JPH06104752B2 - Porous film and sheet manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a porous film or sheet which is soft and has micropores and which is suitable for a diaphragm material, a filtration material or the like.

[Prior Art] Conventionally, as a method for producing a polypropylene porous film, sheet, etc., a film obtained by mixing polyolefin, an organic liquid and an inorganic filler and melt-extruding the mixture, and then extracting the organic liquid by solvent extraction to make it through-porous. (JP-B-59-37292) A water-soluble organic filler (gelatin) is put into the resin and extracted to make it porous so that it has a good touch due to surface irregularities and low light reflection. Manufacturing method (JP-A-1-
No. 186320) Method for simply extracting filler in cast film A method for producing a porous membrane using paraffin and a polyolefin resin (Japanese Patent Laid-Open No. 55-60537) is disclosed.

[Problems to be Solved by the Invention] However, the above-described conventional method for producing a porous film or sheet has the following problems.

In the case of Japanese Patent Publication No. 59-37292, the diameter of the micropores easily changes depending on the particle size of the filler and the dispersion state of the organic liquid, and it is difficult to produce a film or sheet having uniform micropores.

The one described in JP-A-1-186320 has a low extraction efficiency due to the resin skin layer. Therefore, a large amount (30 ~
There is a problem that a filler of 40% by weight or more and 80% extraction) is required.

The method of simply extracting the filler in the cast film depends on the amount of the filler added, but the efficiency of extraction decreases due to the resin skin layer, and the efficiency of extraction improves when craze is generated by strong stretching and extraction. Had a problem of becoming fibrillated. That is, when the film with filler is made porous, it is desirable to perform extraction after stretching or to obtain a high filler concentration, but in the method of generating craze by stretching, pores are fibrillated. In addition, if the μ-order filler is filled at a high concentration, secondary agglomeration becomes a problem.

In the method of manufacturing a porous membrane using paraffin and a polyolefin resin, since the polyolefin resin used is not basically a soft polypropylene, it is necessary to mix a large amount of paraffin for extraction with a solvent. A kneading process with a Bunbury mixer or the like was necessary, which inevitably resulted in high costs.

The present inventor has found that when a special soft polypropylene is used, it is possible to obtain a soft porous film or sheet which could not be obtained by a conventional composition of polypropylene and an organic filler.

That is, the special polypropylene contains a high-molecular atactic polypropylene having a poor solvent resistance, which is rarely contained in ordinary polypropylene, in a uniform dispersion. Further, the soft block polypropylene also has an island structure in which high-molecular atactic polypropylene is attached to ethylene propylene rubber which has been used so far. Therefore, a soft and porous polypropylene film or sheet can be obtained by extracting atactic polypropylene (ethylene propylene rubber).

With this porous film or sheet, a molded article having high moisture permeability and air permeability can be obtained.

[Means for Solving Problems] The present invention has been made based on the above findings, and according to the present invention, a polypropylene homopolymer (a) composed of atactic propylene shown in (A) below: Random copolymer (b) of propylene and α-olefin shown in (B) below, and polypropylene-based block copolymer having an island structure in which atactic propylene is attached to ethylene propylene rubber (internal to polyethylene) shown in (C) below. Polymer (c), (c '), or a mixture (composition) (d) containing the polymer shown in the following (D) and (E),
(E) A soft polypropylene 40 to 100% by weight and a water-soluble organic filler 60 to 0% by weight from a film or sheet, and a low polar solvent from the group consisting of atactic polypropylene, ethylene propylene rubber, and polyethylene. Provided is a method for producing a porous film or sheet, which comprises extracting one or more selected substances and then extracting the water-soluble organic filler with water.

(A) (i) 10 to 90% by weight of boiling heptane-soluble polypropylene having an intrinsic viscosity of 1.2 dl / g or more, and (ii) 90 to 10% by weight of boiling heptane-insoluble polypropylene having an intrinsic viscosity of 0.5 to 9.0 dl / g. A polypropylene homopolymer (a) (B) having an α-olefin unit content of 0.1 to 5 mol%,
20 parts soluble in boiling hexane with an intrinsic viscosity of 1.2 dl / g or more
~ 99.9% by weight and a tensile elastic modulus of 5000 kg / cm ² or less, a random copolymer of propylene and an α-olefin having 4 to 30 carbon atoms (b) (C) an ethylene unit content of 10 to 60 Intrinsic viscosity in mol%
The ethylene-propylene block copolymer (c) is 0.5 to 7.0 dl / g and / or the ethylene unit content is 10 to 60 mol%, the polyene unit content is 1 to 10 mol%, and the intrinsic viscosity is 0.5. ~ 7.0 dl / g ethylene-propylene-polyene block copolymer (c ') (D) (i) polypropylene homopolymer (a) 10
To 95% by weight, and (ii) the ethylene-propylene block copolymer (c) and / or the ethylene-propylene-polyene block copolymer (c ') 90 to 5% by weight (a propylene-based mixture). Composition) (d) (E) (i) 10-95% by weight of the random copolymer (b)
And (ii) the ethylene-propylene block copolymer (c) and / or the ethylene-propylene-polyene block copolymer (c ') 90 to 5% by weight (propylene-based composition) ( e) In addition, the polypropylene homopolymer (a) made of atactic propylene shown in (A), the random copolymer (b) of propylene and α-olefin shown in (B), and the above (C). The polypropylene block copolymer (c), (c ') having an island structure in which atactic propylene is attached to the ethylene propylene rubber (internal to polyethylene), or a polymer thereof shown in the following (D) and (E) A mixture (composition) containing (d),
(E) After extracting the water-soluble organic filler with water from a film or sheet comprising 40 to 100% by weight of soft polypropylene and 60 to 0% by weight of the water-soluble organic filler,
There is provided a method for producing a porous film or sheet, which comprises extracting one or more substances selected from the group consisting of atactic polypropylene, ethylene propylene rubber and polyethylene with a low-polarity solvent.

Hereinafter, the present invention will be described in detail.

In the present invention, the “soft polypropylene” means a polypropylene homopolymer (a) shown in (A) below,
A random copolymer of propylene and α-olphin shown in (B), a block copolymer of propylene and α-olefin shown in (C) (c), (c ′), or (D),
The mixture (composition) (d) or (e) containing the polymer shown in (E) is meant.

(A) (i) 10 to 90% by weight of boiling heptane-soluble polypropylene having an intrinsic viscosity of 1.2 dl / g or more, and (ii) 90 to 10% by weight of boiling heptane-insoluble polypropylene having an intrinsic viscosity of 0.5 to 9.0 dl / g. A polypropylene homopolymer (a) (B) having an α-olefin unit content of 0.1 to 5 mol%,
20 parts soluble in boiling hexane with an intrinsic viscosity of 1.2 dl / g or more
~ 99.9% by weight and a tensile elastic modulus of 5000 kg / cm ² or less, a random copolymer of propylene and an α-olefin having 4 to 30 carbon atoms (b) (C) an ethylene unit content of 10 to 60 Intrinsic viscosity in mol%
The ethylene-propylene block copolymer (c) is 0.5 to 7.0 dl / g and / or the ethylene unit content is 10 to 60 mol%, the polyene unit content is 1 to 10 mol%, and the intrinsic viscosity is 0.5. ~ 7.0 dl / g ethylene-propylene-polyene block copolymer (c ') (D) (i) polypropylene homopolymer (a) 10
To 95% by weight, and (ii) the ethylene-propylene block copolymer (c) and / or the ethylene-propylene-polyene block copolymer (c ') 90 to 5% by weight (a propylene-based mixture). Composition) (d) (E) (i) 10-95% by weight of the random copolymer (b)
And (ii) the ethylene-propylene block copolymer (c) and / or the ethylene-propylene-polyene block copolymer (c ') 90 to 5% by weight (propylene-based composition) ( e) The polypropylene homopolymer (a) is particularly preferably one having the following properties (i) to (iv).

(I) In the pentad fraction by ¹³ C-NMR, rrrr / 1
-Mmmm is 20% or more.

(Ii) The melting peak temperature (Tm) measured by a differential calorimeter (DSC) is 150 ° C or higher.

(Iii) The melting enthalpy (△ H) measured by DSC is 10
It is less than 0 J / g.

(Iv) Upon observation with a transmission electron microscope, a domain structure is observed.

Among the soft polypropylenes used in the present invention, the polypropylene homopolymer (a) and the random copolymer (b) may be, for example, one of the gas phase one-step polymerization method and the slurry one-step polymerization method described below. Can be prepared by.

Hereinafter, these preparation methods will be described in order.

Gas-Phase One-Step Polymerization Method The catalyst system used in the gas-phase one-step polymerization method is, for example, (I) (i) a crystalline polyolefin and (ii) a solid catalyst component composed of magnesium, titanium, a halogen atom and an electron-donating compound. A solid component consisting of (II), an organoaluminum compound (III), an aromatic compound containing an alkoxy group (III), and an electron donating compound (IV).

The solid component (I) is a crystalline polyolefin (i).
The solid catalyst component (ii) is contained in an amount of 0.005 to 30 parts by weight (preferably 0.02 to 10 parts by weight) per 1 part by weight.

The solid component (I) is, for example, a solid catalyst component (ii)
It can be prepared by a method of prepolymerizing an olefin in the presence of an organoaluminum compound, and optionally an electron donating compound (preliminary polymerization method).

Here, the solid catalyst component (ii) contains magnesium, titanium, a halogen atom and an electron donating compound as essential components, and is prepared by contacting a magnesium compound, a titanium compound and an electron donating compound. can do.

Examples of the magnesium compound include magnesium dihalide such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxy magnesium such as diethoxy magnesium, aryloxy magnesium, alkoxy magnesium halide, and aryloxy magnesium. Alkyl magnesium such as halide and ethyl butyl magnesium, alkyl magnesium halide, or organic magnesium compound and electron donor, halosilane,
Examples thereof include alkoxysilane, silanol, and a reaction product with an aluminum compound. Among these, magnesium halide, alkoxymagnesium,
Alkyl magnesium and alkyl magnesium halide are preferable. In addition, these magnesium compounds are 1
They may be used alone or in combination of two or more.

Examples of the titanium compound include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetracyclohexyloxy titanium, and tetraphenoxy titanium. Titanium tetrahalides such as tetraalkoxytitanium, titanium tetrachloride, titanium tetrabromide and titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-
Trihalogenated alkoxytitanium such as butoxytitanium trichloride, ethoxytitanium tribromide,
Dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, Examples of the mono-hagogenized trialkoxy titanium such as tri-n-butoxytitanium chloride include
Among these, high halogen content titanium compounds, particularly titanium tetrachloride, are preferable. These titanium compounds may be used alone or in combination of two or more.

The electron-donating compound is an organic compound containing oxygen, nitrogen, phosphorus, sulfur, silicon and the like, and can basically improve the regularity in the polymerization of propylene.

Examples of such an electron-donating compound include esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, Examples thereof include organic acids. Furthermore, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxylane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane,
Organosilicon compounds such as methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltomimethoxysilane, and benzyltrimethoxysilane, aromatic dicarboxylic acid esters such as n-butyl phthalate and diisobutyl phthalate, benzoic acid , P-
Alkyl ester having 1 to 4 carbon atoms of aromatic monocarboxylic acid such as methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid, isopropyl methyl ether, isopropyl ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t Asymmetric ethers such as -butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether and t-amyl ethyl ether, 2,2'-azobis (2-ethylpropane), 2,2
-Azobis (2-ethylpropane), 2,2'-azobis (2-methylpentane), a, a'-azobisisobutyronitrile, 1,1'-azobis (1-cyclohexanecarboxylic acid), (1 -Phenylmethyl) -azodiphenylmethane, 2-phenylazo-2,4-dimethyl-4-trixypentanenitrile, and other azo compounds having a sterically hindering substituent bonded to the azo bond, and the like. They may be used, or two or more kinds may be used in combination.

Specifically, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate,
Methyl ethyl phthalate, methyl propyl phthalate,
Methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propyl terephthalate, ethyl isobutyl terephthalate, propyl Isobutyl terephthalate,
Aromatic such as dimethylisophthalate, diethylisophthalate, dipropylisophthalate, diisobutylisophthalate, methylethylisophthalate, methylpropylisophthalate, methylisobutylisophthalate, ethylpropylisophthalate, ethylisobutylisophthalate and propylisobutylisophthalate Dicarboxylic acid diester, methyl formate, ethyl acetate,
Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, ethyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate,
Dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate,
Monoesters such as amyl toluate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate,
γ-valerolactone, coumarin, phthalide, esters of C2-18 such as ethylene carbonate, benzoic acid, organic acids such as p-oxybenzoic acid, succinic anhydride, benzoic anhydride, p-toluic anhydride, etc. Acid anhydrides, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms, acetaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthyl aldehyde and other aldehydes having 2 to 15 carbon atoms C2 to C15 acid halides such as compounds, acetyl chloride, benzyl chloride, toluic acid chloride, anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole , Ethers having 2 to 20 carbon atoms such as diphenyl ether, ethylene glycol butyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N, N′-dimethylpiperazine, tribenzylamine, aniline, Examples thereof include amines such as pyridine, picoline and tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile and tolunitrile.

Among these, esters, ethers, ketones and acid anhydrides are preferable, and especially di-n-butyl phthalate,
Aromatic dicarboxylic acid diesters such as diisobutyl phthalate, benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid and alkyl esters of aromatic monocarboxylic acids such as toluic acid having 1 to 4 carbon atoms are preferable. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence.

The above-mentioned solid catalyst component (ii) can be prepared by a known method (JP-A-53-43094, JP-A-55-135102, JP-A-5-135102).
5-135103, JP-A-56-18606). For example, (1) a method of pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor and a pulverization aid optionally used and reacting with a titanium compound, (2 ) A liquid material of a magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of an electron donor,
A method of depositing a solid titanium complex, (3) a method of reacting a titanium compound with the one obtained in (1) or (2) above, (4) a method obtained in (1) or (2) above A method of further reacting an electron donor with a titanium compound, (5) a magnesium compound or a complex compound of a magnesium compound and an electron donor, an electron donor, a titanium compound, and a grinding aid optionally used It can be prepared by pulverizing in the presence of, and then treating with halogen or a halogen compound, (6) treating the compound obtained in the above (1) to (4) with halogen or a halogen compound, and the like. .

Furthermore, methods other than these methods (JP-A-56-166205, JP-A-57-63309, JP-A-57-190004, JP-A-57-300407, and JP-A-58-58). 47003), the solid catalyst component (ii) can be prepared.

Further, oxides of elements belonging to Groups II to IV of the periodic table, for example,
Oxides such as silicon oxide, magnesium oxide, and aluminum oxide, or composite oxides containing at least one oxide of an element belonging to Groups II to IV of the periodic table, for example, a solid product obtained by supporting the magnesium compound on silica alumina or the like. And an electron donor and a titanium compound in a solvent,
℃, preferably 2 minutes to 2 depending on the temperature in the range of 10 ~ 150 ℃
The solid catalyst component (ii) can be prepared by contacting for 4 hours.

In preparing the solid catalyst component (ii), an organic solvent which is inert to the magnesium compound, the electron donor and the titanium compound as a solvent, for example, an aliphatic hydrocarbon such as hexane or heptane, or an aromatic solvent such as benzene or toluene. Group hydrocarbons or halogenated hydrocarbons such as mono- or poly-halogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used.

The composition of the specific catalyst component (ii) thus prepared is usually in the range of magnesium / titanium atomic ratio of 2 to 100, halogen / titanium atomic ratio of 5 to 200, and electron donor / titanium molar ratio of 0.1 to 10. It is in.

The specific component (I) can be prepared by prepolymerizing an olefin in the presence of the specific catalyst component (ii) thus obtained, an organoaluminum compound and optionally an electron donating compound.

Examples of the organoaluminum compound used here include AlR ³ pX _3- p (1) (wherein R ³ is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom such as chlorine or bromine, and p is 1 to 1). A number represented by 3). Examples of such an aluminum compound include, for example, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, and trioctyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum. Dialkylaluminum monohalides such as monochloride and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

Further, as the electron-donating compound that can be optionally present, the compounds described in connection with the solid catalyst component (ii) can be used. In the method for preparing the solid component (I), examples of olefins include ethylene, propylene, butene-1,4-methylpentene-1.
Such as C2-C10 α-olefin, usually 30 ~
Prepolymerization is carried out at a temperature of 80 ° C., preferably in the range of 55 to 70 ° C., to form a crystalline polyolefin having a melting point of 100 ° C. or higher. At this time, the aluminum / titanium atomic ratio of the catalyst system is usually 0.1 to 100, preferably 0.5 to 5
And the electron donating compound / titanium molar ratio is 0 to 50, preferably 0.1 to 2.

The solid component (I) comprises crystalline powder such as crystalline polypropylene or polyethylene having a uniform particle size, the solid catalyst component (ii), an organoaluminum compound, an electron donating compound (having a melting point of 100 ° C. or higher). Can also be prepared by a method of dispersing (dispersion method).

Furthermore, the solid component (I) can be prepared by combining the above-mentioned prepolymerization method and dispersion method.

As described above, the catalyst system used in the gas-phase one-step polymerization method is the solid component (I), the organoaluminum compound (II), the alkoxy group-containing aromatic compound (III), and the electron-donating compound (I).
The organic aluminum compound (II) and the electron donating compound (IV) may be the compounds described above, respectively.

In addition, the alkoxy group-containing aromatic compound (III) can be represented by the general formula [In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is 1 carbon atom
To a hydrocarbon group, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is an integer of (0 to 6-m)], specifically, for example, m- Methoxytoluene, o-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole, p- (1-propenyl) anisole,
p-allylanisole, 1,3-bis (p-methoxyphenyl) -1-pentene, 5-anyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzyl alcohol, methoxy Monoalkoxy compounds such as benzyl alcohol, nitroanisole and nitrophenetol, o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene, 2,6-dimethoxyphenol, 1-allyl-3, Dialkoxy compounds such as 4-dimethoxybenzene and 1,3,5-trimethoxybenzene, 5
-Allyl-1,2,3-trimethoxybenzene, 5-allyl-1,2,4-trimethoxybenzene, 1,2,3-trimethoxy-5- (1-propenyl) benzene, 1,2,4- Examples thereof include trialkoxy compounds such as trimethoxy-5- (1-propenyl) benzene, 1,2,3-trimethoxybenzene, and 1,2,4-trimethoxybenzene. Among these, dialkoxy compounds and trialkoxy compounds are included. Alkoxy compounds are preferred. The alkoxy group-containing aromatic compounds of these are
Each may be used alone, or two or more kinds may be used in combination.

In the above catalyst system, the solid component (I) is used in an amount of 0.0005 to 1 mol per liter of reaction volume in terms of titanium atom. In addition, an alkoxy group-containing aromatic compound (III)
The amount used is 0.01 to 500 mol, preferably 1 to 300 mol, per 1 mol of titanium atom in the solid component (I).
If the amount used is less than 0.01 mol, the physical properties of the produced polymer deteriorate, and if it exceeds 500 mol, the catalyst activity decreases, which is not preferable. In this catalyst system, the atomic ratio of aluminum to titanium is 1: 1 to 3000 (preferably Is 1:40 to 800). If the atomic ratio is out of this range, sufficient catalytic activity cannot be obtained. Furthermore, the alkoxy machine is an aromatic compound (III)
And the electron donating compound (IV) have a molar ratio of 1: 0.01-100
(Preferably 1: 0.2 to 100).

In the gas-phase one-step polymerization method, homopolymerization of propylene gives the polypropylene homopolymer (a),
The random copolymer (b) can be obtained by copolymerizing propylene with an α-olefin having 4 to 30 carbon atoms.
The molecular weight can be adjusted by known means (for example, adjustment of hydrogen concentration). Polymerization temperature is generally 40-90 ℃
(Preferably 60 to 75 ° C), and the polymerization pressure is 10 to 45 kg / c.
m ² (preferably 20 to 30 kg / cm ² ), and the polymerization time is 5 minutes to 10 hours.

Slurry one-step polymerization method In the slurry one-step polymerization method, for example, either of the following two types of catalyst systems can be used. That is, (1) a catalyst comprising a combination of (a) a solid component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an alkoxy group-containing aromatic compound, and (c) an organoaluminum compound. System, or (2) (X) the solid catalyst obtained by reacting the above-mentioned (a) solid component and (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organoaluminum compound. A catalyst system comprising a combination of components and (Y) an organoaluminum compound.

First, the catalyst system of (1) above will be described. The solid component (a) contains magnesium, titanium, a halogen atom and an electron donor as essential components, and a magnesium compound, a titanium compound and an electron donor are contacted with each other. Can be prepared.

In preparing the solid component (a), an organic solvent inert to the magnesium compound, the electron donor and the titanium compound as a solvent, such as an aliphatic hydrocarbon (hexane, heptane, etc.), an aromatic hydrocarbon ( benzene,
Toluene, etc.) or halogenated hydrocarbons (1 carbon atom)
~ 12 saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbon mono- and polyhalogen compounds etc.) can be used alone or in combination of two or more kinds.

The magnesium compound, titanium compound and electron donating compound used in preparing the solid component (a) of the catalyst system (1) are each compound described in relation to the catalyst system of the gas phase one-step polymerization method described above. Can be the same. From these compounds, the solid component (a) can be prepared by a known method (for example, the method described in the gas-phase one-step polymerization method).

As the alkoxy group-containing aromatic compound (b) and the organoaluminum compound (c) which are brought into contact with the solid component (a) thus obtained, the compounds described in connection with the catalyst system of the gas phase one-step polymerization method can be used. Can be used.

Regarding the amount of each component constituting the catalyst system (1) used, the solid component (a) is usually converted into titanium atoms to give a reaction volume of 1
It is used in an amount of 0.0005 to 1 mol per liter, and the alkoxy group-containing aromatic compound (b) has a molar ratio to the titanium atom of the solid component (a) of usually 0.01 to 500 (preferably 1).
~ 300) is used in the ratio. If this molar ratio is less than 0.01, the physical properties of the polymer produced will deteriorate, and if it exceeds 500, the catalyst activity will decrease, which is not preferable. The organoaluminum compound (c) is used in an amount such that the aluminum / titanium atomic ratio is usually 1 to 3000 (preferably 40 to 800). If this amount deviates from the above range, the catalytic activity will be insufficient.

Next, the catalyst system (2) will be described. The solid catalyst component (X) in the catalyst system (2) is the solid component (a) of the catalyst system (1) and the alkoxy group-containing aromatic compound (ro). ) With the organoaluminum compound (c) in the presence or absence of the organoaluminum compound (c). For this preparation, a hydrocarbon solvent (for example, a hydrocarbon solvent used for preparing the catalyst system (1)) is generally used.

The reaction temperature is usually 0 to 150 ° C. (preferably 10 to 50 ° C.), and if this temperature is less than 0 ° C., the reaction does not proceed sufficiently, and if it exceeds 150 ° C., a side reaction occurs and the activity decreases. .

The reaction time varies depending on the reaction temperature, but is usually 1 minute to 20 hours, preferably 10 to 60 minutes.

When the solid catalyst component (X) is prepared in the presence of the organoaluminum compound (c), the concentration of the aluminum compound (c) is usually 0.05 to 100 mmol / l (preferably 1 to 10 mmol / l). is there. If this concentration is less than 0.05 mmol / liter, the effect of carrying out the reaction in the presence of the organoaluminum compound (c) is not sufficiently obtained, and if it exceeds 100 mmol / liter, the reduction of titanium in the solid component (a) is caused. As it progresses, the catalytic activity decreases.

On the other hand, when the solid component (a) is reacted with the alkoxy group-containing aromatic compound (b) in the absence of the organoaluminum compound (c) to prepare the solid catalyst component (X), the alkoxy group-containing compound (B) is used in such a proportion that the molar ratio to the titanium atom in the solid component (A) is usually 0.1 to 200 (preferably 1 to 50), and the concentration of the compound (B) is Usually, it is selected in the range of 0.01 to 10 mmol / liter (preferably 0.1 to 2 mmol / liter). If the molar ratio to the titanium atom is out of the above range, it is difficult to obtain a catalyst having a desired activity. On the other hand, if the concentration is less than 0.01 mmol / liter, the volumetric efficiency is low, which is not practical, and if it exceeds 10 mmol / liter, overreaction is likely to occur and the catalytic activity is lowered.

As the organoaluminum compound (Y) in the catalyst system (2), the organoaluminum compounds exemplified for the catalyst in the vapor phase one-step method can be used.

Regarding the amount of each component used in the catalyst system (2), the solid catalyst component (A) is converted into titanium atoms and the reaction volume is 1
The amount used is usually 0.0005 to 1 mmol / liter per liter, and the organoaluminum compound (Y) has an aluminum / titanium atomic ratio of usually 1 or less.
It is used in an amount so as to be in the range of to 3000 (preferably 40 to 800). If this atomic ratio deviates from the above range, the catalytic activity will be insufficient.

When the homopolymerization of propylene is carried out in the slurry one-stage polymerization method of the present invention, the above-mentioned polypropylene homopolymer (a) can be obtained, and propylene is copolymerized with an α-olefin having 4 to 30 carbon atoms. And the above random copolymer (b) can be obtained.

In the case of slurry one-stage polymerization, the polymerization temperature is usually 0 to 200 ° C.
(Preferably 60 to 100 ° C.), and the propylene pressure is usually selected in the range of 1 to 50 kg / cm ² . Polymerization time is 5
Minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, adjusting the hydrogen concentration in the polymerization vessel.

Next, among the soft polypropylenes used in the present invention, a mixture (propylene composition) (d) {the polypropylene homopolymer (a) and ethylene-propylene block copolymer (c) and / or ethylene-propylene. -Composition with polyene block copolymer (c ')} and mixture (propylene-based composition) (e) {said random copolymer (b) and ethylene-propylene block copolymer (c)
And / or the composition with the ethylene-propylene-polyene block copolymer (c ′)} can be prepared, for example, by any of the following gas phase multistage method, slurry multistage method or blending method.

Gas phase multi-stage polymerization method The catalyst used in the gas phase multi-stage polymerization method is the same as the catalyst used in the gas phase one-stage polymerization method.

In the gas phase multi-stage polymerization method, the first polymerization (first stage polymerization) is the same as the above-mentioned gas phase one stage polymerization. Therefore, the molecular weight can be adjusted by known means (for example, adjustment of hydrogen concentration). The polymerization temperature is generally 40 to 90 ° C (preferably 60 to 90 ° C).
75 ° C) and the polymerization pressure is 10 to 45 kg / cm ² (preferably 20).
30 kg / cm ^2), and the polymerization time is 5 minutes to 10 hours.

The second to the final polymerization (nth stage polymerization) is carried out with ethylene-
Propylene block copolymer or ethylene-propylene-polyene block copolymer.

Examples of the non-conjugated polyene that can be used in the copolymer include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,
5-isopropenyl-2-norbornene, 5- (1-butenin) -2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene,
6-methyl-4,7,8,9-tetrahydroindene, 2-
2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-hexadiene, 4-methyl-1,4-
Hexadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, Examples include 1,4,7-octatriene, 5-methyl-1,8-nonadiene, norbornadiene, vinylnorbornene and the like. Of these non-conjugated polyenes,
Particularly, dicyclopentadiene, 5-ethylidene-2-norbornene and 1,7-octadiene are preferable.

In each polymerization step, the molecular weight can be adjusted by a known means (for example, adjustment of hydrogen concentration). In the case of ethylene-propylene block copolymer,
The ethylene unit content can be adjusted by adjusting the composition of the charged gas. Also in the case of ethylene-propylene-polyene block copolymer, the polyene unit content can be adjusted by adjusting the charged amount of the polyene compound. The polymerization temperature is 20 to 90 ° C (preferably 40 to 50 ° C), and the polymerization pressure is 5 to 30 kg / cm ² (preferably 10 to 20 kg / c).
m ² ), and the polymerization time is 5 minutes to 10 hours.

Slurry multi-stage polymerization method In the slurry multi-stage polymerization method, either the catalyst system (1) or (2) used in the slurry one-stage polymerization method can be used.

The polymerization order and the number of polymerization stages in the slurry multi-stage polymerization method are not particularly limited and can be arbitrarily selected. For example, propylene homopolymerization or copolymerization of propylene with an α-olefin having 4 to 30 carbon atoms is carried out in the first and third stage polymerizations, and ethylene-propylene block copolymerization is carried out in the second and fourth stage polymerizations. Alternatively, ethylene-propylene-polyene block copolymerization can be performed. Number of polymerization stages (n
As with the gas phase multi-stage method, the optimum number of stages may be selected in order to obtain the desired product. As the polymerization method, either a continuous polymerization method or a discontinuous polymerization method can be used.

Propylene homopolymerization or propylene and α with 4 to 30 carbon atoms
-In the case of copolymerization with olefins, the polymerization temperature is usually 0-20.
The range of 0 ° C. (preferably 60 to 100 ° C.) and the propylene pressure are usually selected in the range of 1 to 50 kg / cm ² . In the case of ethylene-propylene block copolymer or ethylene-propylene-polyene block copolymer, the polymerization temperature is usually in the range of 0 to 200 ° C (preferably 40 to 80 ° C), and the olefin pressure is usually 1 to 50 kg / Selected in the cm ² range.

In any of the above polymerizations, a reaction time of about 5 minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, adjusting the hydrogen concentration in the polymerization vessel.

The ethylene unit content in the case of ethylene-propylene block copolymer can be adjusted by adjusting the feed gas composition, and the adjustment of the polyene unit content in the case of ethylene-propylene-polyene block copolymer can be performed by adjusting the charge amount. Can be done. As the polyene monomer, the polyene monomer described in the vapor phase multi-stage method can be used.

Blending Method Mixture (propylene composition) (d) and (e)
The polypropylene homopolymer (a) or the random copolymer (b) and the ethylene-propylene block polymer (c) and / or the ethylene-propylene-polyene block copolymer (c ′) are known methods ( For example, it can be prepared by blending by dry blending or kneading. The polypropylene homopolymer (a) and the random copolymer (b) can be obtained by the gas phase one-step polymerization method or the slurry one-step polymerization method, and the ethylene-propylene block copolymer (c). ) Or an ethylene-propylene-polyene block copolymer (c ') can be obtained by known methods.

The post-treatment of the polymerization method can be performed by a conventional method. That is, in the gas-phase one-stage polymerization method or the gas-phase multi-stage polymerization method, after polymerization, the polymer powder discharged from the polymerization vessel is passed through a nitrogen stream or the like in order to remove unreacted olefins and the like contained therein. You may let me. If desired, pelletization may be carried out by an extruder, and in that case, a small amount of water, alcohol, etc. may be added in order to completely deactivate the catalyst. Further, in the slurry one-stage polymerization method or the slurry multi-stage polymerization method, after the polymerization, the monomer can be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

As the filler, a water-soluble organic filler which has an average particle diameter of 30 μm or less and is in the form of fine powder particles or short fibers and is soluble in water is mainly used. Organic fillers that are easily dissolved in water include low molecular weight gelatin, low molecular weight collagen, starch, agar and the like. If the mixing ratio of the filler exceeds 60% by weight, the heat generated during kneading becomes large and the organic filler is apt to deteriorate, and when a molded product is made from the composition, the surface becomes rough.

Further, it is also possible to use a combination of large-grained and small-sized organic fillers. Generally, a particle size of 1/3 or less of the thickness is preferable. In the case of short fibers, a particle diameter whose major axis is 1/2 or less of its thickness is preferable. If the particle size of 1/3 or more or the major axis is 1/2 or more, the surface of the film or sheet becomes rough, which is not preferable.

Furthermore, an inorganic filler can also be used. As the inorganic filler, an oxide, hydroxide, carbonate, sulfate, carbide or silica filler of one kind of metal selected from the group consisting of Group IIA, Group IIIA and Group IVB of the Periodic Table is used. It is preferably used. For example, the Group IIA metal of the periodic law is an alkaline earth metal such as calcium, magnesium, and barium, the Group IIIA metal is a metal such as boron and aluminum, and the group IVB metal is Are preferably metals such as titanium, zirconium and hafnium. Oxides, hydroxides, carbonates or sulfates of these metals can be used without particular limitation. In particular, inorganic fillers that can be preferably used are more specifically illustrated. Calcium oxide, magnesium oxide, barium oxide, aluminum oxide, boron oxide, titanium oxide, zirconium oxide, and other oxides; calcium carbonate, magnesium carbonate, carbonate Carbonates such as barium; hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide; sulfates such as calcium sulfate, barium sulfate and aluminum sulfate.

The particle size of the inorganic filler is not particularly limited, but usually 0.1 to 3
The one with 0 μm is used. If a water-soluble inorganic filler is used, a porous film or sheet having a pore size corresponding to the diameter of the inorganic filler can be obtained by water extraction.

Known additives such as an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, an antiblocking agent, or a flame retardant can be added to the filler.

Films and sheets produced by mixing, molding and extracting these materials include the following embodiments.

A film or sheet with micropores on the surface.

A film or sheet that has micropores throughout.

The micropores have a maximum size of 1.2 μm and an average size of 0.6 to 0.9 μm.

Pore diameter of average 0.6-0.9μm at maximum of 1.2μm and 3-30μ
Those with a micropore distribution of two different pore sizes, with a pore size of m.

These can be appropriately produced by changing the mixed state, size, etc. of the filler.

Next, a method for manufacturing the porous film or sheet will be described.

The method for producing a porous film or sheet according to the present invention comprises a soft polypropylene 40 to 100% by weight and a water-soluble organic filler 60.
After extracting one or more substances selected from the group consisting of atactic polypropylene, ethylene propylene rubber and polyethylene with a low-polarity solvent from a film or sheet consisting of ~ 0% by weight, a water-soluble organic filler is extracted with water. Is done.

If necessary, soft polypropylene 40 to 100% by weight
And a film or sheet comprising 60 to 0% by weight of a water-soluble organic filler, the water-soluble organic filler is extracted with water and then selected from the group consisting of atactic polypropylene, ethylene propylene rubber and polyethylene with a low-polarity solvent. It is designed to extract more than one substance.

More specifically, this manufacturing method includes the following steps of drying the filler, kneading, molding, and extracting.

Drying process The water-soluble organic filler or the compound containing the water-soluble organic filler is dried at 100 to 120 ° C for 1 to 24 hours before molding, and has a water content of 2% or less, preventing foaming due to water and deterioration of the water-soluble organic filler. From the viewpoint of preventing decomposition, it is preferably 0.5% or less.

In the case of soft polypropylene alone, the drying step may be omitted.

Kneading process As a kneading device, a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, or a twin roll is used.

The kneading temperature is 170 ° C to 320 for a single soft polypropylene
C., preferably 190 to 280.degree. If the temperature at this time is low, defective melting of the soft polypropylene occurs, and if the temperature is high, thermal deterioration easily occurs.

In the case of the soft polypropylene and the water-soluble organic filler, the kneading temperature is 170 ° C to 220 ° C, preferably 190 to 210 ° C. If the temperature is low, the water-soluble organic filler may deteriorate due to poor melting of the soft polypropylene and high shear during kneading. When the temperature is high, the resin is easily deteriorated by heat, and the water-soluble organic filler is easily deteriorated by heat and decomposed.

Molding process Select an appropriate molding machine and molding method according to the molded product and its application. Usually, inflation molding and T-die molding are used.

Molding temperature is 170 ℃ to 280 when using soft polypropylene alone.
℃, compound of soft polypropylene and water-soluble organic filler is 170 ℃ ~ 220 ℃. The temperature is preferably 190 to 210 ° C.

When the temperature is low, the water-soluble organic filler deteriorates due to poor melting of the soft polypropylene and high cutting during molding. Further, when the temperature is high, the resin is easily deteriorated by heat, and the water-soluble organic filler is easily deteriorated by heat and decomposed.

Extraction process In this process, water-soluble organic filler,
Extract atactic polypropylene and ethylene propylene rubber (internal to polyethylene) to make films and sheets porous.

a) In the case of a homopolypropylene molded product (extraction of atactic polypropylene part), a low-polarity solvent (boiling hexane,
Extract for 5 minutes or more with boiling heptane.

If the extraction time is 5 minutes or less, the extraction becomes poor, and even if extraction is performed for 5 minutes or more, only isotactic polypropylene remains selectively.

Since only the pure isotactic polypropylene part remains, the solvent resistance and other properties are the same as those of general homopolypropylene.

b) In the case of a molded product of block polypropylene (ethylene propylene rubber (internal to polyethylene), extraction of atactic polypropylene) Extract with a low-polarity solvent (boiling hexane, boiling heptane) for 5 minutes or more.

If the extraction time is 5 minutes or less, the extraction becomes poor, and even if extraction is performed for 5 minutes or more, only isotactic polypropylene remains selectively.

c) In the case of a homopolypropylene + water-soluble organic filler molded product, it is extracted twice.

Extraction of the atactic polypropylene part is carried out according to a). Next, the water-soluble organic filler is extracted with water for 5 minutes or more. As a result, a film with more voids than a),
I can make a sheet. By selecting the particle size and amount of the water-soluble organic filler, a porous filler with a varied pore size distribution is obtained.

d) In the case of block polypropylene + water-soluble organic filler molded product Ethylene propylene rubber (internal to polyethylene) and atactic polypropylene are extracted according to b).
Next, the water-soluble organic filler is extracted with water for 5 minutes or more.

A filler having more voids than b) is formed. By selecting the particle size and amount of the water-soluble organic filler, a porous filler with a varied pore size distribution is obtained.

[Example] Kneading process Using a Banbury mixer, the resin temperature during kneading is 200 ° C.
The compound was obtained by adjusting the number of revolutions of Banbury mixer and the degree of pressurization so that kneading would occur. The initial set temperature of the device was 170 ° C.

The obtained compound was made into a sheet with a roll (temperature 140 ° C.), cooled, and then pelletized with a sheet pelletizer.

A single piece of soft polypropylene was directly molded.

Molding process (in the case of single-piece soft polypropylene) The resin temperature was set to 220 ° C with a T-die molding machine (TLC35-20 manufactured by Tsukada Kiki Seisakusho). With a screw speed of 50 rpm, a width of 17
Extruded at a rate of 1.2 kg / Hr from a die with 0 mm and a lip interval of 0.6 mm, bring an air knife into contact with a 170 mm diameter cooling roll in which water at 30 ° C circulates, take it out at 5.3 m / min, and obtain a thickness of 30
A film of μm was obtained.

(In the case of soft polypropylene containing a water-soluble organic filler) The resin temperature was set to 200 ° C with a T-die molding machine (TLC35-20 manufactured by Tsukada Kiki Seisakusho). With a screw speed of 50 rpm, a width of 17
It is extruded at a rate of 1.1 kg / Hr from a die with 0 mm and a lip interval of 0.6 mm, an air knife is brought into contact with a 170 mm diameter cooling roll in which water at 30 ° C circulates, and it is taken out at 5.0 m / min.
A film of μm was obtained.

Extrusion Process After the kneading process and molding process, the following process was performed.

Example 1 A film and sheet obtained by molding a homo-soft polypropylene produced as follows were placed in an extraction device equipped with a reflux condenser, and a 10 cm square film was immersed in 100 ml of boiling heptane for 60 minutes to remove the atactic polypropylene component. It was extracted to obtain a porous film or sheet. The porous film or sheet had a net structure having a maximum micropore size of 1.2 μm or less and an average of 0.6 to 0.9 μm communicating holes, and the porosity was 49.5%.

The maximum micropore size was obtained from the observation results with a scanning electron microscope, and the confirmation of the communication holes was confirmed using the liquid paraffin permeation time of the film or sheet.

The porosity was determined from the weight before and after immersion in liquid paraffin.

Example-2 A film and sheet obtained by molding a block soft polypropylene produced as follows were placed in an extraction device equipped with a reflux condenser of 10 cm square and immersed in 100 ml of boiling heptane for 60 minutes. Polyethylene intrinsic), atactic polypropylene component extracted to obtain a porous film,
Got the sheet. The porous film or sheet had a network structure having a maximum micropore diameter of 1.2 µm or less and an average of 0.6 to 0.9 µm communicating pores, and the porosity was 75%.

Example 3 A film or sheet obtained by kneading and molding dry polypropylene (average molecular weight: 5000, manufactured by Nitta Gelatin Co., Ltd.) into a powder having an average particle size of 5 μm by a ball mill and compounding 30% by weight was formed. Similarly to Example-1, the atactic polypropylene component was extracted by immersing it in boiling heptane for 30 minutes, and then by extracting gelatin in water at 80 ° C. for 30 minutes to obtain a porous film or sheet. This film or sheet has a network structure composed of communicating holes made up of pores with a maximum pore size of 1.2 μm or less and an average of 0.7 μm and pores with a maximum pore size of 7 μm or less and an average of 5 μm with a porosity of 71%. It was

Example-4 60% by weight homo-soft polypropylene produced as follows
And gelatin (average molecular weight 5000, manufactured by Nitta Gelatin Co., Ltd.)
In a dry state, a ball mill was used to mix and knead 40 wt% with an average particle size of 5 μm, and the resulting film and sheet 10 cm square were extracted with 100 ml of boiling heptane for 30 minutes to extract atactic polypropylene and further boiled water. Soaked in
Gelatin was extracted for 30 minutes to obtain a porous film or sheet.

Porous films and sheets have a maximum pore size of 7 μm or less, average 5 μm pores and maximum pore size of 1.2 μm or less, average 0.6 to 0.9 μ
It has a net-like structure consisting of communicating holes in which m holes are mixed,
The porosity was 70%.

Example of production of soft polypropylene Homo-soft polypropylene (1) Preparation of fixed catalyst component A glass three-necked flask with an internal volume of 500 ml, which had been sufficiently purged with nitrogen, had 20 ml of purified heptane, 4 g of Mg (OEt) ₂ and 1.2 g of di-n-butyl phthalate. g was added, keeping the inside of the system to 90 ° C., was added dropwise TiCl ₄ 4 ml while stirring, further adding introducing TiCl ₄ 111 ml, and heated to 110 ° C.. After reacting for 2 hours at 110 ° C., it was washed with purified heptane at 80 ° C. 115 ml of TiCl ₄ was added to the obtained solid phase portion, and the mixture was reacted at 110 ° C. for 2 hours. After completion of the reaction, the product was washed several times with 100 ml of purified heptane to give a solid catalyst component [corresponding to the solid catalyst component (ii) in the gas phase method].

(2) Preparation of solid component In a glass pressure-resistant _three- necked flask with an internal volume of 2.5 liters, which had been sufficiently replaced with nitrogen, 1.7 liters of purified heptane and AlEt ₃ 0.07
Mol, 0.05 mmol of diphenyldimethoxysilane (DPDMS) and 120 g of the catalyst component of (1) above were added. In the system
The temperature was maintained at 30 ° C., propylene was continuously supplied while stirring, and the internal pressure was maintained at 05 kg / cm ² . This reaction was continued for 1 hour and then washed 5 times with 1 liter of purified heptane to obtain a solid component [corresponding to the solid component (I) in the gas phase method].

(3) Gas-phase first-stage polymerization In a 5 liter stainless steel pressure-resistant autoclave containing 20 g of polypropylene powder, AlEt ₃ 3 mmol, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.15 mmol, diphenyldimethoxysilane (DPDMS). 20 ml of a heptane solution containing 0.23 mmol and 100 mg (0.06 mmol in terms of Ti atom) of the solid component (I) of the above (2) was added. After evacuating the system for 5 minutes, gas phase polymerization was carried out at 70 ° C. for 1.7 hours while supplying propylene gas until the total pressure reached 28 kg / cm ² . 640 g of soft polypropylene having a melt index (MI) of 0.5 g / 10 min was obtained. The boiling heptane-soluble content (HSP content) of this soft polypropylene is 49.5% by weight,
The intrinsic viscosity was 1.99 dl / g. The boiling heptane insoluble content (HIP content) was 50.5% by weight, and the intrinsic viscosity was 4.13 dl / g.
Met. Furthermore, the rrrr / 1-mmmm was 34.5% in the pentad fraction by ¹³ C-NMR, the melting peak temperature (Tm) measured by DSC was 158 ° C, and the melting enthalpy (ΔH) measured by DSC was 58.2J. / g, and the domain structure was observed when observed with a transmission electron microscope.

Block Soft Polypropylene Similar to the homo-soft polypropylene, the solid catalyst component and the solid component A were prepared, and then the following procedure was performed.

(1) Gas-phase first-stage polymerization In a pressure-resistant stainless steel autoclave of 5 liter containing 20 g of polypropylene powder, AlEt ₃ 3 mmol, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.15 mmol, diphenyldimethoxysilane (DPDMS). 20 ml of a heptane solution containing 0.23 mmol and 100 mg (0.06 mmol in terms of Ti atom) of the solid component (I) prepared in the above Production Examples 1 (1) and (2) was added. After evacuating the system for 5 minutes, hydrogen gas was introduced up to 0.6 kg / cm ² , and the total pressure was 2
At 70 ° C while supplying propylene gas to 8 kg / cm ^2.
Gas phase polymerization was carried out for 1.7 hours.

(2) Gas-Phase Second Stage Polymerization After the reaction of (1) above was completed, the system was depressurized and evacuated, then hydrogen gas 0.5 kg / cm ² , ethylene-propylene mixed gas (molar ratio 1/4) Was supplied to 10 kg / cm ² and vapor phase polymerization was carried out at 50 ° C. for 1.4 hours.

550 g of a propylene elastomer having a melt index (MI) of 3.9 g / 10 min was obtained. This elastomer consisted of 72% by weight of polypropylene homopolymer and 28% by weight of ethylene-propylene copolymer, and the homopolymer had a boiling heptane-soluble content (HSP content) of 48.2% by weight with an intrinsic viscosity of 1.18 dl / g.
And boiling heptane-insoluble matter (HIP content) with an intrinsic viscosity of 1.84 dl / g 5
1.8 wt%, rrrr / 1-mmmm was 34.5% in pentad fraction by ¹³ C-NMR, melting peak temperature (Tm) measured by DSC was 158 ° C, melting enthalpy measured by DSC (ΔH ) Was 62.6 J / g, and the domain structure was observed under the transmission electron microscope. On the other hand, the ethylene unit content of the copolymer was 30 mol% and the intrinsic viscosity was 1.77 dl / g.

[Characteristic measuring method and effect evaluating method] Next, regarding the measuring method and the evaluating method relating to the present invention,
Shown together.

(1) Average Pore Size and Maximum Pore Size Measure the major axis and uniaxial of the pore size by observing the sample surface with a scanning electron microscope (SEM), and take the geometric mean of the average major axis and the uniaxial axis as the average pore size. Similarly, the major axis of the maximum hole found on the sample surface or the cleavage plane is the maximum hole diameter.

(2) Porosity: Pr sample (10 x 10 cm) was immersed in liquid paraffin for 24 hours, and the weight (W2) after the surface liquid paraffin was sufficiently wiped off
Is measured, and the pore volume (Vo) is obtained from the weight (W1) of the sample before immersion and the density (ρ) of liquid paraffin by the following formula.

Vo = (W2-W1) ρ Porosity (Pr) is calculated from apparent volume (value calculated from thickness and dimensions) V and pore volume Vo.

Pr = Vo / V × 100 (%) (3) Intrinsic viscosity ([η]) Sequentially according to ASTM D1601, 0.1g sample is added to 135 ° C tetralin 100ml.
The solution was completely dissolved in the solution, and the solution was measured with a viscometer in a thermostat at 135 ° C. to obtain the intrinsic viscosity from the specific viscosity S according to the following equation.

[Η] = S / (0.1 × 1 + 0.22 × S)) (4) Isotactic Index (II) and Isotactic Ventad Fraction The sample is dried at 130 ° C. for 2 hours. From now on, weight W (mg)
Of the sample is placed in a Soxhlet extractor and extracted with boiling n-heptane for 12 hours.

Next, this sample was taken out, thoroughly washed with acetone, and then vacuum dried at 130 ° C. for 6 hours, and then the weight W ′ (mg)
Is calculated and calculated by the following formula.

II = (W ′ / W) × 100% Further, regarding the above extraction residue, the peak area attributed to the five consecutive meso bond region (mmmmm) of the propylene monomer unit in the total absorption peak of the methyl carbon region of the ¹³ C-NMR spectrum The ratio is defined as the isotactic pentad fraction. The attribution of peaks is based on Hacromelecules 8,687 (1975).

(5) Melting point and melting crystallization temperature of polypropylene Using a scanning calorimeter system DSC-2 type (manufactured by Perkin Elmer), sample 5
mg is measured from room temperature in a nitrogen stream at a temperature rising rate of 20 ° C./minute, and the endothermic peak temperature associated with melting is taken as the melting point.

Subsequently, the latent heat peak temperature associated with the crystallization of polypropylene is taken as the melting and condensing temperature in the process of raising the temperature to 280 ° C., holding it for 5 minutes, and then lowering the temperature at a descending rate of 20 / min.

[Effects of the Invention] As described above, according to the porous film or sheet of the present invention, a molded article having flexibility, high moisture permeability, and air permeability can be obtained.

Moreover, according to the manufacturing method of the present invention, a film or a sheet can be easily manufactured.

Claims (2)

[Claims] 1. A polypropylene homopolymer of atactic propylene (a) shown below (A), a random copolymer of propylene and α-olefin (b) shown below (B), and below (C). Polypropylene block copolymers (c) and (c ') having an island structure in which atactic propylene is attached to ethylene propylene rubber (internal to polyethylene) shown in (4) or their weights shown in (D) and (E) below. A mixture (composition) (d) containing a coalescence,
(E) a soft polypropylene 40 to 100% by weight and a water-soluble organic filler 60 to 0% by weight from a film or sheet, and a low polar solvent from the group consisting of atactic polypropylene, ethylene propylene rubber, and polyethylene. A method for producing a porous film or sheet, which comprises extracting one or more selected substances and then extracting the water-soluble organic filler with water. (A) (i) 10 to 90% by weight of boiling heptane-soluble polypropylene having an intrinsic viscosity of 1.2 dl / g or more, and (ii) 90 to 10% by weight of boiling heptane-insoluble polypropylene having an intrinsic viscosity of 0.5 to 9.0 dl / g. A polypropylene homopolymer (a) (B) having an α-olefin unit content of 0.1 to 5 mol%,
20 parts soluble in boiling hexane with an intrinsic viscosity of 1.2 dl / g or more
~ 99.9% by weight and a tensile elastic modulus of 5000 kg / cm ² or less, a random copolymer of propylene and an α-olefin having 4 to 30 carbon atoms (b) (C) an ethylene unit content of 10 to 60 Intrinsic viscosity in mol%
The ethylene-propylene block copolymer (c) is 0.5 to 7.0 dl / g and / or the ethylene unit content is 10 to 60 mol%, the polyene unit content is 1 to 10 mol%, and the intrinsic viscosity is 0.5. ~ 7.0 dl / g ethylene-propylene-polyene block copolymer (c ') (D) (i) polypropylene homopolymer (a) 10
To 95% by weight, and (ii) the ethylene-propylene block copolymer (c) and / or the ethylene-propylene-polyene block copolymer (c ') 90 to 5% by weight (a propylene-based mixture). Composition) (d) (E) (i) 10-95% by weight of the random copolymer (b)
And (ii) the ethylene-propylene block copolymer (c) and / or the ethylene-propylene-polyene block copolymer (c ') 90 to 5% by weight (propylene-based composition) ( e) 2. A polypropylene homopolymer of atactic propylene (a) shown in (A), a random copolymer of propylene and α-olefin (b) shown in (B), and (C). Polypropylene block copolymers (c) and (c ') having an island structure in which atactic propylene is attached to ethylene propylene rubber (internal to polyethylene) shown in (4) or their weights shown in (D) and (E) below. A mixture (composition) (d) containing a coalescence,
(E) After extracting the water-soluble organic filler with water from a film or sheet comprising 40 to 100% by weight of soft polypropylene and 60 to 0% by weight of the water-soluble organic filler,
A method for producing a porous film or sheet, which comprises extracting one or more substances selected from the group consisting of atactic polypropylene, ethylene propylene rubber and polyethylene with a low-polarity solvent.