JPH03163115A - Oriented polypropylene film - Google Patents

Abstract

PURPOSE:To improve the transparency by polymerizing propylene using a prepolymerized catalyst which is obtd. by the polymn. of a specific olefin in the presence of an olefin polymn. catalyst contg. a solid titanium catalyst component, and then forming the resulting polymer into a film. CONSTITUTION:In the presence of an olefin polymn. catalyst comprising a solid titanium catalyst component essentially contg. magnesium, titanium, halogen, and an electron donor, an organoaluminum compd. catalyst component, and if necessary an electron donor, 3-methyl-1-butene is polymerized and then a 2-5C liner alpha-olefin is polymerized, giving a prepolymerized catalyst. In the presence of the prepolymerized catalyst and, if necessary, the organoaluminum compd. catalyst component and the electron donor, propylene is polymerized to give a polymer contg. 3-methyl-1-butene units (in an amt. of 10-10000ppm) and the alpha-olefin units. The resulting polymer is used to produced an oriented film.

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention is produced from compositions containing 8-methyl-1-butene polymer units in which 3-methyl-1-butene polymer units are intimately blended into propylene polymer units. Regarding polypropylene stretched film. Technical Background of the Invention There have already been many proposals regarding methods for producing solid titanium catalyst components containing magnesium, titanium, halogen, and electron donors as essential components. It is also known that by use in the polymerization of α-olefins, especially propylene, polymers with high stereoregularity can be produced in high yields. In addition, when producing a propylene polymer using an olefin polymerization catalyst component consisting of a solid titanium catalyst component and an organoaluminum compound catalyst component as described above, 3-methyl- It is known that by combining 1,000 Qm of -butene, a brobylene m-group having excellent properties can be obtained. The inventors of the present invention conducted further intensive studies based on the above findings, and found that the above method could be used. By forming the recycled resin composition into a film, it is possible to create a film with excellent transparency that could not be achieved with conventional polypropylene. The present invention was achieved based on the discovery that the rate of conversion is increased. 11th aspect of the invention The present invention was made in view of the prior art as in the above, and specifically aims at making a stretched polypropylene film with excellent transparency. Outline of the polypropylene stretched film according to the present invention, [A]
A solid titanium catalyst containing magnesium, titanium, halogen, and an electron donor as essential components [B] An olefin polymer catalyst formed from an organoaluminum compound catalyst component and optionally [C] an electron donor [In the presence of N 3
- A prepolymerized catalyst formed by prepolymerizing methyl-1-butene and then prepolymerizing a straight triangular α-olefin having 2 to 5 carbon atoms, and optionally the above [B] Organoaluminum compound catalyst component and [C] 71
Propylene is polymerized using a K-child donor, or a linear α-olefin having 2 to 5 carbon atoms is prepolymerized in the presence of R of the olefin polymerization catalyst [I], and then 3-methyl- Pre-1ii polymerization catalyst component [I] formed by prepolymerizing 1-butene, and optionally the above [B] organoaluminum compound catalyst component [C]
A 3-methyl-1-butene polymer unit obtained by polymerizing propylene using a 71 child donor, a Joki α-olefin polymer unit, and a propylene polymer f
li-position, and the content of the 3-methyl-1-butene polymer units is in the range of 10 to 10,000 pp+n by weight. It is characterized by The polypropylene rolled film according to the present invention is a composition in which specific amounts of 3-methyl-i-butene polymer units and propylene polymer units are intimately blended (in the present invention, such a composition is It is particularly excellent in transparency because it has the shape of an r3-methyl-1-butene polymer (sometimes also referred to as a "composition containing a polymer in a positional position"). Detailed Description of the Invention The polypropylene stretched film according to the present invention will be described in detail below. The polypropylene spread film according to the present invention is a combination of 3-methyl-1-butene! 11. It is formed from a phase-containing H phase composition. This 3-methyl-1-butene polymer? A composition containing a 3-methyl-1-butene polymer position in which the 11th position and the 11i position of a propylene polymer are intimately blended is, for example, a composition containing an olefin polymerization catalyst as described below. Produced by polymerizing propylene using a prepolymerized catalyst [I] obtained by prepolymerizing 3-methyl=1-butene and a straight button α-olefin having 2 to 5 carbon atoms. Compositions can be exemplified. The 3-methyl-1-butene polymer + 1t-position H-containing composition used in the present invention is formed from a 3-methyl-1-butene polymer unit and a linear α-olefin having 2 to 5 carbon atoms. α-olefin polymer unit and propylene f
This is a composition in which the fl coalescence and the 11th position are homogeneously blended in the same manner as above. Such an intimately blended 3-methyl-1-butene polymer matrix composition is
In some cases, it is also called a block copolymer of poly-3-methyl-1-butene, a linear poly-α-olefin having 2 to 5 carbon atoms, and polybrobylene. Next, the 3-methyl-1-butene polymer il used to form the polypropylene stretched film according to the present invention
The method for producing the composition containing the j-position will be specifically explained. This 3-methyl-1-butene polymer tit position-containing composition can be produced using, for example, 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]. . Figure 1 shows 3 using the above-mentioned olefin polymerization catalyst.
- An example of a flowchart of a method for producing a methyl-1-butene-containing composition is shown. The solid titanium catalyst component [A] used in the present invention 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, the titanium compound used for preparing the solid titanium catalyst component [A] is, for example, TI (OR
) X (R is a hydrocarbon atom, X is a g4-g halogen atom, 05g≦4) and tetravalent titanium compounds can be mentioned. More specifically, Ti(OCH3)(13, Tl(OC2H5)Cρ3, Tl(On-C4Hta) C1' 3
, TI(OC2H5)B'3, TI(O Iso C 4H ta ) B ra
Trihalogenated alkoxy titanium such as; TI(OCH3)2CfI2, TI(QC2H5)2 Cll2, T I(O n-C4H9 > 2 C12
, T1(OC2H5)2Br2; monohalogenated trialkoxy titanium such as TI(OCH3) 3(1, TI(QC2H5) 3Cl, TI(On-C4H9) 3CD . TI(QC2H5) 3Br Titanium; TI(OCH3)4, TI(OC2H5)4, Tt(on-c,aH9)4TI
Examples include tetraalkoxytitanium such as (Olso-C4H9)4TI(02-ethylhexyl)4. Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is more preferred. These titanium compounds #11 may be used alone, or two or more types may be used in combination. Furthermore, 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 in the preparation of the isoformic titanium catalyst component [A] include magnesium compounds that have reducing properties and magnesium compounds that do not have reducing properties. Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium, diprobylmagnesium, diptyltmagnesium, diamylmagnesium, dihexylmagnesium, dioctylmagnesium, didecylmagnesium, decylbutylmagnesium, and ethylmagnesium. Dialkylmagnesiums such as butylmagnesium; alkylmagnesium halides such as ethylmagnesium chloride, probylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butylmagnesium halide; alkylalkoxymagnesiums such as butylethoxymagnesium, etc. can. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid. Furthermore, the alkyl group in the above-mentioned magnesium compound 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; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxychloride. Alkoxymagnesium halides such as magnesium and octoxymagnesium chloride; Allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; Ethoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n-octoxymagnesium,
Alkoxymagnesiums such as 2-ethylhexoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate; and the like. These non-reducing magnesium compounds may be compounds derived from the above-mentioned magnesium compound having reducing properties or compounds 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 can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. It may be brought into contact with a compound such as. In addition, in the present invention, the magnesium compound includes, in addition to the above-mentioned reducing magnesium compounds and non-reducing magnesium compounds, complex compounds, composite compounds, or other metal compounds of the above-mentioned magnesium compounds and other metals. It may be a mixture of. Magnesium metal can also be used as a starting material. Furthermore, a mixture of two or more of the above compounds may be used. Any magnesium compound other than those mentioned above can be used in the present invention. In any case, part or all of it must ultimately be halogenated. Among these magnesium compounds, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride, and alyloxymagnesium chloride are preferably used. . In the present invention, the electron donor used in the preparation of the solid titanium catalyst component [A] is preferably a polyhydric carboxylic acid ester, specifically, an ester represented by the following formula: I ' Compounds having a J- rating are mentioned. In the above formula, R1 is a substituted or unsubstituted hydrocarbon group, R 2 R 5 R 6 is a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and RR is a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and RR is a hydrogen atom or a substituted or unsubstituted hydrocarbon group. It is a hydrocarbon group. In addition, R3
It is preferable that at least one of R4 is a substituted or unsubstituted hydrocarbon group. Also R3 and R4. may be connected to each other to form a cyclic structure. Here, as the substituted hydrocarbon group,
Examples include substituted hydrocarbon groups containing different atoms such as N, O, and S, such as -C-0-C- -COOR, -COOH, -OH,
Examples include substituted hydrocarbon groups having structures such as -So3H and -C-N-C- -NH2. l2 Among these, diesters derived from dicarboxylic acids in which at least one of RR is an alkyl group having 2 or more carbon atoms are preferred. Specific examples of polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate,
Diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethyl malonate,
Diethyl isobrobyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl allyl malonate, diethyl diisobutyl malonate, diethyl di-n-butyl malonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, Fats such as diisobutyl maleate, diisobutyl butyl maleate, diethyl butyl maleate, diisoprobyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconate, dimethyl citraconate, etc. Group polycarboxylic acid ester; diethyl 2-cyclohexanecarboxylate, l. Aliphatic polycarboxylic acid esters such as diisobutyl 2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl phthalate Isobutyl, mono-n-butyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate,
Diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, diptyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate aromatic polycarboxylic acid esters such as; esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid; and the like. Other examples of polyhydric carboxylic acid esters include long complexes such as diethyl adipate, diisobutyl adipate, diisobrobyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. Mention may be made of esters derived from dicarboxylic acids. Among these polyhydric carboxylic acid esters, compounds having a skeleton represented by the above-mentioned general formula are preferred, and compounds derived from phthalic acid, maleic acid, substituted malonic acid, etc. and an alcohol having 2 or more carbon atoms are more preferred. Preferred are esters, phthalic anhydride, and phthalic acid chloride, and particularly preferred are diesters obtained by reacting phthalic acid with an alcohol having 2 or more carbon atoms, phthalic anhydride, phthalic acid chloride, and the like. As these polyvalent carboxylic acid esters, it is not necessarily necessary to use the above-mentioned polyvalent carboxylic acid esters as starting materials, but for example, carboxylic acids, acid halides, and acid anhydrides corresponding to the aforementioned esters can be used. , a compound capable of inducing these polyvalent carboxylic acid esters is used in the preparation process of the solid titanium catalyst component [A] to generate the polyvalent carboxylic acid esters in the preparation process of the solid titanium catalyst component [A]. You can. In the present invention, when preparing the solid titanium catalyst component [A], an electron donor other than the polyvalent carboxylic acid ester may be used, and an electron donor other than the polyvalent carboxylic acid that can be used in the present invention may be used. Examples of donors include alcohols, amines, amides, ethers, ketones, nitriles, phosphines, stipines, arsines, phosphoramides, esters, thioethers, thioesters, and acids, as described below. Organosilicon compounds such as anhydrides, acid halides, aldehydes, alcoholates, alkoxy(anoyloxy)silanes, organic acids, and amides of metals belonging to Groups 1 to 2 of the periodic table; Examples include salts. In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-described magnesium compound (or metallic magnesium), electron 9 bodies, and titanium compound into contact with each other. 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 compound can be employed. Note that the above-mentioned components may be brought into contact in the presence of other reaction reagents such as silicon, phosphorus, and aluminum. Several examples of methods for producing these solid titanium catalyst components [A] will be briefly described below. (1) A method of reacting a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor with a titanium compound in i&IO. This reaction may be carried out in the presence of 7r such as a grinding aid. Moreover, when reacting as described above, a solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. In addition, in this method, at least all of the above electron donors are used. (2) a liquid magnesium compound that does not have reducing properties;
A method of reacting with an ifl-like titanium compound under the conditions of electron 1j and body production to produce a solid titanium compound. (3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound. (4) To the reaction product obtained in (1) or (2),
Electronics Ij. How to further react titanium compounds with titanium compounds. (5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with either a halogen, a halogenated compound, or an aromatic hydrocarbon. How to process. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground under 7T rE such as a grinding aid. In addition, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor can be used as a titanium compound.
r: After being pulverized in the presence of water, it may be pretreated with a reaction aid, and then treated with a halogen or the like. Note that examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds. Note that in this method, an electron donor is used at least once. (6) A method of treating the compound obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of contacting a contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor and a titanium compound. (8) Magnesium compounds such as magnesium salts of organic acids, alkoxymagnesiums, aryloxymagnesiums, etc. are reacted with electron donors, titanium compounds and/or halogen eEt4 hydrocarbons. (9) Magnesium compound and alkoxytitanium and/
Alternatively, a method in which a catalyst component in a hydrocarbon compound containing at least an electron donor such as an alcohol or an ether is reacted with a titanium compound and/or a halogen-containing compound in a halogen-containing silicon compound cage, the method comprising: Electron (
n How to make Li coexist. The solid titanium catalyst components listed in (1) to (9) above [A
Among the preparation methods, preferred are methods using liquid titanium halide during catalyst preparation, methods using a halogenated hydrocarbon after using a titanium compound, or methods using a halogenated hydrocarbon when using a titanium compound. The amount of each of the above-mentioned components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor per mol of magnesium compound is about 0. 0.01 to 5 mol, preferably 0.05 to 2 mol, the titanium compound is about 0.01 to 5 mol, preferably 0.05 to 2 mol.
It is used in an amount of 0.01 to 500 mol, preferably 0.05 to 300 mol. The solid titanium catalyst component [A] thus obtained contains magnesium, titanium, halogen, and an electron donor as essential components. In the interstitial titanium catalyst component [A], the atomic ratio of norogen/titanium is about 4 to 200, preferably about 5 to 200.
100, the electron donor/titanium (molar ratio) is about 0.1 to 10, preferably about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is about 1 to 100, preferably about It is desirable that it is 2-50. This solid titanium catalyst component [A] contains magnesium halide that is smaller in size than commercially available magnesium halides, and usually has a specific surface area of about 30.
ryf/g or more, preferably about 60-100
0 rd/g, more preferably about 100-800
rf/g. Such a solid titanium catalyst component [A] can be used alone, but it can also be used diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin. Note that when a diluent is used, high catalytic activity is exhibited even if the specific surface area is smaller than the above-mentioned specific surface area. Regarding the preparation method of such a highly active titanium catalyst component, for example, Japanese Patent Application Laid-Open No. 150-108385,
5G-128590, 51-20297, 51-28189, 51-64586, 5'l-92885, 51-1368
Publication No. 25, Publication No. 52-87489, Publication No. 52-10
No. 0596, No. 52-14768FJ, No. 5
Publications No. 2-104593 and No. 53-2580! d-40093 publication J 53-40094 publication,
No. 53-43094, No. 55-135102, No. 55-135103, No. 55-15271
Publication No. 0, Publication No. 56-811, Publication No. 5B-11908
No. 5B-18806, No. 51t-430
No. 06, No. 58-138705, No. 5g-1
No. 38706, No. 58-138707, No. 5
g-138708, same. No. 58-138709, No. 58-138710, No. 58-13871
Publication No. 5, Publication No. 60-23404, Publication No. 81-211
Publication No. 09, Publication No. 81-37802, Publication No. 61-37
It is disclosed in Publication No. 803 and the like. As the aluminum compound catalyst component [B], a compound having at least one All-carbon bond in the molecule can be used. Examples of such compounds include (i) general formula R'lIIA[ (OR2) H
Xn p q (wherein Rl and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a halogen atom, 0<m≦3, n is 0≦n<3, p is 0≦p<3, q
is a number such that O≦q<3, and m + n + p
+ q - 3), an organoaluminum compound represented by the general formula M Examples include complex alkylated products of Group 1 metals and aluminum. Examples of organoaluminum compounds belonging to the above (i) include the following compounds: 2 General formula R' lll (OR ) 3 −m (in the formula,
R and R2 are the same as above. m is preferably a number of 1.5≦m≦3), general formula R' m
, l X3-, (wherein Rl is the same as above; AIH3-, (wherein R1 is the same as above. m is preferably 2≦m<3
), general formula R'IIIAj? (OR2) Xn9 (In the formula, R and R2 are the same as above.
n+q-3). More specifically, the aluminum compounds belonging to (i) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisobrenylaluminum; dialkylaluminum such as diethylaluminum ethoxide and dibutylaluminum butoxide. Alkoxide; Alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, 2.5 represented by the formula R i (OR), etc.
0.5 Partially alkoxylated alkylaluminums having a uniform composition; dialkylaluminum halides such as diethylaluminium chloride, diptylaluminum chloride, diethylaluminium bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride; Alkylaluminum sesquihalides such as bromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, probylaluminum dichloride, butylaluminum dibromide; dialkylaluminums such as diethylaluminum hydride, dibutylaluminum hydride Hydrides; Other partially hydrogenated alkyl aluminum dihydrides such as ethyl aluminum dihydride, probylaluminum dihydride; Partially hydrogenated alkylaluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide Mention may be made of alkoxylated and halogenated alkyl aluminums. Compounds similar to (i) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2 H5 ) 2 AρOA
R (C2H5)2, (C4H9)2AgOAD
(C4H9)2, methylaluminoxane, and the like. Examples of compounds belonging to the above (i) include LiAg (C2H5)4 and L t AN (C7H1.)4. Among these, especially trialkyl aluminum or the above-mentioned 2FI! It is preferable to use an alkyl aluminum to which the above aluminum compounds are bonded. In the present invention, when producing an olefin polymerization catalyst, an electron donor [C] can be used as necessary. Such electron donors [C] include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxysilanes. Nitrogen-containing electron bodies such as ammonia, amines, nitriles, and isocyanates; or polyhydric carboxylic acid esters such as those mentioned above 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, isopropyl benzyl alcohol Alcohols with 1 to 18 carbon atoms such as; phenols with 6 to 20 carbon atoms that may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, probylphenol, nonylphenol, cumylphenol, and naphthol; Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, penzophenone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde. Classes: Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, probyl acetate, octyl acetate, cyclohexyl acetate, ethyl probionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methi benzoate? , ethyl benzoate, brovyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-maleate
Butyl, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisobrobyl tetrahydrophthalate, diethyl phthalate,
G-acid esters having 2 to 30 carbon atoms, such as diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride, penzoyl Acid halides having 2 to 15 carbon atoms such as chloride, toluic acid chloride, anisyl chloride; methyl ether, ethyl ether, isobrobyl ether, butyl ether, amyl ether, tetrahydride ■Furan, anisole, diphenyl ether,
Ethers and di-ethers having 2 to 20 carbon atoms such as epoxy-p-menthane; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Methylamine, ethylamine, diethylamine, tributylamine, piperidine, and toluic acid amide; Amines such as livenzylamine, aniline, viridine, picoline, and tetramethylenediamine; nitriles such as acetonitrile, penzonitrile, and tolnitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride; and the like. Further, as the electron donor [C], the following general formula [I
Organosilicon compounds represented by al can also be used. RSi(OR') 4-n-[I a
ln [wherein R and R゜ are hydrocarbon groups, 0<n<
4] As the organosilicon compound represented by the above general formula [I al, specifically, l-limethylmethoxysilane, trinotylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyl Dimethoxysilane, 1-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis O-1lyldimethoxysilane, Bis alpha monotolyl dimethoxysilane, bis p monotolyl dimethoxysilane, bis I) lyldiethoxysilane, bisethyl phenyl dimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyl dimethoxysilane, cyclohexylmethyl diethoxysilane, ethyltri Methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chlorotrimethoxysilane, methyl Triethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, Iso-
Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisobuboxysilane,
Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornantrie-1-xysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane , methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane),
Vinyltriacetoxysilane, dimethylte1-raethoxydisiloxane, etc. are used. Among these, trimethylmethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, L-butyltriethoxysilane, vinyltriethoxysilane,
Phenyltriethoxysilane, vinyl!・Ributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p
-I-lylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenylgel 1.
Kinshiran is preferred. Furthermore, an organosilicon compound represented by the following general formula [I1a] can be used as the electron 1% donor [C]. [In the formula, R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is an alkyl group selected from the group consisting of a cyclopentyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, and R3 is a hydrocarbon group. , m is 0≦m≦2. ] In the above formula [IIa], Rl is cyclopentyl or cyclobentyl having an alkyl group, and R
Specifically, l is a cyclopentyl group having an alkyl moiety, such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, or a 2,3-dimethylcyclobentyl group, in addition to a clopentyl group. can be mentioned. Further, in formula [I1a], R2 is an alkyl group, a cyclopentyl group, or a cyclobentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a propyl group, an isobrobyl group, a butyl group, An alkyl group such as a hexyl group, or a cyclopentyl group having an alkyl group and a cyclobentyl group exemplified as Rl can be similarly mentioned. Further, in formula [I1a], R3 is a hydrocarbon group, and examples of R3 include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Among these, R1 is cyclopentyl, and R2
is an alkyl group or a cyclopentyl group, and R3 is an alkyl group, particularly a methyl group or an ethyl group. Specific examples of such silicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 23-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane; , bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dime!・Dialkoxysilanes such as xysilane, dicyclopentyldiethoxysilane ・Tricyclopentylmethoxysilane, 1-lycyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclobentyl Examples include monoalkoxysilanes such as dimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. As the electron donor [C], the above-mentioned organic carboxylic acid esters and organosilicon compounds are preferable, and organosilicon compounds are particularly preferable. The olefin polymerization catalyst used in the present invention comprises the above-mentioned solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and, if necessary, an electron donor [
C] It is shaped like this. In the present invention, 3-
Preliminary polymerization catalyst component [I] formed by preliminarily polymerizing methyl-1-butene and linear α-olefin having 2 to 5 carbon atoms, and optionally the above [B
] A composition containing a 3-methyl-1-butene polymer can be obtained by polymerizing propylene using an organoaluminum compound catalyst and an electron donor [C]. At this time, 3-methyl-1-butene is 3-methyl-1-butene in the above composition.
-Methyl-1-butene polymer content at qt position is 10 to 1
It is prepolymerized in such an amount that it becomes 0000ρpII1. 3-Methyl-1-butene is a solid titanium catalyst [A] (
Solid portion in olefin polymerization catalyst) 0.1 to Ig
100g, preferably 0.5-50g, more preferably 1
It is desirable to prepolymerize in an amount of ~10 g. Also,
When prepolymerizing 3-methyl-1-butene, 3
- A small amount of α-olefin other than methyl-1-butene may be copolymerized, and the amount of copolymerization is within 20 mol%,
It is preferably within 10 mol%, particularly preferably within 5 mol%. In particular, in the present invention, 3-methyl-
The a content at position 711 of the 1-butene polymer is preferably 10
0 to 3000 weight ppm, more preferably 1. O
By carrying out prepolymerization in an amount within the range of O to 1000 ppm, a composition capable of forming a film with even better transparency is formed. In addition, in the present invention, as mentioned above, 3-methyl-l
-P(ii!) using a linear α-olefin having 2 to 5 carbon atoms before or after polymerization
Perform lm matching. In this case, the α-olefin is
Ethylene, brobylene, n-butene-1, n-pentene-1, etc. can be used. Since the linear α-olefin is prepolymerized as described above in addition to the prepolymerization of 3-methyl-1-butene, polymer particles with less fine powder and a higher bulk specific gravity tend to be obtained. be. Among these, it is particularly preferable to use propylene or ethylene for prepolymerization. In particular, when ethylene is used for P6im combination, a film with excellent blocking resistance tends to be obtained. The α-olefin that is pre-fW polymerized in this way is pre-fW polymerized.
α-olefin polymer formed by fffl reaction!
The amount of prepolymerization at the l position is 0.1 to 1000 g per 1 g of solid portion in the olefin polymerization catalyst formed from the above [A] component, [B] component, and optionally [C] component, preferably 0.1 to 1000 g. 1 to 500g, more preferably 2 to 200g
It is desirable that the amount is such that . In the prepolymerization as described above, the concentration of the catalyst in the reaction system can be as high as or higher than the concentration of the catalyst in the main polymerization. That is, the solid titanium catalyst component [A
] is usually 0.001 to 200 mmol, preferably 0.001 to 200 mmol in terms of titanium atom per hydrocarbon solvent 11 described later.
．． It is used in amounts of 1 to 100 mmol, particularly preferably 1 to 500 mmol. The organoaluminum catalyst component [B] is usually used in an amount of 0.1 to 500 moles, preferably 1 to 100 moles, per mole of titanium atoms in the solid titanium catalyst component [A]. Electron donor [C] is used as necessary. When electron 1j donor [C] is used, electron 11
[C] is a solid titanium catalyst component [Usually used in an amount of 0.1 to 100 mol, preferably 1 to 50 mol, particularly preferably 1 to 10 mol, per 1 mol of titanium atoms in AE. . Such pre-polymerization is carried out using 3-methyl-1-butene and C2-5 α-polymerization in the presence of a catalyst as described above.
This is preferably carried out by polymerizing the olefin in an inert hydrocarbon medium or in a monomer solvent under mild conditions. Specifically, the inert hydrocarbon medium used in this case includes aliphatic hydrocarbons such as propane, butane, pentane, hexane, hebutane, octane, decane, dodecane, and kerosene; Examples include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, 1-toluene, and bovine sirene; 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, the prepolymerization can also be carried out using the monomer itself as a solvent instead of or in conjunction with the inert hydrocarbon medium mentioned above, and even prepolymerization can be carried out substantially in the absence of a solvent. You can also do that. The temperature during prepolymerization may be any temperature at which the prepolymer to be dissolved is not substantially dissolved in the hydrocarbon medium, and is usually -20 to +100°C, preferably -20 to +100°C.
The temperature is set at 80°C, more preferably within the range of 0 to +40°C. Further, the secondary fijlTr combination can also be carried out using a molecular weight modifier such as hydrogen gas. T-8 polymerization can be carried out in a homogeneous or continuous manner. Moreover, [I-part type and continuous type can be combined and carried out. For example, after preliminary polymerization of 3-methyl-1-butene is carried out in a homogeneous manner, the polymerization of α-olefin may be carried out in a continuous manner. In this way, by performing T-prepolymerization of 3-methyl-1-butene and the above-mentioned α-olefin using the above-mentioned olefin polymerization catalyst, an olefin! ]! The qt and α positions of the 3-methyl-1-butene polymer are located around the Aikawa catalyst.
- an olefin polymer unit (that is, an olefin polymerization catalyst that has been subjected to a process of prepolymerization) is formed. The composition containing a 3-methyl-1-butene ffi-coupled intermediate used in the present invention is obtained by polymerizing at least propylene using the preglow polymerization catalyst obtained as described above. For example, it can be obtained by copolymerizing propylene+11, or by copolymerizing propylene with an α-olefin having 2 to 10 carbon atoms other than propylene. (The following is a blank space) The main polymerization can be carried out using any of liquid river polymerization methods or gas phase polymerization methods such as solution polymerization, suspension polymerization, and monomer solution polymerization. For example, suspension polymerization can be carried out in an inert hydrocarbon medium. Examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, or mixtures thereof, as exemplified in the T-bill polymerization described above. can be mentioned. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Further, as in the preliminary polymerization, the monomer white body can be used as a solvent, and furthermore, the main polymerization can be carried out in a state substantially free of solvent. During the main polymerization, the solid titanium catalyst residue [A] is usually about 0.00 Ti atoms per polymerization volume ID.
1-0.5 mmol, preferably about 0.005-0.1
Used in millimolar amounts. In addition, the organoaluminum compound catalyst component [B] is used as necessary, but the metal atom in the organoaluminum compound catalyst component is usually about 1 mole of titanium atom in the reaction system of the main polymerization. It is desirable to use an amount of ~2000 moles, preferably about 5-500 moles. Further, the electron donor [C] is used as necessary, but is usually about 0.001 to 10 mol per mol of metal atom in the organoaluminum compound catalyst component [B].
Preferably about 0.01 to 2 mol, particularly preferably about 0
．． It is desirable to use an amount of 0.5 to 1 mole. During this main polymerization, a molecular weight regulator such as hydrogen gas may also be used. The main polymerization temperature is usually about 0 to 200°C, preferably about 1
From 0 to 100℃, the pressure is usually normal pressure to 100kg/(
4. Preferably, the pressure is set at about normal pressure to 40 kg/c. The main polymerization can be carried out in any of the batch, semi-continuous and continuous methods. The 3-methyl-1-butene polymer unit-containing composition formed as described above contains 10 to 10 3-methyl-1-butene polymer units in terms of ffIIJ1.
Within the range of 0 0 0 ppl, preferably 100-3
00Of)flllll, more preferably in an amount within the range of 100 to 1000 ppII1. The stretched polypropylene film according to the present invention is formed by stretching or while stretching an unstretched polypropylene film formed from a composition containing a 3-methyl-1-butene polymer unit as described above. It can be obtained by That is, the above-mentioned 3-methyl-■-butene polymer q
Using a composition containing the t-position, an unstretched film is prepared by a conventionally known molding method, and the stretched film is molded to produce the stretched film of the present invention, which has particularly excellent transparency. The unstretched film used here is obtained by forming the above-mentioned 3-methyl-1-butene polymer unit-containing composition into a film using a forming method such as compression molding or injection molding. It can be prepared by: In this case, the certain temperature may be at least the temperature at which the above-mentioned composite containing 3-methyl-1-butene ffi combined units is melted, and is usually 220-. The temperature is set at 300°C, preferably within the range of 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, this unstretched film includes what is called a 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 monoaxially stretched film and a biaxially stretched film. The stretching temperature of the unstretched film as described above is usually 13
It is desirable that the temperature is 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 to 70 times, preferably 40 to 60 times, and in the case of a uniaxially stretched film, the stretching ratio is usually 20 to 70 times, preferably 40 to 60 times. ~10 times, preferably 2
~6 times. Furthermore, the stretched film of the present invention can be used in addition to a biaxial or uniaxial g-shaped film prepared by preparing an unstretched film and stretching it as described above, as well as a 3-methyl-1-butene polymer containing a polymer at the tp position. Inflation may also be used, in which the material is molten and stretched while blowing in a gas such as air. The stretching ratio of 'MN' is usually set within a range of 4 to 50 times, preferably 9 to 16 times. The stretched film of the present invention obtained in this way has particularly excellent transparency. This is due to the 3-methyl-1-butene ff! contained in this composition. It is thought that this is because the coalesced units reduce the size of the spheres of the propylene-based polymer and speed up the rate at which the polypropylene forms into spheres. That is, by using a composition containing a 3-methyl-■-butene polymer unit, the sphere size of the propylene polymer is miniaturized and crystallization is accelerated. It is estimated that the stretched film of the present invention with high 3-methyl i-
Butene polymer qt tx and polypropylene polymer il1
It can be assumed that the above effect is produced because the dispersion and mixing state, such as the position, is extremely good. Further, the composition containing the 3-methyl-1-butene polymer position used in the present invention contains a predetermined amount of the 3-methyl-1-butene polymer at the j116 position, which becomes a polymer cough suppressant, as described above. Therefore, the rate of crystallization is fast, and therefore, by using this homogeneous composition, it is also possible to shorten the production cycle of stretched films. In addition, when producing the polypropylene stretched film of the present invention, other resins, as well as known additives, stabilizers, fillers, etc. are added to the above-mentioned composition containing the 3-methyl-1-butene polymer at the ili position. Can be blended. In the polypropylene stretched film of the present invention, it is preferable that a phenolic stabilizer is blended, since a stretched film with excellent heat resistance and transparency can be obtained, and in particular, a phenolic stabilizer and an organic phosphite stabilizer are blended. It is preferable that this is blended, since a stretched film having particularly excellent heat resistance stability and transparency can be obtained. In addition, in the molding of the polypropylene stretched film of the present invention, when a higher fatty acid metal salt is blended, the thermal stability of the resin during molding is improved, and the shapeability is improved, resulting in Jl- due to the catalyst. Nail of a precept machine using halogen gas! And troubles caused by corrosion can be suppressed. In particular, when the above-mentioned stabilizer, phenolic stabilizer and/or organic phosphite stabilizer, is used in combination with the higher fatty acid metal salt, the resulting stretched film has excellent moldability, transparency, and heat resistance. It is preferred because the effect is achieved. Examples of phenolic stabilizers include 2,6
-di-t-butyl-4-methylphenol, 2.6-di-L-butyl-4-ethylphenol, 2.6-dicyclohexyl-4-methylphenol, 2.6-diisobutyl-4-ethylphenol, 2 .6-di-L-amy-4-methylphenol, 2.6-di-t-octyl-4-n-propylphenol, 2.6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4- Methyl-et-butylphenol, 2-L-butyl-2-ethyl-6-L-octylphenol, 2-isobutyl-4-ethyl-5-L-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropyl Phenol, styrenated mixed cresol, dρ-α-tocophenol, t-butylhydroquinone, 2,2°-methylenebis(4-methyl-6-t-butylphenol), 4.4°-butylidenebis(3-methyl-6 -t-butylphenol), 4,4°-thiobis(3-methyl-et-butylphenol), 4.4°-thiobis(4-methyl-et-butylphenol), 4.4°-methylenebis( 2,2゜-methylenebis IJ-(1-methylcyclohexyl)-p-cresol], 2,2゜-ethylidenebis (4,6-di-L-butylphenol), 2.2"-butylidenebis(2-L-butyl-4-methylphenol), 1,1.3-tris(2-methyl-4-hydroxy-5
-L-butylphenyl)butane, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], l,6-hexanediol bis[3-(3.5- di-L-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis[3-(3.5-di-t-butyl-4-4hydroxyphenyl)propionate], N. N'-hexamethylenebis(3.5-dit)
-butyl-4-4-hydroxyhydrocinamide), 3
．． 5-di-t-butyl-4-hydroxybendimephosphonate diethyl ester, 1,3.5-1-lis(2,6-dimethyl-3-hydroxy-4-t-4butylbenzyl)isocyanurate,
1.3.5-}Lis((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-t-butyl-4-hydroxyphenyl)probionate comethane, bis(3,5-di-t-butyl-4-hydroxybenzyl ethyl)phosphonate calcium, bis(3,5-di-t-butyl-4-hydroxybenzyl ethyl phosphonate) ) Nickel, Bis[3.3-bis(3-t-butyl-4-hydroxyphenyl)butylic acid] glycol ester, N,N-bis[3-(3.5-di-t-butyl-4-hydroxyphenyl) enyl)propionyl]hydrazine, 2.2
゜-Ogizamide bis[ethyl-8-(3.5-di-t-
Butyl-4-hydroxyphenyl)propionate]
, bis[2-t-butyl-4-methyl-8-(3-L-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 1.3.5-trimethyl-2.4.8-tris(3,
5-di-t-butyl-4-hydroxybenzyl)benzene, 3.9-bis[I. 1-dimethyl-2-(β-(3
−

[-butyl-4-hydroxy-5-methylphenyl)
probionyloxy)ethyl]-2.4.111. 1
0-tetraoxaspiro[5.5]undecane, 2,2-bis[4-(2-(3.5-di-t-butyl-4-hydroxyhydrocinnamoyloxy))ethoxyphenyl]propane, β-( Examples include 3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester. As the above phenolic stabilizer, β-<3,5-di-t-
When using a butyl-4-hydroxyphenyl) propionic acid alkyl ester, an alkyl ester having 18 or less carbon atoms is particularly preferably used. Furthermore, phenolic stabilizers having a structure represented by or in the molecule are preferred. However, in the above formula, R is a hydrogen atom or has 4 carbon atoms.
R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, and R3 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R4 is an alkyl group having 1 to 22 carbon atoms or has the following structure. (Here, m+n=3, n-0.1.2.3.) R5 (Here, R5:) 1.2 Among these, 2.8-di-tart-butyl-4-
Methyl-p-cresol, stearyl-β-(4-hydroxy-3,5-di-tart-butylphenol) propionate, 2.2゜-ethylidene bis(4,6-di-tart-butylphenol), tetrakis[methylene-3- (3.5-di-tert-butyl-4-hydroxyphenyl)propionate]methane is preferred. These phenolic stabilizers can be used alone or in combination. Examples of phosphite stabilizers include trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, trisisodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl diisodecyl phosphite, and phenyl diisodecyl phosphite. (tridecyl)phosphite 1, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,
4-di-t-butylphenyl) phosphite 1., tris(butylphenyl) phosphite, tetratridecyl-4.4"-butylidenebis(3-methyl-e-
t-butylphenol)-diphosphite, 4,4゜-
Isopropylidene-diphenol alkyl phosphite (alkyl has about 12 to 15 carbon atoms), 4,4゜-isopropylidene bis(2-t-butylphenol) di(nonylphenyl) phosphite, Tris (biphenyl)phosphite, tetra(tridecyl) -1.1.3- }Lis(2-
Methyl-5-tobutyl-4-hydroxyphenyl)butane diphosphite, tetra(tridecyl)-4,4'-butylidenebis(
3-methyl-6-t-butylphenol) diphosphite, tris(3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4.4°-isopropylidenediphenol polyphosphite, bis(octylphenyl) )・Bis[4,4'-butylidenebis(3-methyl-et-butylphenol)]・
1,6-hexaneol diphosphite, hexatridecyl-t,t,a-tris(2-methyl-4hydroxy-5-t-butylphenol) diphosphite, tris[4,4°-isopropylidene bis(2- tert-butylphenol)] Phosphi-1., Tris(l,3-distearyloxyisoprobil)
Phosphite, 9,10-dihydro-9-phosphaphenanthrene-1
0-oxide, tetrakis (2,4-di-t-butylphenyl) 4.4
- Biphenylene diphosphonite and the like can be mentioned. Among these, tris(2,4-di-tart-butylphenyl) phosphite, tris(nonylphenyl) phosphite and tetrakis(2,4-di-tert)
t-butylphenyl) -4,4'-biphenylene diphophite is preferred, and tris(2,4-di-t
Particularly preferred is art-butylphenyl) phosphite. Furthermore, a phosphite stabilizer derived from pentaerythritol represented by the following formula can also be used. (1) In the above formulas (1) and (2), R1 and R2 represent an alkyl group. Such organic phosphite 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. Moreover, the above-mentioned 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, cabric acid, arachidonic acid, palmitic acid, behenic acid, l2-hydroxystearic acid, and mongkun. Higher fatty acids such as acids can be mentioned, and metals that react with these higher fatty acids to form salts include:
Magnesium, calci. Mention may be made of alkaline earth metal salts such as aluminum and barium, alkali metals such as sodium, potassium and lithium, as well as cadmium, zinc and arsenic. 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 arachidonate, barium behenate, zinc stearate,
Zinc oleate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate and calcium l2-hydroxystearate, sodium montanate, calcium montanate, zinc montanate, etc. can be mentioned. Among these higher fatty acid metals, especially those with 12 to 12 carbon atoms
Particularly preferred are the zinc salts of No. 35 saturated fatty acids. Such higher fatty acid metal salts can be used alone or in combination. The blending 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 preformed raw material resin. Similarly, the blending ratio of the organic phosphite stabilizer was 0.
01-1.0% by weight, preferably 0.02-0.5ff
The amount of i is 96, particularly preferably 0.03 to 0.2% by weight, and the blending ratio of higher fatty acid metal salt is similarly 0.01 to 0.2% by weight.
1. Offl amount%, preferably 0.02-0.5ffl
% by weight, particularly preferably from 0.03 to 0.2% by weight. Effects of the Invention The polypropylene stretched film according to the present invention is particularly excellent in transparency because it is formed from a composition containing 3-methyl-1-butene polymer units. Moreover, by using this 3-methyl-1-butene polymer unit-containing composition, the crystallization rate of the resin becomes faster, so a film with excellent transparency can be produced in a short time. Hereinafter, the present invention will be explained by examples, but the present invention is not limited to these examples. Example 1 [Preparation of solid titanium catalyst component [A]] 7.14 kg of anhydrous magnesium chloride, 37 kg of decane. 'l
and 2-ethylhexyl alcohol 35.16 to 14
A heating reaction was carried out at 0° C. for 4 hours to form a homogeneous solution. Then, 1.67 kg of phthalic anhydride was added to this solution,
Mixing was continued for another 1 hour at 130°C, and phthalic anhydride was dissolved in the above-mentioned homogeneous solution for 7 nights. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped over 3 hours into 20 Cl of titanium tetrachloride maintained at -20°C. After the dropwise addition, the temperature of the resulting solution was raised to 110°C over 4 hours, and when it reached 110°C, 5.03N of diisobutyl phthalate was added. The mixture was stirred for an additional 2 hours at a temperature in the upper range. After 2 hours of reaction, the solid part was collected by filtration while hot, and this solid part was
T i C j of ρ! After resuspending at step 4, resuspend at step 1.
A heating reaction was carried out at 10° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration and washed with hexane. This cleaning was continued until no titanium compound was detected during the cleaning r&. Solid titanium catalyst component [A
] was obtained as a hexane slurry. A portion of this catalyst was collected and dried. Analysis of this dried material revealed that the composition of the solid titanium catalyst component [A] obtained as described above was 2.4% by weight of titanium and 5% by weight of chlorine.
9% by weight, 18% by weight of magnesium and 11.6% by weight of diisobutyl phthalate. [100 g of hexane from Kozue, 3 moles of triethylaluminum, and the titanium catalyst component [A
] was added in terms of titanium atoms, and the suspension was stirred and pressed at 2130 N while maintaining the lH degree of this suspension at 15 to 20°C.
Propylene was fed over a period of 1.5 hours at a rate of . After the supply of propylene was completed, the reactor was sealed and the remaining propylene was polymerized for 30 minutes.
mol and 5.9 kg of 3-methyl-1-butene were added, stirred at 20°C for 3 hours, and mixed with 3-methyl-1-butene.
Prepolymerization of 1-butene was carried out. After prepolymerization, $
It was thoroughly washed with hexane manufactured by No. 7. In the analysis, the amount of polymerized propylene polymer at Clt position was 2.8 g/g.
The pre-Fam content of the 3-methyl-1-butene polymer units was 2.4 g/g catalyst solids. [Polymerization] Content ffi2 5 04? Homopolymerization of propylene was carried out continuously using a polymerization vessel. Polymerization pressure is 8kg/c
JG, the polymerization temperature was controlled at 70°C. The catalyst components were 18 mmol/hour of triethylaluminum, 1.8 mmol/hour of dicyclohexyldimethoxysilane, and a titanium catalyst component prepared by prepolymerizing propylene and 3-methylbutene-1 as described above, at a rate of 0.24 mmol/hour in terms of titanium atoms. Feed was carried out continuously, based on a rate of mmol/hour. The polypropylene obtained was continuously discharged. The average production rate of the obtained polypropylene is about 10k
g/hour. 3-methyl-1 in polypropylene
-The medium content of butene verticles is 140 weight! nppn+
Met. [Method for producing biaxially stretched intermediate film] To 100 parts by weight of the 3-methylbutene-1 polymer lj-containing composition obtained as described above, 0.1 parts ffi of calcium stearate and B}fT( 2.6
- tertiary butylated hydroxytoluene) 0, 1
! 1 part rIE, Irganox 1010 (manufactured by Ciba Geigy, antioxidant + L agent, Te1 Rakis [methylene-3
Add 0.1 part by weight of (3',5'-tertiarybutylhydroxyphenyl)probione 1.]methane, mix in a Henschel mixer, and mix in a 650 mm diameter extruder at a temperature of 220°C. It became 1.0 grains of pellets. Next, the obtained pellets were passed through a φ seat presser for 90 minutes.
Squeezed at 80°C, cooled to 1.5 nus with cooling roll at 30°C
It was made into a thick sheet. Next, the rolled sheet was stretched in the longitudinal direction using a tenter-type sequential biaxial stretching machine at a temperature of 145°C for 5 minutes.
The film was stretched twice, and then stretched 10 times in the transverse direction in a tenter with an inner layer temperature of 170° C. to obtain a biaxially stretched film having a thickness of about 30 μm. [Film evaluation method] (1) Transparency [I glare evaluation] Five sheets of 30 μm thick film are stacked and the transparency is evaluated when the light from a fluorescent lamp is seen through the film.
. . . Good, 1 . . . Bad) evaluation was performed. (2) Scattering transmitted light intensity (LSI) Measured using an LSI tester manufactured by Toyo Kasuki Co., Ltd. (3) Haze Measured according to ASTM D1003. (4) Spherulite diameter The diameter of the spherulites in the original sheet before biaxial stretching was measured using a stereomicroscope (xl00). The smaller the ball size of the original sheet, the better the transparency of the rolled film tends to be, so this was used as a measure for obtaining a film with good transparency. The results are shown in Table 1. Example 2 [Preliminary polymerization] In a reactor purged with nitrogen, purified hexane 10 (1, 10 mol of triethylaluminum, 10 mol of trimethylmethoxysilane, 1 mol of the titanium catalyst component [A] in terms of titanium atoms and 3 - After adding 10 kg of methyl-1-butene, the suspension was kept at 20°C and kept under stirring for 3 hours to perform a pre-combination of 3-methyl-1-butene.As a result of the analysis, The preliminarily positive content of 3-methyl-1-butene polymer units was 3.9 g/g catalyst homogeneous portion.The stirring was then stopped, the solid portion was allowed to settle, and the supernatant liquid was removed. After washing twice with
i1 Polymerization temperature was maintained at 15-20°C. After the supply of brobylene was completed, the reactor was sealed, and the remaining propylene was mixed for 30 minutes, and then washed twice with hexane. As a result of the analysis, the pre-Q polymerization amount of propylene polymer units is 2.7
g/g catalyst solids fraction. [Polymerization] Polymerization of propylene was carried out in the same manner as in Example 1. As a result, the content of 3-methyl-1-butene polymer units in the produced polypropylene was 220 ppm. A film was prepared by the same operation as in Example 1, and the film was also evaluated. The results are shown in Table 1. Comparative Examples 1 and 2 Comparative Examples 1 and 2 were carried out in the same manner as in Examples 1 and 2, except that the T-01 polymerization of 3-methyl-1-butene and brobylene was omitted. The results are shown in Table 1. Example 3 Solid titanium catalyst component [A] was prepared in the same manner as in Example 1.
was prepared. After adding 100 ft of purified hexane, 10 moles of triethylaluminum, 10 moles of trimethylmethoxysilane, 1 mole of the titanium catalyst component [A] in terms of titanium atoms, and 10 kg of 3-methyl-1-butene into a reactor purged with nitrogen. The suspension was maintained at 20° C. and stirred for 3 hours to perform prefill combination of 3-methyl-1-butene. As a result of the analysis, the pref of 3-methyl-1-butene
The i1 polymerization amount was 3.9 g/g catalyst solid fraction. Then, stirring was stopped, the solid portion was allowed to settle, and the supernatant liquid was removed. After washing twice with hexane, the total volume was adjusted to 120 g, and after adding 3 moles of triethylaluminum, ethylene was supplied at a rate of 3150 NI/hour for 2 hours to prepolymerize ethylene. During that time, the F6i polymerization temperature is 1
The temperature was maintained at 5-20°C. After the supply of ethylene was completed, the reactor was sealed and the remaining ethylene was polymerized for 30 minutes, followed by washing twice with hexane. As a result of analysis, the total pre-Qm amount due to ethylene was 2.8 g/g catalyst solids portion. [ffl Polymerization] Polymerization of propylene was carried out in the same manner as in Example 1. As a result, poly-3-methyl-1 in raw or polypropylene
-Butene content was 260 ppm. A film was prepared by the same operation as in Example 1, and the film was also evaluated. The fruits are shown in Table 1.

[Brief explanation of the drawing]

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

Claims (1)

[Scope of Claims] 1) [A] Solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components [B] Organoaluminum compound catalyst component and optionally [C] Electron donor A prepolymer formed by prepolymerizing 3-methyl-1-butene in the presence of an olefin polymerization catalyst [I] formed from Propylene is polymerized using a polymerization catalyst component and, if necessary, the above [B] organoaluminum compound catalyst component and [C] an electron donor, or carbon is polymerized in the presence of the above olefin polymerization catalyst [I]. Number 2
~5 linear α-olefins are prepolymerized, then 3
- Polymerizing propylene using a prepolymerized catalyst component formed by prepolymerizing methyl-1-butene, and optionally the above [B] organoaluminum compound catalyst component and [C] electron donor. obtained by
Contains a 3-methyl-1-butene polymer unit, the above α-olefin polymer unit and a propylene polymer unit, and has a 3-methyl-1-butene polymer unit content of 10 to 10
1. A stretched polypropylene film, characterized in that it is formed from a composition containing 3-methyl-1-butene polymer units in a range of 0.000 ppm by weight.