JP5347213B2 - Porous film and method for producing porous film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous film which is excellent in penetrativity at a working temperature and which can be immediately shut down at a temperature higher than a working temperature in low temperatures. <P>SOLUTION: This porous film is formed from a polyolefinic resin comprising (A) an ethylene-&alpha;-olefin copolymer which comprises a constitutional unit derived from ethylene and a constitutional unit derived from one or more monomers selected from &alpha;-olefins having a carbon number of 4 to 8 and which satisfies all of the following requirements (I) to (IV): (I) the limiting viscosity number [&eta;] is 9.0 to 15.0 dl/g; (II) the melting point (Tm) is 115&deg;C or higher and lower than 130&deg;C; (III) the content of a cold xylene soluble part (CXS) contained in (A) an ethylene-&alpha;-olefin copolymer is 3 wt.% or less; and (IV) Tm&le;0.54&times;[&eta;]+114. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a porous film and a method for producing a porous film.

  Battery separators require mechanical strength during battery assembly. It is also important to have a function (shutdown) that prevents an excessive current from flowing when an abnormal current flows to the battery due to a short circuit or the like. Development of a porous film made of high molecular weight polyethylene has been promoted as a battery separator having excellent characteristics. In recent years, with the high performance of batteries, a large amount of energy has been stored in a small battery volume, and the shutdown function has been enhanced, that is, when the normal operating temperature is exceeded, the ions can be quickly and as low as possible. There is a strong demand to lose the permeability (cut off current).

As a porous film having an enhanced shutdown function, a copolymer comprising ethylene having an intrinsic viscosity [η] of 3.5 to 10.0 dl / g and an α-olefin having 4 to 8 carbon atoms, A porous biaxially oriented film comprising an ethylene / α-olefin copolymer having an α-olefin content of 1.0 to 7.5 per 1000 carbon atoms of the copolymer, A porous biaxially oriented film composed of microfibrils, characterized in that a structure based on a porous structure remains when observed at room temperature after being melted at 160 ° C. (See Patent Document 1).
JP-A-7-309965

  However, the porous biaxially oriented film described in Patent Document 1 does not satisfy both performances of permeability at use temperature and shutdown at low temperature. An object of the present invention is to provide a porous film that is excellent in permeability at a use temperature when used as a battery separator and can be shut down quickly at a low temperature when the use temperature is exceeded. In addition, the present invention provides a method for producing a porous film that, when used as a battery separator, has excellent permeability at the use temperature and can be shut down quickly at a low temperature when the use temperature is exceeded. Objective.

That is, the present invention comprises a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from α-olefins having 4 to 8 carbon atoms, and includes the following (I) to (IV Is a porous film formed from a polyolefin-based resin containing the ethylene / α-olefin copolymer (A).
(I) Intrinsic viscosity [η] is 9.0 to 15.0 dl / g
(II) Melting point Tm is 115 ° C. or more and less than 130 ° C. (III) Cold xylene soluble part (CXS) contained in ethylene / α-olefin copolymer (A) is 3% by weight or less (IV) Tm ≦ 0.54 × [Η] +114
Moreover, this invention is a manufacturing method of the porous film containing all the following process (1)-(4).
(1) An ethylene / α-olefin copolymer comprising a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from α-olefins having 4 to 8 carbon atoms. The intrinsic viscosity [η] is 9.0 to 15.0 dl / g, the melting point Tm is 115 ° C. or higher and lower than 130 ° C., Tm ≦ 0.54 × [η] +114 is satisfied, and the cold xylene soluble part (CXS ) Of ethylene / α-olefin copolymer (A) having a content of 3% by weight or less, 5-100 parts by weight of low molecular weight polyolefin (B) having a weight average molecular weight of 10,000 or less, and an average particle size Step of obtaining a polyolefin resin composition by kneading 100 to 400 parts by weight of an inorganic filler (C) having a particle size of 0.5 μm or less (2) Step of molding a sheet using the polyolefin resin composition (3 ) Process ( Step of removing inorganic filler from the sheet obtained in 2) (4) Step of stretching the sheet obtained in step (3) to make a porous film

The porous film of the present invention is excellent in permeability at the use temperature, and can be quickly shut down at a low temperature when the use temperature is exceeded. Further, according to the method for producing a porous film of the present invention, a porous film that is excellent in permeability at the use temperature and can be quickly shut down at a low temperature when the use temperature is exceeded can be obtained.

The porous film of the present invention comprises a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from α-olefins having 4 to 8 carbon atoms. It is formed from a polyolefin resin containing an ethylene / α-olefin copolymer (A) that satisfies all of (IV).
(I) Intrinsic viscosity [η] is 9.0 to 15.0 dl / g
(II) Melting point Tm is 115 ° C. or more and less than 130 ° C. (III) Cold xylene soluble part (CXS) contained in ethylene / α-olefin copolymer (A) is 3% by weight or less (IV) Tm ≦ 0.54 × [Η] +114
When the intrinsic viscosity [η] of the ethylene / α-olefin copolymer (A) is less than 9.0 dl / g, the porous film is used as a battery separator, and the battery internal temperature rises abnormally. The porous film may melt and break, and the current may not be interrupted. Also, the strength of the porous film becomes insufficient. On the other hand, an ethylene / α-olefin copolymer having an intrinsic viscosity [η] exceeding 15.0 dl / g is difficult to process into a porous film. In addition, the intrinsic viscosity in this invention is a value measured in 135 degreeC tetrahydro naphthalene (brand name tetralin).

  The ethylene / α-olefin copolymer (A) in the present invention has a melting point Tm of 115 ° C. or higher and lower than 130 ° C., preferably 125 ° C. or lower, more preferably 122 ° C. or lower. When the melting point is lower than 115 ° C., when the porous film of the present invention is used as a battery separator, battery characteristics in a normal use temperature range are deteriorated. On the other hand, when the melting point is 130 ° C. or higher, the temperature at which ion permeation is blocked, that is, the shutdown temperature becomes high. The melting point of the ethylene / α-olefin copolymer (A) in the present invention is the peak top temperature of the melting curve measured by a differential scanning calorimeter (DSC) according to ASTM D3417 unless otherwise specified. . When there are a plurality of peaks in the melting curve, the melting point is the peak temperature having the largest heat of fusion ΔH (J / g).

  Further, the cold xylene soluble part (CXS) contained in the ethylene / α-olefin copolymer (A) of the present invention is 3% by weight or less, preferably 2% by weight or less, more preferably 1.5% by weight. It is as follows. Generally, the ethylene / α-olefin copolymer has a lower melting point of the copolymer as the content of the structural unit derived from the α-olefin in the copolymer is larger, but the proportion of CXS is larger. Become. When a sheet is prepared using a copolymer having a high CXS content and the sheet is stretched, there is a problem that stretching is difficult. Moreover, when the sheet | seat which consists of a copolymer with much content of CXS is extended | stretched, the sheet | seat obtained becomes a thing with low intensity | strength. Furthermore, a porous film obtained by using an ethylene / α-olefin copolymer having a high CXS content has poor ion permeability at the operating temperature, for example, air permeability is 4000 seconds / 100 cc or more, particularly as a battery separator. Is unsuitable. The CXS component in the porous film is preferably 5 wt% or less, more preferably 3 wt%. In the present invention, the cold xylene soluble part means the ethylene / α-olefin copolymer having a weight of a soluble component when 5 g of ethylene / α-olefin copolymer is added to 1000 ml of xylene at 25 ° C. As a percentage of the initial weight (ie, 5 g).

  The ethylene / α-olefin copolymer (A) of the present invention is a polymer satisfying the relationship of Tm ≦ 0.54 × [η] +114. In general, the greater the intrinsic viscosity [η] of the resin constituting the film, the greater the strength of the film. On the other hand, the greater the intrinsic viscosity, the higher the melting point (Tm) of the resin is known. ing. We have also found that the melting point of the resin affects the shutdown temperature of the porous film made of the film. As a result of studying porous films made of resins having various intrinsic viscosities and melting points, we have found that porous films are made of resins satisfying the relationship of intrinsic viscosity [η] and melting point (Tm) of Tm ≦ 0.54 × [η] +114. It was found that a porous film useful as a battery separator having a pin puncture strength higher than 300 g and a shutdown temperature lower than 130 ° C. can be obtained by forming a conductive film. The relational expression is an expression obtained by approximating the experimental result with a linear expression. The least square method was applied to calculate the equation.

The ethylene / α-olefin copolymer (A) used in the present invention contains, for example, a titanium atom, a magnesium atom, a halogen atom and an ester compound, and has a specific surface area of 80 m ² / g or less by the BET method. In the presence of a polymerization catalyst obtained by contacting (α) with an organoaluminum compound (β), one or more monomers selected from ethylene and an α-olefin having 4 to 8 carbon atoms Obtained by copolymerization. Examples of the α-olefin having 4 to 8 carbon atoms include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. A copolymer of ethylene and an α-olefin having 9 or more carbon atoms is difficult to stretch, and it becomes difficult to produce a porous film. A porous film formed from a copolymer of ethylene and propylene has a high non-porous start temperature.

The BET specific surface area of the solid catalyst component (alpha) is less than 80 m ² / g, and preferably is 0.05~50m ² / g, more preferably 0.1~30m ² / g. The specific surface area can be reduced by adding a sufficient amount of the ester compound to the solid catalyst component (α). The content of the ester compound in the solid catalyst component (α) is preferably 15 to 50% by weight when the total amount of the dried solid catalyst component is 100% by weight. More preferably, it is 20-40 weight%, More preferably, it is 22-35 weight%.

Examples of the ester compound in the solid catalyst component (α) include mono- or polyvalent carboxylic acid esters, such as saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic compounds. Group carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, Diphthalic acid (2 Ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate. Among these, from the viewpoint of polymerization activity, dialkyl phthalate is preferable, and dialkyl phthalate having a total of 9 or more carbon atoms of two alkyl groups bonded to each ester bond is more preferable. The ester compound is mainly an ester compound used in the process of preparing the solid catalyst component (A) or an ester compound produced by a reaction in the process of preparing the solid catalyst component (A), as will be described later.
The content of titanium atoms in the solid catalyst component (α) is preferably 0.6 to 1.6% by weight, and more preferably when the dried solid catalyst component (α) is 100% by weight. 0.8 to 1.4% by weight.

  As a method for producing the solid catalyst component (α), an ester compound or a compound capable of producing an ester compound in the reaction system is allowed to coexist in the preparation process of the solid catalyst component described in JP-A-11-322833. Obtained by.

For example, the preparation method in any one of (1)-(5) below is mentioned.
(1) A method of contacting a magnesium halide compound, a titanium compound and an ester compound.
(2) A method in which an ester solution is brought into contact with a solid component obtained by bringing an alcohol solution of a magnesium halide compound into contact with a titanium compound.
(3) A method of bringing a halogenated compound and an ester compound into contact with a solid component obtained by bringing a solution of a magnesium halide compound and a titanium compound into contact with a precipitant.
(4) A method of contacting a dialkoxymagnesium compound, a titanium halide compound and an ester compound.
(5) A method of contacting a solid component containing a magnesium atom, a titanium atom and a hydrocarbyloxy group, a halogenated compound and an ester compound.
Among them, the method (5) is preferable, and a method in which a solid component (a) containing a magnesium atom, a titanium atom and a hydrocarbyloxy group, a halogenated compound (b) and a phthalic acid derivative (c) are brought into contact with each other. preferable. This will be described in more detail below.

（上記一般式［Ｉ］において、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はそれぞれ、ハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同じであっても異なっていてもよい。） (A) Solid component The solid component (a) used in the present invention comprises a titanium compound (ii) represented by the following general formula [I] in the presence of an organosilicon compound (i) having a Si-O bond. And a solid component obtained by reduction with an organomagnesium compound (iii). At this time, if the ester compound (iv) is present as an optional component, the polymerization activity may be further improved.

(In the above general formula [I], a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. X ² is a halogen atom or a carbon atom having 1 to 20 carbon atoms, respectively. Represents a hydrocarbon oxy group, and all X ² may be the same or different.)

Examples of the organosilicon compound (i) having a Si—O bond include compounds represented by the following general formula.
Si (OR ¹⁰ ) _t R ¹¹ _4-t ,
R ¹² (R ¹³ ₂ SiO) _u SiR ¹⁴ ₃ or
(R ¹⁵ ₂ SiO) _v
In the above general formula, R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrocarbon group having 1 to 20 carbon atoms. Or represents a hydrogen atom. t represents an integer satisfying 0 <t ≦ 4, u represents an integer of 1 to 1000, and v represents an integer of 2 to 1000.

Examples of the organosilicon compound (i) include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane, tetrapropoxy. Silane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldi Siloxane, Hexaethyldisilohexane, Hexapropyldisiloxane, Octaethyltrisiloxane, Dimethylpolysiloxane , Diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, and the like. Of these organosilicon compounds (i), an alkoxysilane compound represented by the general formula Si (OR ¹⁰ ) _t R ¹¹ _4- t is preferable. In this case, t preferably satisfies 1 ≦ t ≦ 4. A tetraalkoxysilane with t = 4, most preferably tetraethoxysilane.

（上記一般式［Ｉ］において、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はそれぞれ、ハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同じであっても異なっていてもよい。） The titanium compound (ii) is a titanium compound represented by the following general formula [I].

(In the above general formula [I], a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. X ² is a halogen atom or a carbon atom having 1 to 20 carbon atoms, respectively. Represents a hydrocarbon oxy group, and all X ² may be the same or different.)

R ² is a hydrocarbon group having 1 to 20 carbon atoms. Examples of R ² include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, and dodecyl. Examples thereof include aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group. Among these hydrocarbon groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. More preferably, it is a linear alkyl group having 2 to 18 carbon atoms.

X ² is each a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms. Examples of the halogen atom for X ² include a chlorine atom, a bromine atom, and an iodine atom. Particularly preferred is a chlorine atom. The hydrocarbon oxy group having 1 to 20 carbon atoms in X ² is a hydrocarbon oxy group having a hydrocarbon group having 1 to 20 carbon atoms in the same manner as R ² . X ² is particularly preferably an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

  In the titanium compound (ii) represented by the general formula [I], a is a number of 1 to 20, and preferably a number satisfying 1 ≦ a ≦ 5.

  Examples of the titanium compound (ii) include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraiso-propoxy titanium, tetra n-butoxy titanium, tetraiso-butoxy titanium, n-butoxy titanium trichloride, Di-n-butoxytitanium dichloride, tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate (a mixture in the range of a = 2-10), tetra-n-butylpolytitanate (a mixture in the range of a = 2-10) , Tetra n-hexyl polytitanate (a mixture in the range of a = 2 to 10), tetra n-octyl polytitanate (a mixture in the range of a = 2 to 10). Moreover, the condensate of the tetraalkoxy titanium obtained by making a small amount of water react with tetraalkoxy titanium can also be mentioned.

  The titanium compound (ii) is preferably a titanium compound in which a is 1, 2 or 4 in the titanium compound represented by the above general formula [I]. Particularly preferred is tetra n-butoxy titanium, tetra n-butyl titanium dimer or tetra n-butyl titanium tetramer. In addition, titanium compound (ii) may be used independently and can also be used in the state which mixed multiple types.

The organomagnesium compound (iii) is any type of organomagnesium compound having a magnesium-carbon bond. In particular, a Grignard compound represented by the general formula R ¹⁶ MgX ⁵ (wherein Mg represents a magnesium atom, R ¹⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, and X ⁵ represents a halogen atom), or Dihydrocarbylmagnesium represented by the general formula R ¹⁷ R ¹⁸ Mg (wherein Mg represents a magnesium atom and R ¹⁷ and R ¹⁸ each represent a hydrocarbon group having 1 to 20 carbon atoms) is preferred. Used for. Here, R ¹⁷ and R ¹⁸ may be the same or different. R ^{16 to} R ¹⁸ are, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, Examples thereof include an alkyl group having 1 to 20 carbon atoms such as a phenyl group and a benzyl group, an aryl group, an aralkyl group, and an alkenyl group. In particular, the use of a Grignard compound represented by R ¹⁶ MgX ⁵ in an ether solution is preferable from the viewpoint of polymerization activity and stereoregularity.

  The organomagnesium compound (iii) can also be used as a complex with another organometallic compound solubilized in a hydrocarbon solvent. Specific examples of the organometallic compound include lithium, beryllium, aluminum or zinc compounds.

  The ester compound (iv) which is an optional component includes mono- or polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, aromatic Group carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, Diphthalic acid (2 Ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate. Of these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters, or aromatic carboxylic acid esters such as phthalic acid esters are preferred, and dialkyl phthalates are particularly preferred.

  Solid component (a) is obtained by reducing titanium compound (ii) with organomagnesium compound (iii) in the presence of organosilicon compound (i) or in the presence of organosilicon compound (i) and ester compound (iv). can get. Specifically, a method of introducing the organomagnesium compound (iii) into a mixture of the organosilicon compound (i), the titanium compound (ii) and, if necessary, the ester compound (iv) is preferable.

  The titanium compound (ii), the organosilicon compound (i) and the ester compound (iv) are preferably used in the form of a solution or slurry in an appropriate solvent. Such solvents include aliphatic hydrocarbons such as hexane, heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, diethyl ether, dibutyl ether, di- Examples include ether compounds such as isoamyl ether and tetrahydrofuran.

The temperature range of the reduction reaction temperature is usually −50 to 70 ° C., preferably −30 to 50 ° C., and particularly preferably −25 to 35 ° C.
The charging time of organomagnesium (iii) is not particularly limited, but is usually about 30 minutes to 10 hours. The reduction reaction proceeds with the addition of the organomagnesium (iii), but after the addition, a post reaction may be performed at a temperature of 20 to 120 ° C.

In the reduction reaction, a porous carrier such as an inorganic oxide or an organic polymer can be allowed to coexist, and the porous carrier can be impregnated with the solid component. The porous carrier used may be a known one. Specific examples include porous inorganic oxides represented by SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO _2, etc., or polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-dimethacrylic acid. Methyl copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer And organic porous polymers such as polyvinyl chloride, polyethylene, and polypropylene. Among these, an organic porous polymer is preferably used, and a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferable.

The pore volume at a pore radius of 20 nm to 200 nm of the porous carrier is preferably 0.3 cm ³ / g or more, more preferably 0.4 cm ³ / g or more, from the viewpoint of effectively immobilizing the catalyst component. And a carrier having a pore volume in the pore radius range of preferably 35% or more, more preferably 40% or more of the pore volume at a pore radius of 3.5 nm to 7500 nm. The catalyst component may not be effectively immobilized unless it is sufficiently present in the pore radius range of 20 nm to 200 nm, which is not preferable.

The amount of the organosilicon compound (i) used is the ratio of the number of silicon atoms to the total titanium atoms in the titanium compound (ii), usually Si / Ti = 1 to 500, preferably 1.5 to 300, particularly preferably Is in the range of 3-100.
The amount of the organomagnesium compound (iii) used is usually (Ti + Si) /Mg=0.1 to 10, preferably 0.2 to 5. in terms of the ratio of the sum of titanium atoms and silicon atoms to the number of magnesium atoms. 0, particularly preferably in the range of 0.5 to 2.0.
Further, the value of the molar ratio of Mg / Ti in the solid catalyst component is usually 1 to 51, preferably 2 to 31, and particularly preferably 4 to 26, so that the titanium compound (ii) and the organic The usage-amount of a silicon compound (i) and an organomagnesium compound (iii) is determined.
Moreover, the usage-amount of the ester compound (iv) of an arbitrary component is a molar ratio of the ester compound with respect to the titanium atom of a titanium compound (ii), and is usually ester compound / Ti = 0.05-100, Preferably it is 0.8. It is 1-60, Most preferably, it is the range of 0.2-30.

  The solid component obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane, heptane, and toluene. The solid component (a) thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and generally exhibits amorphous or extremely weak crystallinity. From the viewpoint of polymerization activity and stereoregularity, an amorphous structure is particularly preferable.

(B) Halogenated compound The halogenated compound is preferably a compound that can replace the hydrocarbon oxy group in the solid component (a) with a halogen atom. More preferably, it is a halogen compound of Group 4 element, a halogen compound of Group 13 element or a halogen compound of Group 14 element, and more preferably a halogen compound (b1) of Group 4 element or Group 14 element. This is an elemental halogen compound (b2).

The halogen compound (b1) of the Group 4 element is preferably represented by the general formula M ¹ (OR ⁹ ) _b X ⁴ _4-b (wherein M ¹ represents a Group 4 atom and R ⁹ has 1 carbon atom) Represents a hydrocarbon group of ˜20, X ⁴ represents a halogen atom, and b represents a number satisfying 0 ≦ b <4. Examples of M ¹ include a titanium atom, a zirconium atom, and a hafnium atom. Among these, a titanium atom is preferable. As R ⁹ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, Examples thereof include alkyl groups such as decyl group and dodecyl group, aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. Particularly preferred is a linear alkyl group having 2 to 18 carbon atoms. It is also possible to use halogen compounds of Group 4 elements having two or more different OR ⁹ groups.

Examples of the halogen atom represented by X ⁴ include a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom is particularly preferable.

In the halogen compounds of Group 4 elements represented by the general formula M ¹ (OR ⁹ ) _b X ⁴ _4-b , b is a number that satisfies 0 ≦ b <4, and preferably satisfies 0 ≦ b ≦ 2. Particularly preferably, b = 0. Examples of the halogen compound represented by the general formula M ¹ (OR ⁹ ) _b X ⁴ _4-b include titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, methoxy titanium trichloride, Trihalogenated alkoxy titanium such as ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxy titanium dichloride Examples thereof include dihalogenated dialkoxytitanium such as bromide, and similarly include a zirconium compound and a hafnium compound corresponding to each. Most preferred is titanium tetrachloride

The halogen compound of group 13 element or the halogen compound (b2) of group 14 element of the periodic table is preferably a general formula M ² R ¹ _mc X ⁸ _c (wherein M ² is an atom of group 13 or group 14). R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X ⁸ represents a halogen atom, m represents a number corresponding to the valence of M ² , and c represents 0 <c ≦ m. Represents a satisfactory number.). Examples of the Group 13 atom include a boron atom, an aluminum atom, a gallium atom, an indium atom, and a thallium atom, preferably a boron atom or an aluminum atom, and more preferably an aluminum atom. Examples of the Group 14 atom include a carbon atom, a silicon atom, a germanium atom, a tin atom, and a lead atom, preferably a silicon atom, a germanium atom, or a tin atom, and more preferably a silicon atom or a tin atom. Is an atom.

m is a number corresponding to the valence of M ^2, for example, M ² is an m = 4 when the silicon atoms.
c is a number satisfying 0 <c ≦ m. When M ² is a silicon atom, c is preferably 3 or 4.
Examples of the halogen atom represented by X ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

Examples of R ¹ include alkyl such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, and dodecyl. Group, phenyl group, tolyl group, cresyl group, xylyl group, aryl group such as naphthyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group, alkenyl group such as propenyl group, and aralkyl group such as benzyl group. An alkyl group or an aryl group is preferable, and a methyl group, an ethyl group, a normal propyl group, a phenyl group, or a paratolyl group is particularly preferable.

  Group 13 element halogen compounds include trichloroborane, methyldichloroborane, ethyldichloroborane, phenyldichloroborane, cyclohexyldichloroborane, dimethylchloroborane, methylethylchloroborane, trichloroaluminum, methyldichloroaluminum, ethyldichloroaluminum, phenyl Dichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichlorogallium, cyclohexyldichlorogallium, Dimethylchlorogallium, me Ruethylchlorogallium, indium chloride, indium trichloride, methylindium dichloride, phenylindium dichloride, dimethylindium chloride, thallium chloride, thallium trichloride, methylthallium dichloride, phenylthallium dichloride, dimethylthallium chloride, etc. Also included are compounds in which “chloro” is replaced with “fluoro”, “bromo” or “iodo”.

  Group 14 element halogen compounds (b2) include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2, and the like. , 2-tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane, Methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trimethylchloro Silane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monocrologermane, trimethylchlorogermane, triethylchlorogermane , Trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin, divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, Dichloro lead, methyl chloro lead, phenyl chloro lead, etc. are listed. "Fluoro", compounds obtained by replacing the "bromo" or "iodo" can also be mentioned.

Particularly preferable as the halogenated compound (b), from the viewpoint of polymerization activity, titanium tetrachloride, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane or tetra Chlorotin.
The halogenated compound (b) may be used alone from among the above compounds, or a plurality of types may be used simultaneously or sequentially.

（ただし、Ｒ²⁴〜Ｒ²⁷はそれぞれ独立に水素原子または炭化水素基、Ｓ⁶およびＳ⁷はそれぞれ独立にハロゲン原子であるか、または、水素原子、炭素原子、酸素原子およびハロゲン原子のうちの複数を任意に組み合わせて形成される置換基である。）
Ｒ²⁴〜Ｒ²⁷として好ましくは、水素原子、または炭素原子数１〜１０の炭化水素基であり、Ｒ²⁴〜Ｒ²⁷の任意の組み合わせは互いに結合して環構造を形成していてもよい。Ｓ⁶およびＳ⁷として好ましくは、それぞれ独立に塩素原子、水酸基、または炭素原子数１〜２０のアルコキシ基である。 (C) Phthalic acid derivative Examples of the phthalic acid derivative (c) include compounds represented by the following general formula.

(Wherein R ^{24 to} R ²⁷ are each independently a hydrogen atom or a hydrocarbon group, S ⁶ and S ⁷ are each independently a halogen atom, or a hydrogen atom, a carbon atom, an oxygen atom and a halogen atom) It is a substituent formed by arbitrarily combining a plurality.)
R ^{24 to} R ²⁷ are preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and any combination of R ^{24 to} R ²⁷ may be bonded to each other to form a ring structure. S ⁶ and S ⁷ are preferably each independently a chlorine atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms.

Specific examples of the phthalic acid derivative (c) include phthalic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-normal phthalate, diisopropyl phthalate, di-normal butyl phthalate, phthalic acid Diisobutyl, dipentyl phthalate, di-hexyl phthalate, di-normal heptyl phthalate, di-isoheptyl phthalate, di-normal octyl phthalate, di (2-ethylhexyl) phthalate, di-nordecyl phthalate, diisodecyl phthalate, dicyclohexyl phthalate , Diphenyl phthalate, dichloride phthalate, diethyl 3-methylphthalate, diethyl 4-methylphthalate, diethyl 3,4-dimethylphthalate, dinormal butyl 3-methylphthalate, dinormal butyl 4-methylphthalate, 3 4-normal butyl 4-dimethylphthalate, diisobutyl 3-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl 3,4-dimethylphthalate, di (2-ethylhexyl) 3-methylphthalate, di (2-ethylhexyl) 4-methylphthalate ), 3,4-dimethylphthalic acid di (2-ethylhexyl), 3-methylphthalic acid dichloride, 4-methylphthalic acid dichloride, 3,4-dimethylphthalic acid dichloride, 3-ethylphthalic acid di (2-ethylhexyl), 4- Examples thereof include di (2-ethylhexyl) ethylphthalate and di (2-ethylhexyl) 3,4-diethylphthalate. Among them, diethyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, diisoheptyl phthalate, di (2) phthalate -Ethylhexyl), dii phthalate Decyl are preferred.
When the esters contained in the solid catalyst component of the present invention are dialkyl phthalates, they are derived from phthalic acid derivatives, and are compounds in which S ⁶ and S ⁷ are alkoxy groups in the above general formula. In the preparation of the solid catalyst component, S ⁶ and S ⁷ of the phthalic acid derivative (c) used can be exchanged as they are or with other substituents.

  The solid catalyst component (α) used in the present invention is prepared by replacing the titanium compound (ii) represented by the general formula [I] with the organomagnesium compound (iii) in the presence of the organosilicon compound (i) having a Si—O bond. ), The solid component (a), the halogenated compound (b) and the phthalic acid derivative (c) obtained by reduction with each other. All of these contact treatments are usually performed in an inert gas atmosphere such as nitrogen gas or argon gas.

As a specific method of the contact treatment for obtaining the solid catalyst component (α),
A method for charging (a) with (b) and (c) (arbitrary order) and performing contact processing. (B) for (a) and (c) (arbitrary order) with contact processing. Method (c): (a) and (b) (input order is arbitrary) and contact processing method (a) (b) is input, after contact processing, (c) is input After (c) is added to (a) and contact processing is performed, after (b) is input and after (c) is input to (a) and (c) is subjected to contact processing. , (B) and (c) (arrangement order is arbitrary) and contact treatment method (c) is introduced into (a) and after contact treatment, the mixture of (b) and (c) is introduced. , Contact processing method ・ (b) and (c) (arbitrary order) are input to (a), and after contact processing, (b) is input and contact processing is performed. The method · (a), (b) and the (c) (on sequence Optional) were charged, and after the contact treatment (b) was charged a mixture of (c), and a method of contacting treatment. Among them, (b) and (c) (arbitrary order) are charged into (a), contact processing is performed and then (b1) is charged and contact processing is performed. (A) includes (b2) and ( It is more preferable to add the mixture of (b1) and (c) after the c) (addition order is arbitrary) and the contact treatment, and the contact treatment. Further, the polymerization activity may be improved by repeating the contact treatment with (b1) a plurality of times thereafter.

  The contact treatment can be performed by any known method capable of bringing each component into contact, such as a slurry method or a mechanical pulverizing means such as a ball mill. However, mechanical pulverization generates a large amount of fine powder in the solid catalyst component. In some cases, the particle size distribution may be widened, which is not preferable for stably performing continuous polymerization. Therefore, it is preferable to contact both in the presence of a solvent. After the contact treatment, the next operation can be carried out as it is, but it is preferable to carry out a washing treatment with a solvent in order to remove surplus.

  The solvent is preferably inert to the component to be treated. Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, cyclohexane, cyclohexane, and the like. Alicyclic hydrocarbons such as pentane and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be used. The amount of the solvent used in the contact treatment is usually 0.1 ml to 1000 ml per 1 g of the solid component (a) per one stage of contact treatment. Preferably, the amount is 1 ml to 100 ml per 1 g. In addition, the amount of solvent used in one washing operation is similar. The number of washing operations in the washing treatment is usually 1 to 5 times per one-step contact treatment.

  The contact treatment and washing treatment temperatures are usually -50 to 150 ° C, preferably 0 to 140 ° C, more preferably 60 to 135 ° C. The contact treatment time is not particularly limited, but is preferably 0.5 to 8 hours, and more preferably 1 to 6 hours. The washing operation time is not particularly limited, but is preferably 1 to 120 minutes, and more preferably 2 to 60 minutes.

  The amount of the phthalic acid derivative (c) used is usually 0.01 to 100 mmol, preferably 0.05 to 50 mmol, more preferably 0.1 to 20 mmol with respect to 1 g of the solid component (a). It is. When the amount of the phthalic acid derivative (c) used is excessively large, the particle size distribution of the solid catalyst component (α) may be broadened due to particle collapse.

In particular, the amount of the phthalic acid derivative (c) used can be arbitrarily adjusted so that the content of the phthalic acid ester in the solid catalyst component (α) is appropriate. It is 0.1-100 mmol normally with respect to 1g of solid components (a), Preferably it is 0.3-50 mmol, More preferably, it is 0.5-20 mmol. Moreover, the usage-amount of the phthalic acid derivative (c) per 1 mol of magnesium atoms in a solid component (a) is 0.01-1.0 mol normally, Preferably it is 0.03-0.5 mol. .
The usage-amount of a halogenated compound (b) is 0.5-1000 mmol normally with respect to 1 g of solid components (a), Preferably it is 1-200 mmol, More preferably, it is 2-100 mmol.
When the contact treatment is performed using each compound a plurality of times, the amount of each compound described above represents the amount of each compound used once and for each kind of compound.

  The obtained solid catalyst component (α) may be used in polymerization in a slurry form in combination with an inert solvent, or may be used in polymerization as a fluid powder obtained by drying. Examples of the drying method include a method of removing volatile components under reduced pressure conditions and a method of removing volatile components under a flow of an inert gas such as nitrogen gas or argon gas. Preferably it is 0-200 degreeC as temperature at the time of drying, More preferably, it is 50-100 degreeC. The drying time is preferably 0.01 to 20 hours, more preferably 0.5 to 10 hours. The weight average particle diameter of the solid catalyst component (α) is preferably 1 to 100 μm from an industrial viewpoint.

  By contacting the solid catalyst component (α) with the organoaluminum compound (β), a catalyst for polymerization of the ethylene / α-olefin copolymer (A) used in the present invention is obtained. Further, if necessary, an electron donating compound (γ) can be added and brought into contact.

The organoaluminum compound (β) in the present invention has at least one aluminum-carbon bond in the molecule. A typical organoaluminum compound is represented by the following general formula.
R ¹⁹ _w AlY _3-w
R ²⁰ R ²¹ Al—O—AlR ²² R ²³
(In the above general formula, R ^{19 to} R ²³ represent a hydrocarbon group having 1 to 20 carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group, and w represents a number satisfying 2 ≦ w ≦ 3. Represents.)
Examples of the organoaluminum compound (β) include trialkylaluminum such as triethylaluminum, triisobutylaluminum and trihexylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, Examples include a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of triethylaluminum and diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

  Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane is preferable, and triethylaluminum, triisobutylaluminum, triethylaluminum and diethylaluminum chloride are particularly preferable. Or tetraethyldialumoxane.

  Examples of the electron donating compound (γ) used for forming the olefin polymerization catalyst include an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, and a sulfur-containing compound, preferably an oxygen-containing compound or a nitrogen-containing compound. A compound. Examples of the oxygen-containing compound include alkoxy silicons, ethers, esters, ketones, and the like, preferably alkoxy silicons or ethers.

The alkoxysilicons Motorui general formula _R ³ _r Si (OR ⁴⁾ in _4-r (wherein, R ³ represents a hydrocarbon group, a hydrogen atom or a hetero atom-containing substituent group having a carbon number 1 to 20, R ⁴ Represents a hydrocarbon group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4. When a plurality of R ³ and R ⁴ are present, each R ³ and R ⁴ is the same. Or an alkoxysilicon compound represented by the following formula: When R ³ is a hydrocarbon group, examples of the hydrocarbon group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, an isopropyl group, a sec-butyl group, and a tert-butyl group. Group, branched alkyl group such as tert-amyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, cycloalkenyl group such as cyclopentenyl group, aryl group such as phenyl group and tolyl group. Among these, it is preferable that the carbon atom directly bonded to the silicon atom of the alkoxysilicon compound has at least one R ³ which is a secondary or tertiary carbon. When R ³ is a heteroatom-containing substituent, examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specifically, dimethylamino group, methylethylamino group, diethylamino group, ethyl-n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, Examples include perhydroisoindolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrocarbazolyl, perhydroacridinyl, furyl, pyranyl, perhydrofuryl, and thienyl groups. Preferably, the hetero atom is a substituent that can be directly chemically bonded to the silicon atom of the alkoxysilicon compound.

  Examples of the alkoxysilicones include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert- Butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butyl Isopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyl Methoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyl Dimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, Phenyl isobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldi Ethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxy Silane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane Orchid, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino ) (Perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane , (Perhydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, (perhydroquinolino) (tert-butyl) dimethoxysila , And (perhydroisoquinolino) (tert-butyl) dimethoxysilane.

  Examples of ethers include cyclic ether compounds. The cyclic ether compound is a heterocyclic compound having at least one —C—O—C— bond in the ring structure. Examples of the cyclic ether compound include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, 2,5-dimethoxytetrahydrofuran, tetrahydropyran, hexamethylene oxide, 1,3-dioxepane, 1,3-dioxane, 1,4-dioxane. 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,4-dimethyl-1,3-dioxolane , Furan, 2,5-dimethylfuran, or s-trioxane. Preferred is a cyclic ether compound having at least one —C—O—C—O—C— bond in the ring structure.

  Examples of the esters include mono- or polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. . Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, Diphthalic acid (2 Ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate.

Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenyl ketone, benzophenone, and cyclohexanone.
Examples of the nitrogen-containing compound include 2,6-substituted piperidines such as 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 2,5-substituted piperidines, N, N, N ′. , N′-tetramethylmethylenediamine, substituted methylenediamines such as N, N, N ′, N′-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine. Preferred are 2,6-substituted piperidines.

  The electron donating compound (γ) is particularly preferably cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy. Silane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, 1,3-dioxolane, 1,3-dioxane, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine.

  The polymerization catalyst used in the present invention is obtained by bringing the solid catalyst component (α) and the organoaluminum compound (β) into contact with the electron donating compound (γ) as necessary. The term “contact” as used herein may be by any means as long as the catalyst components (α) and (β) (if necessary (γ)) are in contact with each other and a catalyst is formed. A method of mixing and contacting each of them without dilution, a method of separately supplying them to the polymerization tank and bringing them into contact with each other in the polymerization tank can be employed. As a method of supplying each catalyst component to the polymerization tank, it is preferable to supply the catalyst components in an inert gas such as nitrogen or argon in the absence of moisture. Each catalyst component may be supplied in contact with any two components in advance.

  The ethylene / α-olefin copolymer (A) can be polymerized in the presence of the catalyst, but the prepolymerization described below may be performed before such polymerization (main polymerization). Absent.

  The prepolymerization is usually carried out by supplying a small amount of olefin in the presence of the solid catalyst component (α) and the organoaluminum compound (β), and is preferably carried out in a slurry state. Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of a part or all of the inert hydrocarbon solvent.

The amount of the organoaluminum compound used in the prepolymerization can be selected in a wide range such as 0.5 to 700 mol per mol of titanium atom in the solid catalyst component, but preferably 0.8 to 500 mol. Particularly preferred is 1 to 200 mol.
The amount of olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component.

  The slurry concentration at the time of prepolymerization is preferably 1 to 500 g-solid catalyst component / L-solvent, particularly preferably 3 to 300 g-solid catalyst component / L-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. Further, the partial pressure of the olefin in the gas phase during the prepolymerization is preferably 1 kPa to 2 MPa, and particularly preferably 10 kPa to 1 MPa, but for the olefin that is liquid at the prepolymerization pressure and temperature, This is not the case. The prepolymerization time is not particularly limited, but is usually 2 minutes to 15 hours.

  As a method of supplying the solid catalyst component (α), the organoaluminum compound (β), and the olefin during the prepolymerization, the solid catalyst component (α) and the organoaluminum compound (β) are contacted and then the olefin. Any method may be used, such as a method of supplying the organic aluminum compound (β) after the solid catalyst component (α) and the olefin are brought into contact with each other. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all of the predetermined amount of olefin first is used. Good. In general, a chain transfer agent such as hydrogen is added to adjust the molecular weight, but the ethylene-α-olefin copolymer in the present invention has little or no chain transfer agent such as hydrogen. It can be produced by polymerization under conditions. Specifically, the partial pressure of hydrogen relative to the sum of the partial pressures of hydrogen, ethylene, and α-olefin is usually in the gas phase part of the slurry upper surface in slurry polymerization and in the gas phase part in gas phase polymerization. It is 0.10 or less, preferably 0.05 or less, particularly preferably 0.02 or less.

  When the solid catalyst component (α) is prepolymerized with a small amount of olefin in the presence of the organoaluminum compound (β), an electron donating compound (γ) may coexist if necessary. The electron donating compound used is a part or all of the electron donating compound (γ). The amount used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, per 1 mol of titanium atom contained in the solid catalyst component (α). Yes, with respect to the organoaluminum compound (β), it is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to 2 mol. The method for supplying the electron donating compound (γ) during the preliminary polymerization is not particularly limited, and may be supplied separately from the organoaluminum compound (β) or may be supplied in contact with the organic aluminum compound (β). Further, the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

  After performing prepolymerization as described above, or without performing prepolymerization, in the presence of the polymerization catalyst comprising the above-described solid catalyst component (α) and organoaluminum compound (β), ethylene and carbon atoms One or more monomers selected from α-olefins of several 4 to 8 can be copolymerized.

The amount of the organoaluminum compound used in the main polymerization can usually be selected in a wide range such as 1 to 1000 mol per 1 mol of the titanium atom in the solid catalyst component (α), particularly preferably in the range of 5 to 600 mol. It is.
Moreover, when using an electron-donating compound ((gamma)) at the time of this superposition | polymerization, it is 0.1-2000 mol normally with respect to 1 mol of titanium atoms contained in a solid catalyst component ((alpha)), Preferably 0.3- 1000 mol, particularly preferably 0.5 to 800 mol, and usually 0.001 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to mol of the organoaluminum compound. ~ 1 mole.

Although this superposition | polymerization can be implemented over -30-300 degreeC normally, Preferably it is 20-180 degreeC, More preferably, it is 40-100 degreeC. Although it does not specifically limit regarding a polymerization pressure, From a viewpoint of being industrial and economical, generally it is a normal pressure-10MPa, Preferably the pressure of about 200kPa-5MPa is employ | adopted. As the polymerization method, either batch type or continuous type is possible. Various distributions (molecular weight distribution, comonomer composition distribution, etc.) can be imparted by continuously passing through a plurality of polymerization stages or reactors having different polymerization conditions. In addition, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, bulk polymerization using a liquid olefin as a medium at the polymerization temperature, or gas phase polymerization is also possible.
In the main polymerization, it is preferable not to add a chain transfer agent such as hydrogen in order to increase the molecular weight (intrinsic viscosity) of the polymer, and the ethylene / α-olefin copolymer obtained by adjusting the temperature and time of the main polymerization is preferable. Adjust the intrinsic viscosity of the coalescence.

  The polyolefin-based resin forming the porous film of the present invention has a weight average of 100 parts by weight of the ethylene / α-olefin copolymer (A) and 100 parts by weight of the ethylene / α-olefin copolymer (A). It is preferable that 5-100 weight part of low molecular weight polyolefin (B) with a molecular weight of 10,000 or less is included, and it is further more preferable that 10-70 weight part is included. A polyolefin resin containing an ethylene / α-olefin copolymer (A) and a low molecular weight polyolefin (B) having a weight average molecular weight of 10,000 or less has good stretchability, and a porous film formed by the production method of the present invention described later. It is suitable when manufacturing. The weight average molecular weight of the low molecular weight polyolefin (B) is measured by GPC (gel permeation chromatography), and the content (% by weight) of each component can be obtained by integration of a molecular weight distribution curve obtained by GPC measurement. In many cases, the solvent used in the GPC measurement is o-dichlorobenzene, and the measurement temperature is 140 ° C.

  Specific examples of the low molecular weight polyolefin (B) used in the present invention include polyethylene resins such as low density polyethylene, linear polyethylene (ethylene / α-olefin copolymer) and high density polyethylene, polypropylene, and ethylene-propylene copolymer. Examples thereof include polypropylene resins such as polymers, waxes of poly (4-methylpentene-1), poly (butene-1), and ethylene-vinyl acetate copolymers. When the porous film of the present invention is used as a battery separator, the low molecular weight polyolefin (B) is preferably a wax that is solid at 25 ° C. Even if such low molecular weight polyolefin (B) remains in the porous film, it is difficult to adversely affect the battery characteristics.

  The non-porous start temperature of the porous film in the present invention is the temperature at which it reaches 100Ω when the internal resistance is measured using the porous film, or a resistance value that is 1/100 of the maximum resistance value. The lower temperature of the temperature at which Further, the shutdown temperature is a temperature at which 1000Ω is reached when the internal resistance is measured. The porous film of the present invention preferably has a non-porous start temperature of 110 ° C. or higher and a shutdown temperature of 130 ° C. or lower. Such a porous film of the present invention can ensure ion permeability at the use temperature, and when the temperature rises beyond the use temperature, the current can be cut off at a low temperature and quickly. It can be suitably used as a separator for a battery, particularly as a separator for a non-aqueous battery.

  The porous film of the present invention preferably has an air permeability of 50 to 1000 seconds / 100 cc from the viewpoint of being able to quickly interrupt current at low temperature and ion permeability, and is preferably 50 to 200 seconds / More preferably, it is 100 cc.

As a result of intensive studies on the relationship between the pore structure and the shutdown temperature of a number of porous films, it was found that the pore diameter and film thickness of the porous film and the melting point of the resin have a profound effect on the shutdown temperature. For example, the smaller the hole diameter, the larger the film thickness, and the lower the melting point of the resin, the lower the shutdown temperature.
In the present invention, from these experimental facts, a statistical method was used to find a relational expression between the pore diameter, the film thickness, and the melting point for making the shutdown temperature lower than 130 ° C.
That is, the film thickness y (μm) of the porous film of the present invention, the pore diameter d (μm) measured by the bubble point method, and the ethylene / α-olefin copolymer contained in the polyolefin resin forming the porous film The melting point Tm (° C.) of (A) preferably satisfies the following formula.
Tm + (850 × d ÷ y) <130
A porous film satisfying the above formula has an excellent current blocking function, and can be immediately shut down when a battery using the film as a separator exceeds the operating temperature.

The method for producing the porous film of the present invention is not particularly limited. For example, as described in JP-A-7-29563, a plasticizer is added to a polyolefin resin to form a film, and then the plasticizer Using a film made of a polyolefin resin produced by a known method as described in JP-A-7-304110, and a structurally weak amorphous part of the film is removed. A method of selectively stretching to form micropores can be mentioned. When the porous film of the present invention is formed from a polyolefin-based resin containing an ethylene / α-olefin copolymer (A) and a low molecular weight polyolefin (B) having a weight average molecular weight of 10,000 or less, the production cost is low. From a viewpoint, it is preferable to manufacture by the method as shown below. That is,
(1) An ethylene / α-olefin copolymer comprising a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from α-olefins having 4 to 8 carbon atoms. The intrinsic viscosity [η] is 9.0 to 15.0 dl / g, the melting point Tm is 115 ° C. or higher and lower than 130 ° C., Tm ≦ 0.54 × [η] +114 is satisfied, and the cold xylene soluble part (CXS ) Of ethylene / α-olefin copolymer (A) having a content of 3% by weight or less, 5-100 parts by weight of low molecular weight polyolefin (B) having a weight average molecular weight of 10,000 or less, and an average particle size Step of obtaining a polyolefin resin composition by kneading 100 to 400 parts by weight of an inorganic filler (C) having a particle size of 0.5 μm or less (2) Step of molding a sheet using the polyolefin resin composition (3 ) Process ( 2) a step of removing the inorganic filler from the sheet obtained in (2), (4) a method comprising a step of stretching the sheet obtained in step (3) to form a porous film, or (1) derived from ethylene And an ethylene / α-olefin copolymer comprising a structural unit derived from one or more monomers selected from α-olefins having 4 to 8 carbon atoms, wherein the intrinsic viscosity [η] is 9.0 to 15.0 dl / g, melting point Tm is 115 ° C. or higher and lower than 130 ° C., Tm ≦ 0.54 × [η] +114 is satisfied, and content of cold xylene soluble part (CXS) is 3 wt. % Ethylene / α-olefin copolymer (A) 100 parts by weight, low molecular weight polyolefin (B) 5 to 100 parts by weight with a weight average molecular weight of 10,000 or less, and an average particle size of 0.5 μm or less. Inorganic filler (C) 100-4 Step of obtaining a polyolefin resin composition by kneading 00 parts by weight (2) Step of molding a sheet using the polyolefin resin composition (3) Step of stretching the sheet obtained in step (2) ( 4) A method including a step of removing the inorganic filler (C) from the stretched sheet obtained in the step (3) to obtain a porous film. From the viewpoint of uniformity of the film thickness of the obtained porous film, it is preferable to produce the porous film by the former method, that is, the method of stretching after removing the inorganic filler (C) in the sheet.

  It is preferable that about 100 to 20000 ppm of the inorganic filler (C) remains in the porous film obtained by removing the inorganic filler (C). When the porous film in which a small amount of the inorganic filler remains is used as a battery separator, an effect of preventing a short circuit between the electrodes is expected even when the polyolefin resin constituting the porous sheet is melted. Moreover, the porous film in which a small amount of the inorganic filler remains is more permeable than when the inorganic filler is completely removed. The reason for this is not clear, but it is thought that the film is hardly crushed in the film thickness direction due to the trace amount of filler remaining in the film.

  From the viewpoint of the strength and ion permeability of the porous film, the inorganic filler (C) used preferably has an average particle diameter (diameter) of 0.5 μm or less, and more preferably 0.2 μm or less. In addition, the average particle diameter of the inorganic filler (C) in this invention is a value calculated | required by the SEM photograph of this inorganic filler (C). Specifically, it is observed with a scanning electron microscope SEM at 30000 times, the diameter of 100 particles is measured, and the average is taken as the average particle diameter (μm).

  As the inorganic filler (C), calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, calcium oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium sulfate, silicic acid, zinc oxide, calcium chloride, sodium chloride, Examples thereof include magnesium sulfate. These inorganic fillers can be removed from the sheet or film with an acid or alkaline solution. In the present invention, it is preferable to use calcium carbonate because it is easy to obtain a fine particle size.

  The method for producing the polyolefin resin composition is not particularly limited, but a material for constituting the polyolefin resin composition such as a polyolefin resin or an inorganic filler is mixed with an apparatus such as a roll, a Banbury mixer, a single screw extruder, a twin screw extruder. Etc. are mixed to obtain a polyolefin resin composition. When mixing the materials, additives such as fatty acid esters, stabilizers, antioxidants, ultraviolet absorbers and flame retardants may be added as necessary.

  The manufacturing method of the sheet | seat which consists of polyolefin resin composition used by this invention is not specifically limited, It can manufacture by sheet forming methods, such as an inflation process, a calendar process, T-die extrusion process, and a Skyf method. Since a sheet with higher film thickness accuracy can be obtained, it is preferable to produce the sheet by the following method.

  A preferred method for producing a sheet comprising a polyolefin resin composition is a polyolefin resin composition using a pair of rotational molding tools adjusted to a surface temperature higher than the melting point of the polyolefin resin contained in the polyolefin resin composition. This is a method of rolling a product. The surface temperature of the rotary forming tool is preferably (melting point + 5) ° C. or higher. The upper limit of the surface temperature is preferably (melting point + 30) ° C. or less, and more preferably (melting point + 20) ° C. or less. Examples of the pair of rotary forming tools include a roll and a belt. The peripheral speeds of the two rotary forming tools do not necessarily have to be exactly the same peripheral speed, and the difference between them may be about ± 5% or less. By producing a porous film using a film obtained by such a method, a porous film excellent in strength, ion permeation, air permeability and the like can be obtained. Moreover, you may use what laminated | stacked the sheet | seat of the single layer obtained by the above methods for manufacture of a porous film.

  When a polyolefin resin composition is rolled with a pair of rotary molding tools, the polyolefin resin composition discharged in a strand form from an extruder may be directly introduced between the pair of rotary molding tools, and once pelletized. The polyolefin resin composition may be used.

  When stretching a sheet made of a polyolefin resin composition or a sheet from which the inorganic filler has been removed, a tenter, a roll, an autograph or the like can be used. In view of air permeability, the draw ratio is preferably 2 to 12 times, more preferably 4 to 10 times. The stretching temperature is usually carried out at a temperature not lower than the softening point and not higher than the melting point of the polyolefin resin, and is preferably performed at 80 to 115 ° C. If the stretching temperature is too low, film breakage tends to occur during stretching, and if it is too high, the air permeability and ion permeability of the resulting film may be lowered. Moreover, it is preferable to heat set after extending | stretching. The heat set temperature is preferably a temperature below the melting point of the polyolefin resin.

  In this invention, it can be set as the porous film which laminated | stacked the heat resistant resin layer on the at least single side | surface of the porous film formed from the polyolefin-type resin obtained by an above described method. The heat resistant resin layer may be provided on one side of the porous film, or may be provided on both sides. A porous film having such a heat-resistant resin layer is excellent in film thickness uniformity, heat resistance, strength, and air permeability (ion permeability). Therefore, a separator for a non-aqueous electrolyte battery, particularly a lithium ion secondary battery. It can be suitably used as a separator for a printer.

  The heat-resistant resin constituting the heat-resistant resin layer is preferably a polymer containing a nitrogen atom in the main chain, and particularly preferably contains an aromatic ring from the viewpoint of heat resistance. For example, aromatic polyamide (hereinafter sometimes referred to as “aramid”), aromatic polyimide (hereinafter sometimes referred to as “polyimide”), aromatic polyamideimide and the like can be mentioned. Examples of the aramid include meta-oriented aromatic polyamide and para-oriented aromatic polyamide (hereinafter sometimes referred to as “para-aramid”), and it is easy to form a porous heat-resistant resin layer having a uniform film thickness and excellent air permeability. Therefore, para-aramid is preferable.

  Para-aramid is obtained by condensation polymerization of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond is in the para position of the aromatic ring or an oriented position equivalent thereto (for example, 4, 4′- Biphenylene, 1,5-naphthalene, 2,6-naphthalene and the like, which are substantially composed of repeating units bonded in the opposite direction (orientation positions extending coaxially or in parallel). Specifically, poly (paraphenylene terephthalamide), poly (parabenzamide, poly (4,4′-benzanilide terephthalamide), poly (paraphenylene-4,4′-biphenylenedicarboxylic amide), poly (para Para-oriented or para-oriented, such as phenylene-2,6-naphthalenedicarboxylic acid amide), poly (2-chloro-paraphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer The para-aramid which has a structure according to is illustrated.

When providing the heat resistant resin layer, the heat resistant resin is usually dissolved in a solvent and used as a coating solution. When the heat-resistant resin is para-aramid, a polar amide solvent or a polar urea solvent can be used as the solvent. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Examples include, but are not limited to, 2-pyrrolidone and tetramethylurea.
From the viewpoint of coatability, the heat resistant resin is preferably a heat resistant resin having an intrinsic viscosity of 1.0 dl / g to 2.8 dl / g, and more preferably an intrinsic viscosity of 1.7 dl / g to 2.5 dl / g. Is preferred. If the intrinsic viscosity is less than 1.0 dl / g, the strength of the formed heat-resistant resin layer may be insufficient. If the intrinsic viscosity exceeds 2.8 dl / g, it may be difficult to obtain a stable heat-resistant resin-containing coating solution. The intrinsic viscosity as used herein is a value measured by dissolving a heat-resistant resin once precipitated and making it into a heat-resistant resin sulfuric acid solution, and is a value serving as a so-called molecular weight index. From the viewpoint of coating properties, the heat-resistant resin concentration in the coating solution is preferably 0.5 to 10% by weight.

  When para-aramid is used as the heat-resistant resin, it is preferable to add an alkali metal or alkaline earth metal chloride during para-aramid polymerization for the purpose of improving the solubility of para-aramid in a solvent. Specific examples include lithium chloride or calcium chloride, but are not limited thereto. The amount of the chloride added to the polymerization system is preferably in the range of 0.5 to 6.0 mol, more preferably in the range of 1.0 to 4.0 mol, per 1.0 mol of the amide group produced by condensation polymerization. . If the chloride is less than 0.5 mol, the solubility of the resulting para-aramid may be insufficient, and if it exceeds 6.0 mol, the amount of chloride dissolved in the solvent may be substantially exceeded, which may not be preferable. is there. In general, if the alkali metal or alkaline earth metal chloride is less than 2% by weight, the solubility of para-aramid may be insufficient. If it exceeds 10% by weight, the alkali metal or alkaline earth metal chloride may be insufficient. May not dissolve in polar organic solvents such as polar amide solvents or polar urea solvents.

  The polyimide used in the present invention is preferably a wholly aromatic polyimide produced by condensation polymerization of an aromatic dianhydride and a diamine. Specific examples of the dianhydride include pyromellitic dianhydride, 3, 3 ′, 4, 4′-diphenylsulfone tetracarboxylic dianhydride, 3, 3 ′, 4, 4′-benzophenone tetracarboxylic acid. And acid dianhydrides, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the like. Specific examples of the diamine include oxydianiline, paraphenylenediamine, benzophenone diamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, 1,5 '-Naphthalenediamine and the like can be mentioned, but the present invention is not limited to these. In the present invention, a polyimide soluble in a solvent can be suitably used. An example of such a polyimide is a polycondensate polyimide of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and an aromatic diamine. As a polar organic solvent for dissolving polyimide, dimethyl sulfoxide, cresol, o-chlorophenol, and the like can be suitably used in addition to those exemplified as a solvent for dissolving aramid.

  In the present invention, the coating liquid used for forming the heat-resistant resin layer particularly preferably contains ceramic powder. By forming a heat-resistant resin layer using a coating solution in which ceramic powder is added to a solution having an arbitrary heat-resistant resin concentration, it is possible to form a heat-resistant resin layer having a uniform and fine porous film thickness. it can. The air permeability can be controlled by the amount of ceramic powder added. In the ceramic powder according to the present invention, the average particle diameter of the primary particles is preferably 1.0 μm or less, more preferably 0.5 μm or less, from the viewpoint of the strength of the porous film and the smoothness of the heat resistant resin layer surface. Preferably, it is 0.1 μm or less. The average particle diameter of the primary particles is measured by a method of analyzing a photograph obtained by an electron microscope with a particle diameter measuring instrument. The content of the ceramic powder is preferably 1% by weight or more and 95% by weight or less in the porous film, and more preferably 5% by weight or more and 50% by weight or less. If the ceramic powder content in the porous film is too low, the resulting porous film may be insufficient in ion permeability when used as a battery separator, and if too high, the film becomes brittle and difficult to handle. There is. The shape of the ceramic powder to be used is not particularly limited, and can be spherical or random.

  Examples of the ceramic powder in the present invention include ceramic powders made of electrically insulating metal oxides, metal nitrides, metal carbides, and the like. For example, powders of alumina, silica, titanium dioxide, zirconium oxide or the like are preferably used. The ceramic powders may be used alone, or two or more kinds may be mixed, or the same kind or different kinds of ceramic powders having different particle diameters may be arbitrarily mixed and used.

  The average pore diameter measured by the mercury intrusion method of the heat resistant resin layer is preferably 3 μm or less, and more preferably 1 μm or less. When the average pore diameter exceeds 3 μm, when a porous film having a heat-resistant resin layer is used as a battery separator, a short circuit is likely to occur when carbon powder, which is the main component of the positive electrode or the negative electrode, or a small piece thereof drops off. May cause problems. The porosity of the heat resistant resin layer is preferably 30 to 80% by volume, more preferably 40 to 70% by volume. When the porosity is less than 30% by volume, when the laminated porous film is used as a battery separator, the amount of electrolyte retained may be reduced. When the porosity exceeds 80% by volume, the strength of the heat-resistant resin layer is insufficient. There is a case. The heat-resistant resin layer has a thickness of preferably 1 to 15 μm, more preferably 1 to 10 μm. When the thickness is less than 1 μm, the effect on heat resistance may be insufficient. When the thickness exceeds 15 μm, the thickness is large when a porous film having a heat-resistant resin layer is used as a separator for nonaqueous batteries. In some cases, it is difficult to achieve a high electric capacity.

As a method of laminating a heat-resistant resin layer on a porous film formed from a polyolefin-based resin, a method of separately producing a heat-resistant resin layer and then laminating it with a porous film, ceramic powder and at least one surface of the porous film Although the method etc. which apply | coat the coating liquid containing a heat resistant resin and form a heat resistant resin layer are mentioned, the latter method is preferable from the surface of productivity. Specific examples of a method for forming a heat resistant resin layer by applying a coating liquid containing ceramic powder and a heat resistant resin on at least one surface of the porous film include the following steps.
(A) A slurry-like coating liquid is prepared by dispersing 1 to 1500 parts by weight of ceramic powder in 100 parts by weight of a heat-resistant resin in a polar organic solvent solution containing 100 parts by weight of a heat-resistant resin.
(B) The coating solution is applied to at least one surface of the porous film to form a coating film.
(C) The heat resistant resin is deposited from the coating film by means of humidification, solvent removal, or immersion in a solvent that does not dissolve the heat resistant resin, and then dried as necessary.
The coating liquid is preferably applied continuously by a coating apparatus described in JP-A-2001-316006 and a method described in JP-A-2001-23602.

  The porous film of the present invention is excellent in permeability at the use temperature and can be quickly shut down at a low temperature when the use temperature is exceeded, and is suitable as a separator for non-aqueous batteries. Further, when the porous film of the present invention has a heat-resistant resin layer, it is excellent in heat resistance, strength and air permeability (ion permeability), and is preferably used as a separator for non-aqueous batteries, particularly a lithium ion secondary battery separator. can do.

(1) Composition analysis of solid sample such as solid catalyst component Titanium atom content is about 3 mg% hydrogen peroxide solution which decomposes about 20 milligrams of solid sample with 47 ml of 0.5 mol / L sulfuric acid and becomes excessive. 3 ml was added, and the characteristic absorption at 410 nm of the obtained liquid sample was measured using a Hitachi double beam spectrophotometer model U-2001, and was determined by a separately prepared calibration curve. The alkoxy group content is obtained by decomposing about 2 grams of a solid sample with 100 ml of water, and then determining the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample using a gas chromatography internal standard method. Converted. The phthalate compound content was determined by dissolving about 30 milligrams of a solid sample in 100 ml of N, N-dimethylacetamide and then determining the amount of phthalate compound in the solution by an internal standard method of gas chromatography.
(2) BET specific surface area The specific surface area of the solid catalyst component was determined by the BET method based on the nitrogen adsorption / desorption amount using Flowsorb II 2300 manufactured by Micromeritics.
(3) α-olefin content in ethylene / α-olefin copolymer Infrared spectrophotometry according to the method described in “Polymer Analysis Handbook” (edited by the Analytical Society of Japan, Polymer Analysis Research Conference) P590-594 Using a calibration curve from the characteristic absorption of ethylene and α-olefin using a total (Perkin Elmer 1600 series), it was expressed as the number of short chain branches (SCB) per 1000 carbon atoms.
(4) Bulk specific gravity of polymerization powder It measured according to JIS K-6721 (1966).
(5) Intrinsic viscosity [η] of ethylene / α-olefin copolymer
The polymer was dissolved in a tetralin solvent at 135 ° C. and measured at 135 ° C. using an Ubbelohde viscometer.
(6) A polymer having a CXS amount of 5 g in an ethylene / α-olefin copolymer was dissolved in 1000 ml of boiling xylene, then air-cooled, left in a constant temperature bath at 25 ° C. for 20 hours, and then at the same temperature. The precipitated polymer was filtered off using filter paper (No. 50 manufactured by Advantech).
Xylene in the filtrate was distilled off under reduced pressure, the weight of the remaining polymer was measured, and the weight percentage of the polymer in an initial weight of 5 g was determined to be CXS (unit =%).
(7) Melting point Measured according to ASTM D3417 using a differential scanning calorimeter (Diamond DSC manufactured by PerkinElmer). The test piece in the measurement pan is held at 150 ° C. for 5 minutes, cooled from 150 ° C. to 20 ° C. at 5 ° C./minute, held at 20 ° C. for 2 minutes, and heated from 20 ° C. to 150 ° C. at 5 ° C./minute, The peak top temperature of the melting curve obtained at this time was taken as the melting point. In the case where a plurality of peaks exist in the melting curve, the peak temperature with the largest heat of fusion ΔH (J / g) was taken as the melting point.
(8) Average particle size of inorganic filler The particle size of 100 particles was measured with a scanning electron microscope SEM (S-4200 manufactured by Hitachi) at a magnification of 30000, and the average was taken as the average particle size (μm).
(9) The Gurley value (second / 100 cc) of the Gurley value film was measured with a B-type densometer (manufactured by Toyo Seiki) in accordance with JIS P8117.
(10) Average pore diameter Based on ASTM F316-86, the average pore diameter d (μm) of the porous film was measured by Perm-Porometer (manufactured by PMI) by the bubble point method.
(11) Film thickness Measured according to JISK7130.
(12) Puncture strength The maximum stress (gf) when the porous film was fixed with a 12 mmφ washer and the pin was punctured at 200 mm / min was defined as the puncture strength of the film. A pin with a pin diameter of 1 mmΦ and a tip of 0.5R was used.
(13) Internal Resistance Measurement The shutdown temperature and non-porous start temperature were measured with a shutdown measurement cell (hereinafter referred to as a cell) as shown in FIG.
After a 6 cm square separator (8) is placed on one SUS plate electrode (10) and the electrolyte (9) is vacuum impregnated, an electrode (13) with a spring (12) is placed on the upper side of the spring (12). It put on the separator (8) so that it might become. Another SUS plate electrode (10) is placed on the spacer (11) disposed on the electrode (10), and a surface pressure of 1 kgf is applied to the separator (8) through the spring (12) and the electrode (13). Both electrodes (10) and (10) were fastened so that / cm ² acted, and the cell was assembled. As the electrolytic solution (9), a solution obtained by dissolving 1 mol / L of LiPF ₆ in a mixed solution of ethylene carbonate 30 vol%: dimethyl carbonate 35 vol%: ethylmethyl carbonate 35 vol% was used.
The terminals of the impedance analyzer (7) were connected to the electrodes (10) and (10) of the assembled cell, and the resistance value at 1 kHz was measured. In addition, a thermocouple (14) was installed directly under the separator so that the temperature could be measured at the same time, and impedance and temperature were measured while the temperature was raised at 2 ° C./min. The temperature when the impedance at 1 kHz reached 1000Ω was defined as the shutdown temperature. Further, the lower temperature of the temperature at which the resistance value reached 100Ω or the temperature at which the resistance value was 1/100 of the maximum resistance value was defined as the non-porous start temperature.
(14) Water chromatograph Alliance GPC2000 type was used as a weight average molecular weight measuring apparatus. Other conditions are shown below.
Column: TSKgel GMHHR-H (S) HT 30 cm × 2 manufactured by Tosoh Corporation, TSKgel GMH 6 -HTL 30 cm × 2
Mobile phase: o-dichlorobenzene detector: Differential refractometer flow rate: 1.0 mL / min Column temperature: 140 ° C.
Injection volume: 500 μL
After completely dissolving 30 mg of the sample in 20 mL of o-dichlorobenzene at 145 ° C., the solution was filtered through a sintered filter having a pore size of 0.45 μm, and the filtrate was used as a feed solution.

[Example 1]
(1) Synthesis of solid catalyst component precursor A 200-liter reactor equipped with a nitrogen-substituted stirrer and baffle plate was charged with 80 l of hexane, 20.6 kg of tetraethoxysilane, and 2.2 kg of tetrabutoxy titanium. Next, 50 l of a dibutyl ether solution of butyl magnesium chloride (concentration 2.1 mol / liter) was added dropwise to the stirred mixture over 4 hours while maintaining the temperature of the reactor at 5 ° C. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour and further at 20 ° C. for 1 hour and then filtered. The obtained solid was washed with 70 l of toluene three times, and 63 l of toluene was added to form a slurry. A part of the slurry was collected, the solvent was removed, and drying was performed to obtain a solid catalyst component precursor.
The solid catalyst component precursor contained Ti: 1.86 wt%, OEt (ethoxy group): 36.1 wt%, and OBu (butoxy group): 3.00 wt%.
(2) Solid catalyst component synthesis After replacing the reactor having an internal volume of 210 l equipped with a stirrer with nitrogen, the solid catalyst component precursor slurry synthesized in (1) above was charged into the reactor, and tetrachlorosilane 14. 4 kg and 9.5 kg of di (2-ethylhexyl) phthalate were added and stirred at 105 ° C. for 2 hours. Subsequently, solid-liquid separation was performed, and the obtained solid was repeatedly washed with 90 l of toluene at 95 ° C. three times, and then 63 l of toluene was added. After raising the temperature to 70 ° C., 13.0 kg of TiCl ₄ was added and stirred at 105 ° C. for 2 hours. Next, solid-liquid separation was performed, and the obtained solid was repeatedly washed with 90 l of toluene at 95 ° C. six times, and further washed with 90 l of hexane twice at room temperature, and the washed solid was dried. As a result, 15.2 kg of a solid catalyst component was obtained.
The solid catalyst component contained Ti: 0.93 wt% and di (2-ethylhexyl) phthalate: 26.8 wt%. The specific surface area by the BET method was 8.5 m ² / g.
(3) Ethylene / butene slurry polymerization An autoclave with a stirrer with an internal volume of 3 liters was sufficiently dried and then evacuated, charged with 500 g of butane and 250 g of 1-butene and heated to 70 ° C. Next, ethylene was added so that the partial pressure was 1.0 MPa. Polymerization was initiated by injecting 5.7 mmol of triethylaluminum and 10.7 mg of the solid catalyst component obtained in (2) above with argon. Thereafter, polymerization was carried out at 70 ° C. for 180 minutes while keeping the total pressure constant while continuously supplying ethylene.
After the completion of the polymerization reaction, the unreacted monomer was purged to obtain 204 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 19100 g polymer / g solid catalyst component, and the bulk specific gravity of the polymer powder was 0.38 g / ml.
(4) Production of porous film For 100 parts by weight of ethylene / 1-butene copolymer (A) ([η] = 9.1, melting point 119 ° C., CXS 1.02 wt%) obtained by the above-described method, Low molecular weight polyethylene (B) (weight average molecular weight 1000, manufactured by Mitsui Chemicals, high wax 110P) 37.5 parts by weight, mixture of 100 parts by weight of calcium carbonate (C) 175 parts by weight with an average particle size of 0.1 μm In addition, 0.2 parts by weight of a phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1010) is added to 100 parts by weight of the total of the components (A), (B), and (C), and phosphorous oxidation. A mixture of 0.2 parts by weight of an inhibitor (Ciba Specialty Chemicals Co., Ltd .: IRGAFOS168) was kneaded in a Laboplast mill (manufactured by Toyo Seiki) (210 ° C, 3 minutes, 150 rpm) ), A polyolefin resin composition was obtained. Next, the polyolefin resin composition was rolled using a press (210 ° C.) to prepare a 110 μm sheet. The sheet was stretched 5 times using an autograph at 90 ° C., and then immersed in an aqueous acid solution (containing a surfactant) to extract calcium carbonate. Thereafter, the film was washed with water and dried at 40 ° C. to obtain a porous film. The result of the shutdown measurement of the obtained porous film is shown in FIG. Further, physical property data such as the pore diameter, Gurley, film thickness, and puncture strength of the porous film are shown in Table 1.

[Example 2]
(1) Ethylene / butene slurry polymerization Polymerization was carried out in the same manner as in Example 1 (3) except that 19.3 mg of the solid catalyst component obtained in Example 1 (2) was used and the polymerization temperature was set to 60 ° C. 121 g of a polymer with good powder properties was obtained.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 6270 g polymer / g solid catalyst component, and the bulk specific gravity of the polymer powder was 0.39 g / ml.
(2) Production of porous film Ethylene / 1-butene copolymer (A) obtained by the above-described method ([η] = 13.1, melting point 121 ° C., butene short chain branching degree 4.76, CXS component) 0.25 wt%) 100 parts by weight of low molecular weight polyethylene (B) (weight average molecular weight 1000, Mitsui Chemicals, High Wax 110P) 37.5 parts by weight, calcium carbonate (C) 175 having an average particle size of 0.1 μm To 100 parts by weight of the mixture mixed at a ratio of parts by weight, 100 parts by weight of the above-mentioned components (A), (B), (C), and phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1010) 0.2 parts by weight and 0.2 parts by weight of a phosphorus-based antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGAFOS168) were kneaded in a Laboplast mill (manufactured by Toyo Seiki) (210 ° C). , For 3 minutes, the number of revolutions was 150 rpm) to obtain a polyolefin resin composition. Next, the polyolefin resin composition was rolled using a press (210 ° C.) to prepare a 112 μm sheet. The sheet was stretched 5 times using an autograph at 90 ° C., and then immersed in an aqueous acid solution (containing a surfactant) to extract calcium carbonate. Thereafter, the film was washed with water and dried at 40 ° C. to obtain a porous film. The result of the shutdown measurement of the obtained porous film is shown in FIG. Further, physical property data such as the pore diameter, Gurley, film thickness, and puncture strength of the porous film are shown in Table 1.

[Example 3]
(1) Ethylene / butene slurry polymerization Example 1 (except that 0.57 mmol of 1,3-dioxolane was added before 27.5 mg of the solid catalyst component obtained in Example 1 (2) and before the solid catalyst component was charged. Polymerization was carried out in the same manner as in 3) to obtain 275 g of a polymer having good powder properties.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 10,000 g polymer / g solid catalyst component, and the bulk specific gravity of the polymer powder was 0.42 g / ml.
(2) Production of porous film Ethylene-1-butene copolymer (A) obtained by the above-described method ([η] = 10.1, melting point 119 ° C., butene short chain branching degree 8.45, CXS component 0.78) wt%) 100 parts by weight, low molecular weight polyethylene (B) (weight average molecular weight 1000, Mitsui Chemicals, high wax 110P) 37.5 parts by weight, ratio of 175 parts by weight of calcium carbonate (C) having an average particle size of 0.1 μm In addition to 100 parts by weight of the mixture of the above components (A), (B), and (C), a phenolic antioxidant (manufactured by Ciba Specialty Chemicals: IRGANOX 1010) 2 parts by weight of a phosphorus-based antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGAFOS168) blended with 0.2 parts by weight is kneaded in a lab plast mill (manufactured by Toyo Seiki) (210 ° C, 3 minutes, The number of revolutions was 150 rpm), and a polyolefin resin composition was obtained. Next, the polyolefin resin composition was rolled using a press (210 ° C.) to produce a 150 μm sheet. The sheet was stretched 5 times using an autograph at 90 ° C., and then immersed in an aqueous acid solution (containing a surfactant) to extract calcium carbonate. Thereafter, the film was washed with water and dried at 40 ° C. to obtain a porous film. The result of the shutdown measurement of the obtained porous film is shown in FIG. Further, physical property data such as the pore diameter, Gurley, film thickness, and puncture strength of the porous film are shown in Table 1.

[Comparative Example 1]
Low molecular weight polyethylene (B) (weight average molecular weight 1000, manufactured by Mitsui Chemicals, Inc.) with respect to 100 parts by weight of commercially available high molecular weight polyethylene (A) ([η] = 14, melting point 136 ° C., manufactured by Mitsui Chemicals, Hi-Zex Million 340M) The total amount of the components (A), (B), and (C) was added to 100 parts by weight of a mixture of 37.5 parts by weight of wax 110P and 175 parts by weight of calcium carbonate (C) having an average particle size of 0.1 μm. 0.2 parts by weight of a phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1010) and 100 parts by weight of a phosphorus antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGAFOS168) The components are blended in a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) (210 ° C., 3 minutes, rotation speed 150 rpm), and a polyolefin resin composition is prepared. It was. Next, the polyolefin resin composition was rolled using a press (210 ° C.) to prepare a 110 μm sheet. The sheet was stretched 5 times using an autograph at 90 ° C., and then immersed in an aqueous acid solution (containing a surfactant) to extract calcium carbonate. Thereafter, the film was washed with water and dried at 40 ° C. to obtain a porous film. The result of the shutdown measurement of the obtained porous film is shown in FIG. Further, physical property data such as the pore diameter, Gurley, film thickness, and puncture strength of the porous film are shown in Table 1.

[Comparative Example 2]
Commercially available high molecular weight polyethylene (A) ([η] = 14, melting point 136 ° C., Mitsui Chemicals, Hi-Zex Million 340M) 100 parts by weight, low molecular weight polyethylene (B) (weight average molecular weight 1000, Mitsui Chemicals, high wax 110P ) 37.5 parts by weight, 100 parts by weight of a mixture of 175 parts by weight of calcium carbonate (C) having an average particle size of 0.1 μm, and a total of 100 parts by weight of the components (A), (B) and (C) 0.2 part by weight of a phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1010) and 0.2 part by weight of a phosphorus antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGAFOS168) The blended material is kneaded using a twin-screw kneader (Plastics Engineering Laboratory) designed to be strongly kneaded and polyolefin resin group To obtain things. The polyolefin resin composition was roll-rolled (roll temperature 150 ° C.) to produce a sheet having a thickness of about 60 μm.
The obtained sheet was stretched about 5 times by a tenter stretching machine at a stretching temperature of 110 ° C., and then immersed in an aqueous acid solution (containing a surfactant) to extract calcium carbonate. Thereafter, the film was washed with water and dried at 40 ° C. to obtain a porous film. The result of the shutdown measurement of the obtained porous film is shown in FIG. Further, physical property data such as the pore diameter, Gurley, film thickness, and puncture strength of the porous film are shown in Table 1.
[Comparative Example 3]
190 parts by weight of calcium carbonate (C) having an average particle size of 0.1 μm, 100 parts by weight with respect to 100 parts by weight of commercially available high molecular weight polyethylene (A) ([η] = 14, melting point 136 ° C., Mitsui Chemicals, Hi-Zex Million 340M) 100 parts by weight of a mixture of 10 parts by weight of low density polyethylene (Sumitomo Chemical: FV201, melting point 120 ° C.) and 41 parts by weight of low molecular weight polyethylene (weight average molecular weight 1000, Mitsui Chemicals, high wax 110P), 0.2 parts by weight of a phenolic antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1010) and 100 parts by weight of a phosphorus antioxidant (Ciba Specialty Chemicals Co., Ltd .: IRGAFOS 168) A blend of 2 parts by weight is kneaded in a lab plast mill (manufactured by Toyo Seiki) (210 ° C., 3 minutes, rotation speed 150 rp) ), To obtain a polyolefin resin composition. Next, the polyolefin resin composition was rolled using a press (210 ° C.) to prepare a 145 μm sheet. The sheet was stretched 5 times using an autograph at 90 ° C., and then immersed in an aqueous acid solution (containing a surfactant) to extract calcium carbonate. Thereafter, the film was washed with water and dried at 40 ° C. to obtain a porous film. The result of the shutdown measurement of the obtained porous film is shown in FIG. Further, physical property data such as the pore diameter, Gurley, film thickness, and puncture strength of the porous film are shown in Table 1.

It is a figure which shows the shutdown measurement result of the porous film obtained by the Example and the comparative example. The curves indicated by symbols 1, 2, 3, 4, 5 and 6 indicate Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively. Schematic diagram of internal resistance measuring device

Explanation of symbols

1: Example 1
2: Example 2
3: Example 3
4: Comparative Example 1
5: Comparative example 2
6: Comparative Example 3
7: Impedance analyzer 8: Separator 9: Electrolytic solution 10: SUS plate 11: Teflon (registered trademark) spacer 12: Spring 13: Electrode 14: Thermocouple 15: Data processing device

Claims (7)

Ethylene consisting of a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from α-olefins having 4 to 8 carbon atoms, and satisfying all of the following (I) to (IV) A porous film formed from a polyolefin resin containing an α-olefin copolymer (A).
(I) Intrinsic viscosity [η] is 9.0 to 15.0 dl / g
(II) Melting point Tm is 115 ° C. or more and less than 130 ° C. (III) Cold xylene soluble part (CXS) contained in ethylene / α-olefin copolymer (A) is 3% by weight or less (IV) Tm ≦ 0.54 × [Η] +114   2. The polyolefin resin comprising 100 parts by weight of the ethylene / α-olefin copolymer (A) and 5 to 100 parts by weight of a low molecular weight polyolefin (B) having a weight average molecular weight of 10,000 or less. The porous film according to 1.   The porous film according to claim 1 or 2, wherein the non-porous start temperature is 110 ° C or higher and the shutdown temperature is 130 ° C or lower. At least one side a heat-resistant resin layer is laminated porous film according to any one of claims 1-3. The porous film according to claim 4 , wherein the heat resistant resin layer is a layer containing ceramic powder and a heat resistant resin containing a nitrogen element. Non-aqueous battery separator comprising a porous film according to any one of claims 1-5. The manufacturing method of the porous film including all the following processes (1)-(4).
(1) An ethylene / α-olefin copolymer comprising a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from α-olefins having 4 to 8 carbon atoms. The intrinsic viscosity [η] is 9.0 to 15.0 dl / g, the melting point Tm is 115 ° C. or higher and lower than 130 ° C., Tm ≦ 0.54 × [η] +114 is satisfied, and the cold xylene soluble part (CXS ) Of ethylene / α-olefin copolymer (A) having a content of 3% by weight or less, 5-100 parts by weight of low molecular weight polyolefin (B) having a weight average molecular weight of 10,000 or less, and an average particle size Step of obtaining a polyolefin resin composition by kneading 100 to 400 parts by weight of an inorganic filler (C) having a particle size of 0.5 μm or less (2) Step of molding a sheet using the polyolefin resin composition (3 ) Process ( Step of removing inorganic filler from the sheet obtained in 2) (4) Step of stretching the sheet obtained in step (3) to make a porous film

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