [C] can be used as needed when producing the catalyst for the polymerization of olefins.

Examples of such an electron donor [C] include alcohols, phenols, ketones, aldehydes,
Oxygen-containing electron donors such as esters, ethers, acid amides, acid anhydrides and alkoxysilanes of carboxylic acids, organic acids or inorganic acids; Nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates; Polyvalent carboxylic acid esters and the like can be used.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, noelphenol, cumylphenol and naphthol; acetone , Methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, any ketone having 3 to 15 carbon atoms; acetaldehyde, propiona Aldehydes having 2 to 15 carbon atoms such as aldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate Propyl acetate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, n-butyl maleate, Diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethyl phthalate Organic acid esters having 2 to 30 carbon atoms such as xyl, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride Acid halides; ethers and diethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetotahydrofuran, anisole, diphenyl ether, epoxy-p-menthane; acetate amide, benzoic acid Acid amides such as amide, toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; acetonitrile Nitriles such as toluene, benzonitrile and tolunitrile; and acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

Further, as the electron donor [C], an organosilicon compound represented by the following general formula [Ia] can also be used.

R _n Si (OR ′) _4-n [I a] wherein R and R ′ are hydrocarbon groups, and 0 <n <
4] Specific examples of the organosilicon compound represented by the above general formula [Ia] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t -Butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bism-tolyldimethoxysilane, Bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyl Ethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltri Methoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-
Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane,
Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltrimethylsilane Allyloxy silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like are used.

Among them, trimethylmethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane,
Phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-
Preferred are tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyldiethoxysilane.

Further, as the electron donor [C], an organosilicon compound represented by the following general formula [IIa] can be used.

SiR ¹ R ² _m (OR ³ ) _3-m ... [IIa] wherein R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is an alkyl group, a cyclopentyl group and cyclopentyl having an alkyl group A group selected from the group consisting of groups, R ³ is a hydrocarbon group, and m is 0 ≦ m ≦ 2. In the above formula [IIa], R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and specifically as R ¹ , besides the clopentyl group, for example, 2
And cyclopentyl groups having an alkyl group such as -methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group.

In the formula [IIa], R ² is any one of an alkyl group, a cyclopentyl group and a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, an alkyl group such as hexyl, or cyclopentyl group having an exemplified cyclopentyl group and an alkyl group as R ¹ can be exemplified similarly.

In addition, our in formula [II a], R ³ is a hydrocarbon group, R ³
Examples thereof include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Among these, it is preferable to use an organosilicon compound in which R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, particularly a methyl group or an ethyl group.

Specific examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane and dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane and dicyclopentylmethyl Methoxysilane, dicipopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldi Chill silane, mono-alkoxysilanes such as cyclopentyl dimethylethoxysilane, and the like.

As the electron donor [C], the above-mentioned organic carboxylic acid esters and organic silicon compounds are preferable, and the organic silicon compounds are particularly preferable.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and, if necessary, the electron donor [C]. I have.

In the present invention, in the presence of the olefin polymerization catalyst, 3
-Methyl-1-butene and linear α- having 2 to 5 carbon atoms
Polymerizing propylene using a prepolymerization catalyst component [I] formed by prepolymerizing an olefin, and if necessary, the above [B] organoaluminum compound catalyst component and [C] an electron donor. To give 3-methyl-1
-A composition containing a butene polymer unit is obtained.

At this time, 3-methyl-1-butene has a content of the 3-methyl-1-butene polymer unit in the composition of 10 to 1000.
The prepolymerization is carried out in such an amount that it becomes 0 ppm.

3-methyl-1-butene is a solid titanium catalyst [A]
(Solid part in olefin polymerization catalyst) 0.1-100 per g
g, preferably 0.5-50 g, more preferably 1-10 g. Also, 3-methyl-1-
In pre-polymerizing butene, a small amount of α-olefin other than 3-methyl-1-butene may be copolymerized, and the copolymerization amount is within 20 mol%, preferably 10 mol%.
, Particularly preferably within 5 mol%.

In particular, in the present invention, the content of the 3-methyl-1-butene polymer unit in the composition is preferably from 100 to 3
By performing the prepolymerization in an amount such that the amount falls within the range of 000 ppm by weight, more preferably 100 to 1000 ppm by weight, a composition capable of forming a film having more excellent transparency is formed.

In the present invention, 3-methyl-
Before or after the prepolymerization with 1-butene, the prepolymerization is performed using a linear α-olefin having 2 to 5 carbon atoms. In this case, as the α-olefin, ethylene, propylene, n-butene-1, n-pentene-1 or the like can be used.

Since the pre-polymerization of the linear α-olefin is carried out as described above together with the pre-polymerization of 3-methyl-1-butene, polymer particles having little fine powder and high bulk specific gravity tend to be obtained.

Of these, it is particularly preferable to carry out prepolymerization using propylene or ethylene. In particular, when prepolymerization is performed using ethylene, a film having excellent blocking resistance tends to be obtained.

The α-olefin thus prepolymerized is such that the prepolymerization amount of the α-olefin polymer unit formed by the prepolymerization is from the above component [A], component [B] and, if necessary, component [C]. The amount is desirably 0.1 to 1000 g, preferably 1 to 500 g, more preferably 2 to 200 g per 1 g of the solid portion in the formed olefin polymerization catalyst.

In the prepolymerization as described above, the concentration of the catalyst in the reaction system can be used at a concentration equal to or higher than the concentration of the catalyst in the main polymerization.

That is, the solid titanium catalyst component [A] in the prepolymerization is usually 0.001 to 200 mmol, preferably 0.1 to 1 in terms of titanium atoms per hydrocarbon solvent described below.
It is used in an amount of 00 mmol, particularly preferably 1 to 500 mmol.

The organoaluminum catalyst component [B] is used usually in an amount of 0.1 to 500 mol, preferably 1 to 100 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A].

The electron donor [C] is used as needed. When the electron donor [C] is used, the electron donor [C]
Is usually 0.1 to 100 mol, preferably 1 to 50 mol, per 1 mol of titanium atom in the solid titanium catalyst component [A],
Particularly preferably, it is used in an amount of 1 to 1 mol.

Such prepolymerization is carried out by adding 3-methyl-1-butene and an α-olefin having 2 to 5 carbon atoms in the presence of a catalyst as described above under mild conditions in an inert hydrocarbon medium or a monomer solvent. It is preferred to carry out the polymerization by polymerization.

Specific examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dotecan, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. However, in the prepolymerization, instead of the above-mentioned inert hydrocarbon medium, or using the monomer itself as a solvent together with the inert hydrocarbon medium, the polymerization can be carried out, and the prepolymerization is practically carried out without a solvent. You can also.

The temperature at the time of the prepolymerization may be a temperature at which the produced prepolymer is not substantially dissolved in the hydrocarbon medium,
Usually, the temperature is set in the range of -20 to + 100 ° C, preferably -20 to + 80 ° C, and more preferably 0 to + 40 ° C.

Further, the prepolymerization can be carried out while using a molecular weight modifier such as hydrogen gas.

The prepolymerization can be performed in a batch system or a continuous system. Further, both the batch system and the continuous system can be performed in combination. For example, after preliminary polymerization of 3-methyl-1-butene is performed in a batch system, polymerization of α-olefin can be performed in a continuous system.

As described above, by pre-polymerizing 3-methyl-1-butene and the above-mentioned α-olefin using the olefin polymerization catalyst as described above, the 3-methyl-1-butene weight around the olefin polymerization catalyst. A prepolymerized catalyst having a united unit and an α-olefin polymer unit (that is, an olefin polymerization catalyst that has been subjected to a process called prepolymerization) is formed.

The 3-methyl-1-butene polymer unit-containing composition used in the present invention is obtained by polymerizing at least propylene using the prepolymerized catalyst obtained as described above.
For example, it is obtained by copolymerizing propylene homopolymer or propylene with an α-olefin having 2 to 10 carbon atoms other than propylene.

The main polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization, suspension polymerization and monomer solvent polymerization or a gas phase polymerization method.

For example, suspension polymerization can be performed in an inert hydrocarbon medium.

Examples of the inert hydrocarbon medium used in this case include the aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and mixtures thereof exemplified in the above-described prepolymerization. Can be. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Further, as in the case of the preliminary polymerization, the monomer itself can be used as a solvent, and the main polymerization can be carried out in a substantially solvent-free state.

In the main polymerization, the solid titanium catalyst component [A]
In terms of Ti atom per polymerization volume, usually about 0.001 to
It is used in an amount of 0.5 mmol, preferably about 0.005 to 0.1 mmol. Although the organoaluminum compound catalyst component [B] is used as needed, the metal atom in the organoaluminum compound catalyst component is usually about 1 to 1 mole of titanium atom in the reaction system of the main polymerization. It is desirable that it be used in an amount such that it is 2000 moles, preferably about 5 to 500 moles. Further, the electron donor [C] is used as needed, and is usually about 0.001 to 10 mol, preferably about 0.01 to 2 mol, per 1 mol of metal atom in the organoaluminum compound catalyst component [B]. Especially preferably about 0.
It is desirable to use it in such an amount that it becomes 05 to 1 mol.

In the case of the main polymerization, a molecular weight modifier such as hydrogen gas may be used.

The main polymerization temperature is usually about 0 to 200 ° C, preferably about 10 ° C.
At 〜100 ° C., the pressure is usually set at normal pressure to 100 kg / cm ² , preferably about normal pressure to 40 kg / cm ² .

The main polymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system.

The 3-methyl-1-butene polymer unit-containing composition formed as described above contains 3-methyl-butene as described above.
The 1-butene polymer unit is contained in an amount within the range of 10 to 10,000 ppm, preferably within the range of 100 to 3000 ppm, more preferably within the range of 100 to 1000 ppm by weight.

The stretched polypropylene film according to the present invention is obtained by stretching a propylene unstretched film formed from the above-described composition containing a 3-methyl-1-butene polymer unit or by forming a film while stretching. can get.

That is, using the composition containing a 3-methyl-1-butene polymer unit as described above, an unstretched film is prepared by a conventionally known molding method, and a stretched film is formed. Stretched films can be produced.

The unstretched film used here is prepared by molding the above-mentioned 3-methyl-1-butene polymer unit-containing composition into a film using a molding method such as extrusion molding or injection molding. be able to. The molding temperature in this case may be at least the temperature at which the composition containing the 3-methyl-1-butene polymer unit is melted.
The temperature is set in the range of 220 to 300 ° C, preferably 250 to 290 ° C.

The unstretched film is usually prepared to have a thickness of 800 to 8000 μm, preferably 1000 to 4000 μm. Therefore, the unstretched film includes a so-called sheet-like film and a film-like film.

The stretched film of the present invention is obtained by stretching the unstretched film obtained as described above in at least one of the longitudinal direction and the transverse direction. Therefore, the stretched film of the present invention includes a uniaxially stretched film and a biaxially stretched film.

The stretching temperature of the unstretched film as described above is usually 13
The temperature is desirably 0 to 200 ° C, preferably 140 to 190 ° C. When the stretched film of the present invention is a biaxially stretched film, the stretching ratio under the above conditions is usually 20.
It is usually from 70 to 70 times, preferably from 40 to 60 times, and in the case of a uniaxially stretched film, usually from 2 to 10 times, preferably from 2 to 6 times.

Further, the stretched film of the present invention may be prepared as described above, in addition to a biaxially or uniaxially stretched film obtained by stretching an unstretched film, and a 3-methyl-1-butene polymer unit-containing composition. May be in a melted state and stretched while blowing a gas such as air. In this case, the draw ratio is usually set to be 4 to 50 times, preferably 9 to 16 times.

The stretched film of the present invention thus obtained is particularly excellent in transparency. This is thought to be because the 3-methyl-1-butene polymer unit contained in the composition reduces the spherulite size of the propylene-based polymer and increases the crystallization rate of polypropylene. Can be

That is, by using the composition containing the 3-methyl-1-butene polymer unit, the spherulite size of the propylene-based polymer is reduced and the crystallization is accelerated, and as a result, the transparency is high. It is presumed that the stretched film of the present invention is obtained. Compared with a composition obtained by a conventional method in which a 3-methyl-1-butene polymer unit and a propylene polymer unit are simply melt-blended, 3-methyl-1
-It is estimated that the above effects are exhibited because the dispersion and mixing state of the butene polymer unit and the polypropylene polymer unit is extremely good.

Further, since the composition containing 3-methyl-1-butene polymer unit used in the present invention contains a predetermined amount of 3-methyl-1-butene polymer unit serving as a polymer nucleating agent as described above, Therefore, the use of this dense composition makes it possible to shorten the production cycle of a stretched film.

In the production of the stretched polypropylene film of the present invention, the above-mentioned composition containing 3-methyl-1-butene polymer unit, other resins, further known additives, stabilizers,
A filler or the like can be blended.

In the molded polypropylene stretched film of the present invention,
A phenolic stabilizer is preferred because a stretched film with excellent heat stability and transparency can be obtained, and a phenolic stabilizer and an organic phosphite stabilizer are particularly preferred. This is preferable since a stretched film having excellent properties and transparency can be obtained.

Further, in the polypropylene stretched film molding of the present invention, when a higher fatty acid metal salt is blended, the thermal stability of the resin at the time of molding is improved, and the moldability is improved,
Problems associated with rusting and corrosion of the molding machine due to halogen gas caused by the catalyst can be suppressed. In particular, when the higher fatty acid metal salt is used in combination with the phenol-based stabilizer and / or the organic phosphite-based stabilizer as the stabilizer, an excellent surplus effect on moldability, transparency and heat resistance of the obtained stretched film is obtained. Is preferably achieved.

Specific examples of the phenolic stabilizer include, specifically, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-dicyclohexyl- 4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2, 6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl-2-ethyl-6-tert-octylphenol, 2-isobutyl-4-ethyl-5 t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, dl-α-tocophenol, t-butylhydroquino 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6- t-butylphenol), 4,4'-thiobis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-
t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5- Di-t-
Butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4-4hydroxyphenyl) propionate], N, N'-hexamethylenebis (3 , 5-di-t-butyl-
4-4 hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzyldiphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4)
-T-4butylbenzine) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2) , 6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, bis (ethyl 3,3,5-di-tert-butyl-4-hydroxybenzylphosphonate) calcium, bis ( Ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel, bis [3,3-bis (3-t-butyl-4-hydroxyphenyl) butyric acid] glycol Ether, N, N'-bis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2' Ogizamidobisu [ethyl-3- (3,5-di -t
-Butyl-4-hydroxyphenyl) propionate], bis [2-t-butyl-4-methyl-6- (3-t-
Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- (β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl] -2, 4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3,5-di-t-butyl-4-)
Hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane, and β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester.

As the above-mentioned phenolic stabilizer, β- (3,5-di-t-
When an alkyl ester of (butyl-4-hydroxyphenyl) propionic acid is used, an alkyl ester having 18 or less carbon atoms is particularly preferably used.

Also in the molecule Or A phenolic stabilizer having a structure represented by the following formula is preferred.

However, in the above formulas, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms, R ³ carbons 1
Represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R ₄ has an alkyl group having 1 to 22 carbon atoms or the following structure.

(Here, m + n = 3, n = 0, 1, 2, 3) (Where R ₅ : It is. ) Among them, 2,6-di-tert-butyl-4-methyl-p-cresol, stearyl-β- (4-hydroxy-3,5-di-tert-butylphenol) propionate, 2,2′-ethylidenebis (4,6-di-tert-butylphenol), tetrakis [methylene-3- (3,5-di-t
[ert-butyl-4-hydroxyphenyl) propionate] methane is preferred.

These phenolic stabilizers can be used alone or as a mixture.

Examples of the phosphite-based stabilizer include trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite. Diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris ( Butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4,4'-isopropylidene-diphenolalkylphosphite Aite (however, alkyl has about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl)- 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4,4'-butylidenebis (3
-Methyl-6-t-butylphenol) diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octyl) Phenyl) bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)]
1,6-hexaneol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4
-Hydroxy-5-t-butylphenol) diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, tris (1,3-distearoyloxyisopropyl)
Phosphite, 9,10-dihydro-9-phosphaphenanthrene-10-
Oxide, tetrakis (2,4-di-t-butylphenyl) 4,4'-
Biphenylenediphosphonite and the like can be mentioned.

Among these, tris (2,4-di-tert-butylphenyl) host phyte, tris (nonylphenyl)
Phosphites and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphite are preferred, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred.

Further, a phosphite-based stabilizer derived from pentaerythritol represented by the following formula can also be used.

In the above formulas (1) and (2), R ¹ and R ² represent an alkyl group.

Such organic phosphite-based stabilizers can be used alone or in combination.

Examples of higher fatty acid metal salts include alkali metal salts, alkaline earth metal salts, and other metal salts of saturated or unsaturated carboxylic acids having 12 to 40 carbon atoms. Further, the saturated or unsaturated carboxylic acid having 12 to 40 carbon atoms may have a substituent such as a hydroxyl group. Specifically, examples of saturated or unsaturated carboxylic acids having 12 to 40 carbon atoms include stearic acid, oleic acid, lauric acid, capric acid, arachidonic acid, palmitic acid, behenic acid and 12-hydroxystearic acid, montanic acid Higher fatty acids such as acids; and examples of metals which form salts by reacting with these higher fatty acids include alkaline earth metal salts such as magnesium, calcium and barium, and alkali metals such as sodium, potassium and lithium. Metals and cadmium, zinc and lead can be mentioned.

Specific examples of higher fatty acid salts include magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium arachidinate, behenin Barium acid, zinc stearate, zinc oleate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate and calcium 12-hydroxystearate, sodium montanate, Examples thereof include calcium montanate and zinc montanate.

Among these higher fatty acid metal salts, especially those having 12 to
Zinc salts of 35 saturated fatty acids are particularly preferred.

Such higher fatty acid metal salts can be used alone or in combination.

The compounding ratio of the phenolic stabilizer is 0.01 to 10% by weight, preferably 0.02 to 0.5% by weight, particularly preferably 0.03 to 0.2% by weight, based on the molding raw material resin, and the compounding ratio of the organic phosphite-based stabilizer is the same. 0.01 to 1.0% by weight, preferably 0.02 to 0.5% by weight, particularly preferably 0.03 to 0.2% by weight.
% By weight, and the mixing ratio of the higher fatty acid metal salt is also 0.1%.
It is from 0.01 to 1.0% by weight, preferably from 0.02 to 0.5% by weight, particularly preferably from 0.03 to 0.2% by weight.

Effect of the Invention Since the stretched polypropylene film according to the present invention is formed from the composition containing a 3-methyl-1-butene polymer unit, it is particularly excellent in transparency.

In addition, by using the composition containing a 3-methyl-1-butene polymer unit, the crystallization speed of the resin is increased, so that a film having excellent transparency can be manufactured in a short time.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Solid Titanium Catalyst Component [A] Anhydrous magnesium chloride 7.14 kg, decane 37.5 and 2
-Ethylhexyl alcohol 35.1 was heated and reacted at 140 ° C for 4 hours to obtain a homogeneous solution. Thereafter, 1.67 kg of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above-mentioned homogeneous solution.

After cooling the thus obtained homogeneous solution to room temperature, the whole solution was dropped into titanium tetrachloride 200 kept at -20 ° C over 3 hours. After the dropwise addition, the temperature of the resulting solution was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., 5.03 of diisobutyl phthalate was added.

Stir at the above temperature for another 2 hours. After the completion of the reaction for 2 hours, a solid portion was collected by filtration under hot conditions, and the solid portion was collected for 275 hours.
Was re-suspended in TiCl ₄ and heated again at 110 ° C. for 2 hours.

After the completion of the reaction, a solid portion was collected again by hot filtration and washed with hexane. This washing was performed until no titanium compound was detected in the washing solution.

The solid titanium catalyst component [A] synthesized as described above was obtained as a hexane slurry. A part of the catalyst was collected and dried. When the dried product was analyzed, the composition of the solid titanium catalyst component [A] obtained as described above was determined to be 2.4% by weight of titanium, 59% by weight of chlorine, 18% by weight of magnesium, and 11.6% by weight of diisobutyl phthalate.
% By weight.

[Preliminary polymerization] After adding 100 moles of purified hexane, 3 moles of triethylaluminum and 1 mole of the titanium catalyst component [A] in terms of titanium atoms to a reactor purged with nitrogen, the temperature of the suspension was reduced to 15 to 20 ° C. While maintaining, propylene was fed at a rate of 2130 Nl / hour under stirring over 1.5 hours. After the supply of propylene was completed, the reactor was closed, and polymerization of the remaining propylene was carried out for 30 minutes.
Mol, 5 mol of trimethylmethoxysilane and 5.9 kg of 3-methyl-1-butene were added and stirred and mixed at 20 ° C. for 3 hours to carry out prepolymerization of 3-methyl-1-butene. After the completion of the prepolymerization, it was sufficiently washed with purified hexane.
As a result of analysis, the prepolymerized amount of the propylene polymer unit was 2.8 g.
/ g catalyst solid portion, and the prepolymerized amount of the 3-methyl-1-butene polymer unit was 2.4 g / g catalyst solid portion.

[Polymerization] Using a polymerization vessel having a content of 250, propylene homopolymerization was continuously performed. The polymerization pressure was controlled at 8 kg / cm ² G, and the polymerization temperature was controlled at 70 ° C. The catalyst component is triethyl aluminum
18 mmol / h, dicyclohexyldimethoxysilane
The titanium catalyst component prepolymerized with 1.8 mmol / hr of propylene and 3-methylbutene-1 prepared as described above was continuously supplied based on a rate of 0.24 mmol / hr in terms of titanium atoms. The resulting polypropylene was discharged continuously.

The production rate of the obtained polypropylene is about 10 kg on average
/ H. 3-methyl-1- in polypropylene
The butene polymer unit content was 140 ppm by weight.

[Production method of biaxially stretched film] 0.1 part by weight of calcium stearate as a stabilizer and 100 parts by weight of the composition containing a 3-methylbutene-1 polymer unit obtained as described above, and BHT (2,6-di- Tert-butylhydroxytoluene) 0.1 part by weight, Irganox 101
0 (manufactured by Ciba-Geigy, antioxidant, tetrakis [methylene-3- (3 ', 5'-di-tert-butylhydroxyphenyl) propionate] methane) 0.1 part by weight was added and mixed with a Henschel mixer, followed by 650 mmφ extrusion. The mixture was granulated into pellets at a kneading temperature of 220 ° C.

Next, the obtained pellets were treated with a 90 mmφ sheet extruder for 28 hours.
The sheet was extruded at 0 ° C. and formed into a 1.5 mm thick sheet with a cooling roll at 30 ° C. Next, the obtained sheet is stretched 5 times at a stretching temperature of 145 ° C. in a longitudinal direction with a tenter-type sequential biaxial stretching apparatus,
Subsequently, the film was stretched 10 times in the transverse direction in a tenter having an in-layer temperature of 170 ° C. to obtain a biaxially stretched film having a thickness of about 30 μm.

[Film Evaluation Method] (1) Visual Perspective Evaluation Five 30 μm-thick films were superimposed, and the perceived visual perception when the light of a fluorescent lamp was viewed through the film was visually evaluated in five stages (5...).
Good, 1 bad) evaluations were made.

(2) Dispersed transmitted light intensity (LSI) It was measured by an LSI tester manufactured by Toyo Seiki.

(3) Haze Measured according to ASTM D1003.

(4) Spherulite Diameter The diameter of the spherulite in the cross section of the raw sheet before biaxial stretching was measured by a stereoscopic microscope (× 100).

The smaller the spherulite size of the raw sheet, the better the transparency of the biaxially stretched film tends to be. Therefore, it was used as a scale for obtaining a film with good transparency.

 Table 1 shows the results.

Example 2 [Preliminary polymerization] Purified hexane 100, triethylaluminum 10 mol, trimethylmethoxysilane 10 were placed in a reactor purged with nitrogen.
Moles of the titanium catalyst component [A] is 1 in terms of titanium atoms.
After addition of 10 kg of mol and 3-methyl-1-butene,
The suspension was maintained at 20 ° C. for 3 hours with stirring,
Preliminary polymerization of methyl-1-butene was performed. As a result of the analysis, the prepolymerization amount of the 3-methyl-1-butene polymer unit was
It was 3.9 g / g catalyst solid part. Then, the stirring was stopped, the solid portion was allowed to settle, and the supernatant was removed. After washing twice with hexane, adjusting the total volume to 120, 3 mol of triethylaluminum was added, and propylene was supplied at a rate of 2130 Nl / hour for 1.5 hours to perform prepolymerization of propylene. Meanwhile, the prepolymerization temperature was maintained at 15 to 20 ° C. After the supply of propylene was completed, the reactor was closed, polymerization of the remaining propylene was performed for 30 minutes, and the mixture was washed twice with hexane. As a result of the analysis, the prepolymerized amount of the propylene polymer unit was
It was 2.7 g / g catalyst solid part.

[Polymerization] Propylene was polymerized in the same manner as in Example 1. As a result, the content of the 3-methyl-1-butene polymer unit in the produced polypropylene was 220 ppm. A film was prepared in the same manner as in Example 1, and the film was evaluated.

 Table 1 shows the results.

Comparative Examples 1-2 In Examples 1 and 2, 3-methyl-1-
Except for omitting the prepolymerization of butene and propylene,
It carried out similarly to Example 1 and Example 2.

 Table 1 shows the results.

Example 3 A solid titanium catalyst component [A] was prepared in the same manner as in Example 1.

Purified hexane 100, triethylaluminum 10 mol, trimethylmethoxysilane 10 in a reactor purged with nitrogen
Moles of the titanium catalyst component [A] is 1 in terms of titanium atoms.
After addition of 10 kg of mol and 3-methyl-1-butene,
The suspension was maintained at 20 ° C. for 3 hours with stirring,
Preliminary polymerization of methyl-1-butene was performed. As a result of the analysis, the prepolymerized amount of 3-methyl-1-butene was 3.9 g / g solid catalyst. Then, the stirring was stopped, the solid portion was allowed to settle, and the supernatant was removed. After washing twice with hexane, adjusting the total volume to 120, triethyl aluminum 3
After the moles were added, ethylene was supplied at a rate of 3150 Nl / hour for 2 hours to perform prepolymerization of ethylene. Meanwhile, the prepolymerization temperature was maintained at 15 to 20 ° C. After the supply of ethylene was completed, the reactor was closed, polymerization of residual ethylene was carried out for 30 minutes, and the resultant was washed twice with hexane. As a result of the analysis, the amount of prepolymerization with ethylene was 2.8 g / g solid catalyst part.

[Polymerization] Propylene was polymerized in the same manner as in Example 1. As a result, the content of poly-3-methyl-1-butene in the produced polypropylene was 260 ppm. A film was prepared in the same manner as in Example 1, and the film was evaluated.

 Table 1 shows the results.

[Brief description of the drawings]

FIG. 1 is a flowchart showing the production of the composition containing a 3-methyl-1-butene polymer unit used in the present invention.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FIB29L 7:00 C08L 23:10 (72) Inventor Masaya Yamada 3rd Chigusa Kaigan, Ichihara-shi, Chiba Mitsui Oil Chemical Industry Co., Ltd. (56) References JP-A-1-217014 (JP, A) JP-A-1-311106 (JP, A) JP-A-2-265905 (JP, A) JP-A-2-283704 (JP, A) (58) Fields investigated (Int.Cl. ⁶ , DB name) C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18 C08L 23/00-23/36 C08F 4/60-4/70

Claims (1)

(57) [Claims] [A] A magnesium, a titanium, a halogen and an electron donor obtained by reacting a liquid magnesium compound having no reducing property with a liquid titanium compound in the presence of an electron donor are essential. 3-methyl-1-butene in the presence of a solid titanium catalyst component [B], an organoaluminum compound catalyst component and, if necessary, [C] an olefin polymerization catalyst [I] formed from an electron donor. Is preliminarily polymerized and then preliminarily polymerized with a linear α-olefin having 2 to 5 carbon atoms, and if necessary, the above [B] organoaluminum compound catalyst component and [C] The propylene is polymerized using an electron donor, or the olefin is polymerized in the presence of the olefin polymerization catalyst [I].
The pre-polymerization catalyst component formed by pre-polymerizing the linear α-olefin of the above and then pre-polymerizing 3-methyl-1-butene, and if necessary, the [B] organoaluminum compound catalyst component and [ C] 3-olefin obtained by polymerizing propylene using an electron donor.
Containing a methyl-1-butene polymer unit, the α-olefin polymer unit and a propylene polymer unit, and
Methyl-1-butene polymer unit content is 10 to 10,000 weight p
A stretched polypropylene film, which is formed from a composition containing a 3-methyl-1-butene polymer unit in the range of pm.