JPH03168229A - Porous film or sheet and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject porous film or sheet by extracting filler and/or ethylene-propylene rubber (containing polyethylene) from film or sheet comprising specific soft polypropylene optionally containing filler. CONSTITUTION:(A) 90-40wt.% soft homopolypropylene is mixed with 10-60wt.% organic filler having 3-30mum particle diameter or inorganic filler having 0.1-30mum particle diameter and formed to film or sheet, then the filler on at least the surface is extracted with solvent, or (B) soft blocked polypropylene is optionally mixed with the filler and formed to film or sheet, then ethylenepropylene rubber (containing polyethylene) and/or the filler on at least the surface layer is extracted with a solvent to afford the aimed porous film or sheet containing fine pores having 0.1-100mum pore diameter in a range of 2-85% of the surface area.

Description

[Detailed Description of the Invention] [Industrial Application Field J] The present invention is a porous film that is soft and has micropores and is suitable for wall materials, automobile interior molded products, sheet materials, moisture permeable waterproof blood, etc. , regarding sheets and their manufacturing methods. [Conventional Technique #i] Conventionally, there are the following methods for producing porous polypropylene films, sheets, etc. ■A method of mixing a polyolefin with an organic liquid and/or an inorganic filler, melt-extruding the mixture, and then extracting the organic liquid with a solvent to produce a porous film.
9-37292, JP-A-63-108041).

■A manufacturing method in which a water-soluble organic filler (gelatin) is added to the resin and extracted with water to make it porous, giving it a good touch due to the uneven surface and low light reflection (Japanese Patent Application Laid-Open No.
-186320). ■There is also a method that attempts to simply extract the filler from the cast film. [Problems to be solved by the invention] However, the above-mentioned conventional porous film. There were the following problems with the sheet or its manufacturing method. ■Special Publication No. 59-37292, Japanese Patent Publication No. 63-10804
The film described in No. 1 has uniform micropores, with the diameter of the micropores easily changing depending on the filler particle size and the dispersion state of the organic liquid. It was difficult to manufacture the sheet. Also, because it does not have 2 flexibility, it cannot be used in products that require flexibility.
There were problems such as flaws and limited uses. ■Also, in the method described in JP-A-1-186320, the extraction efficiency is lowered due to the resin skin layer. For this reason, there was a problem in that a large amount of filler (80% extraction at 30 to 40 f% by weight or more) was required.

■Furthermore, although it depends on the amount of filler added, the method of simply extracting the filler in the cast film has a low extraction efficiency due to the skin layer of the resin. Although it improved, there was a problem of fibrillation. In other words, when making a filler-containing film porous, it is desirable to perform extraction after stretching or use a high filler concentration, but methods that generate crazes by stretching result in the pores becoming fibrillated. Also, IL
Secondary aggregation becomes a problem when filled with a high concentration of filler of the order of magnitude. The present invention has been made in view of the above problems, and has the following advantages: low light reflection due to porous structure, good touch due to the addition of a filament filler, and high moisture absorption and desorption properties due to the removal of the skin layer.
The purpose of this invention is to provide porous films and sheets that have excellent properties such as high moisture permeability and high air permeability due to the presence of through holes, and to provide a method for manufacturing these porous films and sheets. In order to achieve the above objective, the inventor of the present invention has conducted intensive research and found that by using a special soft polypropylene, a combination of conventional polypropylene and organic (inorganic) filler can be obtained! & Soft porous film that could not be made with physical materials. After discovering that it was possible to obtain a sheet, he completely abandoned the invention. [Means for Solving the Problems] The porous film or sheet of the present invention, which was developed based on the above findings, is a film made of soft polypropylene. At least on the surface of the sheet, over 2 to 85% of its surface area, the pore size is 0.
．． It is designed to have micropores of 1 to loOpLm. In addition, if necessary, the porous film of the present invention may be used. The sheet is a film made of soft polypropylene, and at least the surface of the sheet has micropores with a pore diameter of 3 to 30 μm over 3 to 60% of the surface area.

In addition, if necessary, the porous film or sheet of the present invention may have a maximum pore size of 1.2 μm or less and an average pore size of 0.6 μm or less over 5 to 50% of the surface area of the film or sheet made of soft polypropylene. ~0.9μm
It is designed to have micropores of. In addition, if necessary, the porous film of the present invention may be used. The sheet is made of 90-40% by weight of soft polypropylene and has a pore size of 3-40% by weight.
A film consisting of 10-5 Qfflli% of a 30 μm organic filler. At least on the surface of the sheet, micropores with a maximum pore diameter of 1.2 JLm or less and an average pore diameter of 0.6 to 0.9 μm are formed over 2 to 45% of the surface area. In addition, if necessary, the porous film or sheet of the present invention may include, at least on the surface of the film or sheet,
Maximum pore size of 1.2μ over 2-45% of its surface area
micropores with an average pore size of 0.6 to 0.9 μm, and pores with a pore size of 3 to 30 μm over 10 to 60% of the surface area.
It is designed to have micropores of. In this case, the surface area of the micropores should not exceed 85% of the total area. In addition, if necessary, the porous film or sheet of the present invention may contain 99 to 40% by weight of soft polypropylene and a pore size of 0.5% by weight.
At least on the surface of a film or sheet containing 1 to 60% by weight of an inorganic filler with a diameter of 1 to 30 μm,
45% of the sample has micropores with a maximum pore diameter of 1.2 μm or less and an average pore diameter of 0.6 to 0.9 μm. In this case, the surface area of the micropores should not exceed 85% of the total area. The present invention will be explained in detail below. The porous film or sheet of the present invention has a structure in which ethylene propylene rubber (containing polyethylene) is extracted from homo-flexible polypropylene or block-flexible polypropylene. In addition, porous films and sheets made by mixing, molding, and extracting soft polypropylene and fillers (ethylene propylene rubber (containing polyethylene), water-soluble organic fillers, and inorganic fillers) are made of isotactic polypropylene, atactic polypropylene, or even fillers. It is structured as follows. The material for this porous film or sheet is 40 to 1
00fii% soft polypropylene, 60-0% by weight
filler is used. Next, soft polypropylene will be explained.

[Margin below] In this specification, "soft polypropylene" refers to the homopolymers or copolymers described in (1) to (4) below,
Furthermore, it means any of the bottoms containing these polymers. (1) (i) 10 to 90% by weight of boiling hebutane-soluble polypropylene having an intrinsic viscosity of 1.2djL/g or more, and (ii) an intrinsic viscosity of 0.5 to 9. OdjL/g boiling hebutane insoluble polypropylene 90-10% by weight
A polypropylene polymer (a), (2) (i
) The α-olefin unit content is 0-1 to 5 mol%. (ii) Boiling hexane soluble content with an intrinsic viscosity of 1.2 db/g or more is 20 to 99.9 fwt%, and a tensile modulus (by weight) is 5000 Kg/c+s
"The following random copolymer of propylene and α-1-year-old reflexine having 4 to 30 carbon atoms (b), (3) (i) the polypropylene polymer (a) 10 to
95% by weight and (it) ethylene unit content 10-6
At 0 mol%, the % intrinsic viscosity is 0.5 to 7. OdJl/g, the ethylene-brobylene copolymer (C) and/or (it) has an ethylene unit content of 10 to 60 mol%, a polyene unit content of 1 to 10 mol%, and an intrinsic viscosity of O.
A brobylene composition (d) consisting of 90 to 5% by weight of an ethylene-brobylene-boriene copolymer (c') having a molecular weight of S to 7.0djL/g, and (4)(i) the random copolymer Combined (b) 10-95f wt%. (ii) The ethylene-propylene copolymer (c) and/or the ethylene-propylene-boriene copolymer (c') 90-5
'YfL content% (e). The above polypropylene polymer (a) has the following properties*
Particularly preferred are those having (i) to (iv). (i) “In bentad fraction by C-NMH, r
rrr/l-msms is 20% or more. (ii) Melting peak temperature measured with a differential calorimeter (DSC) (
Tm) is 150°C or higher. (Weight) Enthalpy of fusion (△H) measured by DSC is 100 J
/g or less. (iv) A domain structure is observed when observed using a transmission electron gA microscope. Among the flexible polypropylenes used in the present invention, the above-mentioned polypropylene polymer (a) and random copolymer (b)
For example, the gas phase one-stage heavy stage method or the slurry method described below can be used.
It can be prepared by any one-stage polymerization method.
The catalyst systems used in the gas-phase one-stage polymerization method, which will be explained below in order about their preparation methods, are, for example, (I)
(i) a solid component consisting of a crystalline polyolefin and (11) a solid catalyst component consisting of magnesium, titanium, a halogen atom, and an electron-donating compound; (n) an organoaluminum compound; (m) an aromatic compound containing an alkoxy group; (ff)
It consists of a combination of electron-donating compounds. The above-mentioned prison substance (1) is a crystalline polyolefin (i)
A certain part (it) of the solid catalyst is added to 1 part by weight. oos~
30 parts by weight (preferably 0.02 to 10 parts). The solid component (I) may be, for example, a solid catalyst component (ii).
), an organoaluminium compound, and optionally an electron-donating compound, by a method of prepolymerizing an olefin. 2 (prepolymerization method). Here, the solid catalyst component (ii) essentially contains magnesium, titanium, a halogen atom, and an electron donating compound, and this is achieved by bringing the magnesium compound, titanium compound, and electron donating compound into contact. a
ll! can do. Examples of magnesium compounds include magnesium dihalides such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hytrotalcite, magnesium carponates, alkoxymagnesiums such as diethoxymagnesium, allyloxymagnesium, alkoxymagnesium halides, and allyloxymagnesium halides. Examples include alkylmagnesium halides such as hydroxymagnesium halide and ethylbutylmagnesium, alkylmagnesium halides, or reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, and aluminum compounds. Magnesium halide,
Preferred are alkoxymagnesium, alkylmagnesium, and alkylmagnesium halides. In addition, these magnesium compounds may be used only in 1s, or in 2s.
More than one species may be used in combination. Examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-broboxytitanium, tetraisopropoxytitanium, tetrarobetoxytitanium, tetranebutoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium. Tetrahalogenated titanium such as tetraalkoxytitanium, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium trichloride Trihalogenated alkoxytitanium such as Yoto, dimethoxytitanium dichloride, diethoxytitanium dichloride, diproboxytitanium dichloride, di-n-broboxytitanium dichloride, dithoxytitanium dibromite, and trimethoxy Titanium chloride, triethoxytitanium chloride, tribroboxytitanium chloride. Examples include monohalogenated trialkoxytitanium such as tri-n-butoxytitanium chloride, and among these, highly halogen-containing titanium compounds, particularly titanium tetrachloride, are preferred. These titanium compounds may be used alone or in combination of two or more. Electron-donating compounds are organic compounds containing oxygen, nitrogen, phosphorus, sulfur, silicon, etc., and basically can improve the regularity in the polymerization of brobylene. Examples of such electron-donating compounds include esters, thioesters, akines, ketones, nitriles, phosphines, ethers, and thioethers. Acid anhydrides, acid halides, acid amides. Examples include aldehydes and organic acids. Furthermore, for example, diphenyldimethoxysilane. diphenyldiethoxysilane,
Organosilicon compounds such as dibenzyldimethoxylane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane, penzyltrimethoxysilane, phthalic acid -n-butyl. Aromatic dicarboxylic acid esters such as diimptyl phthalate, alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid, isobrobyl methyl ether, Asymmetrical compounds such as isobrobyl ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t-butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether, t-amyl ethyl ether, etc. ether, 2
, 2゜-azobis(2-ethylbroban), 2,2-azobis(2-ethylpropane), 2,2゜-azobis(
2-methylbentane), a,a゜-azobisinbutyronitrile, l,1゜azobis(1-cyclohexanecarboxylic acid), (1-phenylmethyl)-1azodiphenylmethane, 2-phenylazo-2,4-dimethyl Examples include azo compounds in which a sterically hindering substituent is bonded to an azo bond such as -4-trixybentanenitrile;
Seeds may be used, or two or more types may be used in combination. Specifically, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl brobyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, probyl isobutyl phthalate, dimethyl terephthalate. , diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methylpropyl terephthalate, methyl isobutyl terephthalate, ethylpropyl terephthalate, ethyl isobutyl terephthalate, probyl inbutyl terephthalate, dimethyl isophthalate 2 diethyl isophthalate, dibrobyl isophthalate Phthalate, diimbutyl isophthalate,
Aromatic dicarboxylic acid diesters such as methyl ethyl isophthalate, methyl probyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and probyl isophthalate, methyl formate, ethyl acetate, vinyl acetate, acetic acid Provil, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dicrotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, benzoic acid Ethyl, brovyl benzoate, butyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate, amyl toluate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate , monoesters such as ethyl 0-chlorobenzoate and ethyl naphthoate, γ-
Esters with 2 to 18 carbon atoms such as valerolactone, coumarin, phthalide, and ethylene carbonate; organic acids such as benzoic acid and p-oxybenzoic acid; acids such as succinic anhydride, benzoic anhydride, and p-toluic anhydride. anhydrides, acetone,
Carbon a such as methyl ethyl ketone, methyl isobutyl ketone 2 acetophenone, penzophenone, benzoquinone, etc.
Ketones having 3 to 15 carbon atoms, aldehydes having 2 to 5 carbon atoms such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthylaldehyde, and 2 to 15 carbon atoms such as acetyl chloride, pendyl chloride, toluyl chloride, anisyl chloride, etc. acid halides, ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, acetate amide, benzoic acid , acid ades such as toluic acid ade, tributylamine. N,N'
-Amines such as dimethylbiverazine, tribenzylamine, aniline, pyridine, vicolin, tetramethylethylenediamine, acetonitrile, penzonitrile,
Examples include nitriles such as tolnitrile. Among these, esters, ethers, ketones and acid anhydrides are preferred, particularly di-n-butyl phthalate,
Aromatic dicarboxylic acid diesters such as diynbutyl phthalate, benzoic acid. C1-4 alkyl esters of aromatic monocarboxylic acids such as p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid are suitable. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence. The solid catalyst part (ii) can be prepared by a known method (JP-A-53-43094, JP-A-55-13510).
Publication No. 2, JP-A-55-135103, JP-A-5
6-Hl606). 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 grinding aid used as desired, and reacting it with a titanium compound; ) A method in which a liquid magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of a two-electron donor to precipitate a solid titanium complex, (3) the above (1) or (2). ), (4) a method of reacting the material obtained in (1) or (2) with an electron donor and a titanium compound, (5) a magnesium compound or A method in which a complex compound of a magnesium compound and an electron donor is ground in the presence of an electron donor, a titanium compound, and a grinding aid used as desired, and then treated with a halogen or a halogen compound, (6) Said (
It can be prepared by a method of treating the compounds obtained in steps 1) to (4) with a halogen or a halogen compound. Furthermore, methods other than these methods (Japanese Unexamined Patent Publication No. 56-166
205, JP 57-63309, JP 57-190004, JP 57-300407
(Japanese Patent Application Laid-Open No. 58-47003),
The solid catalyst fraction (ii) can be prepared. In addition, oxides of elements belonging to groups n to ■ of the periodic table, such as S
At least one oxide of silicon oxide, magnesium oxide, aluminum oxide, etc., or an oxide of an element belonging to groups ■ to ■ of the periodic table! ! A composite oxide containing the magnesium compound, such as silica alumina, supported on the magnesium compound, an electron donor, and a titanium compound are mixed in a solvent at a concentration of 0 to 200%.
℃, preferably in the range of 10 to 150℃ for 2 minutes to 24 hours.
can be prepared. In addition, in preparing the solid catalyst component (ii), an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, benzene or toluene, may be used as a solvent. Aromatic hydrocarbons or halogenated hydrocarbons such as mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used. The composition of the solid catalyst component (i+) prepared in this way is usually a magnesium/titanium atomic ratio of 2 to 100, a halogen/titanium atomic ratio of 5 to 200, and a t-child donor/titanium molar ratio of 0.1 to 1. It is in the range of 10. The above-mentioned solid component (1) can be prepared by pre-combining the solid catalyst fraction (ii) thus obtained with an olefin in the presence of an organoaluminum compound and optionally an electron-donating compound. can. The organoaluminum compound used here has the general formula A I R "I)X 3-p (
1) (R1 in the formula is an alkyl group having 1 to 10 carbon atoms,
is a halogen atom such as chlorine or bromine, and p is a number from 1 to 3). Examples of such aluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisoprobylaluminum, triisobutylaluminum, and trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, and diisobutylaluminum monochloride. , dialkyl aluminum monohalides such as dioctyl aluminum monochloride, and alkyl alkyl aluminum sesquihalites such as ethyl aluminum sesquichloride can be suitably used. These aluminum compounds may be used alone or in combination of two or more. Furthermore, as the electron-donating compound that may be present if necessary, the compounds described in connection with the solid catalyst precept (ii) can be used. In the method for preparing solid component (I), an α-olefin having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1,4-methylbenten-l, is used as the olefin, and usually 30
The child fn polymerization is carried out at a temperature in the range from ~80°C, preferably from 55 to 70°C, to form a crystalline polyolefin preferably 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,
It is preferably selected in the range of 0.5 to 5, and the electron donating compound/titanium molar ratio is 0 to 50, preferably 0.1 to 5.
Selected from a range of 2. The above-mentioned solid ingredient (1) is made by adding the above-mentioned solid catalyst substance, an organoaluminum compound, and an electron-donating compound (with a melting point of 10 O°C or more) to a crystalline powder such as crystalline polypropylene or polyethylene with a uniform particle size. It can also be prepared by dispersing (dispersion method). Furthermore, the solid component (1) can also be prepared by combining the prepolymerization method and the dispersion method described above. As mentioned above, the catalyst system used in the gas phase one-stage polymerization method includes a solid component (I), an organoaluminum compound (n), an alkoxy group-containing aromatic compound (m), and an electron-donating compound (1'V). The organic aluminum compound (n) and the electron-donating compound (Ilr) can be prepared by bringing them into contact with each other, and the compounds described above can be used, respectively. Further, the alkoxy group-containing aromatic compound (m) can be prepared by, for example, the general formula [wherein R1 is an alkyl group having 1 to 20 carbon atoms, R2 is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, n is an integer of O to (6-m)], and specifically, for example, m-methoxytoluene, 0-methoxyphenol, m-methoxyphenol, Phenol, 2-methoxy-4-methylphenol,
vinylanisole, p-(1-brobenyl)anisole, p-allylanisole, 1,3-bis(p-methoxy7enyl)-1-bentene, 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4
- Monoalkoxy compounds such as hydroxybenzene 3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole, nitrophenethole, o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene. Dialkoxy compounds such as 2,6-dimethoxyphenol, l-allyl-3,4-dimethoxybenzene, and 1,3,5-trimethoxybenzene, 5-allyl 1,2,3-trimethoxybenzene, 5-allyl ,2.4-trimethoxybenzene,! , 2,3-trimethoxy-5-(1-brobenyl)benzene, 1,2,4-trimethoxy-5-(
Examples include trialkoxy compounds such as 1-probenyl)benzene, 1,2,3-trimethoxybenzene, and 1,2,4-trimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferred. be. These alkoxy group-containing aromatic compounds may be used alone, or 2.1! You may use a combination of the above. In the above catalyst system, the solid fraction (I) has an o. It is used in an amount of oos to 1 mole. The amount of the alkoxy group-containing aromatic compound (m) to be used is 0.00000000000000000000000000 with respect to 1 mole of titanium atom in the solid component (I). The amount of O is 1 to 500 mol, preferably 1 to 300 mol. This usage amount is 0. If the amount is less than 1 mol, the physical properties of the raw polymer will deteriorate. Exceeding the SOO mole is not preferred because the catalyst activity decreases.In this catalyst system, the atomic ratio of aluminum to titanium is 1:1 to 3000 (preferably 1:40 to 800). If the atomic ratio is outside this range, sufficient catalytic activity cannot be obtained. Furthermore, an alkoxy group-containing aromatic compound (m) and an electron-donating compound (f
The molar ratio with f) is. 1:0. O1 to 100 (preferably l: 0.2 to 100). In the gas phase one-stage polymerization method, homopolymerization of brobylene yields the polypropylene polymer (a), while copolymerization of propylene with an α-olefin having 4 to 30 carbon atoms yields the random copolymer (a). Polymer (b) is obtained. Molecular weight im can be determined by known means (eg, adjusting hydrogen concentration). Polymerization temperature is generally 40-90℃
(preferably 60~75℃), and the polymerization pressure is 10~75℃.
45 Kg/am' (preferably 20-30 K
g/cm'), and the polymerization time is 5 minutes to 10 hours. Slurry I In the slurry one-stage polymerization method, for example, either of the following two types of catalyst systems can be used. That is, from a combination of (l) (a) a solid that essentially includes magnesium, titanium, a halogen atom, and an electron donor, (b) an aromatic compound containing an alkoxy group, and (c) an organoaluminum compound. or (2) (A) obtained by reacting a certain amount of the above (a) solid with (b) an alkoxy group-containing aromatic compound in the presence or absence of (viii) an organoaluminum compound. A certain catalyst system is obtained from a combination of a solid catalyst component, and (B) an organic alkunium compound. First, to explain the catalyst system (1) above, the solid component (a) essentially contains magnesium, titanium, a halogen atom, and an electron donor, and a magnesium compound, a titanium compound, and an electron donor. It can be prepared by bringing them into contact with each other. In addition, in the preparation of this solid bokubun (a), a solvent inert to the magnesium compound, electron donor and titanium compound, such as aliphatic hydrocarbons (hexane, heptane, etc.), aromatic Hydrocarbons (benzene,
toluene, etc.), or halogenated hydrocarbons (mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms, etc.) alone or in combination of two or more. It can be used. The magnesium compound, titanium compound, and electron-donating compound used in preparing the solid component (a) of the catalyst system (1) are each of the above-mentioned catalyst systems for the gas phase one-stage polymerization method. It can be the same as a compound. From these compounds, a solid fraction (a) can be prepared by a known method (for example, the method described in the gas phase one-stage polymerization method).
The alkoxy group-containing aromatic compound (b) and organoaluminum compound (c) to be brought into contact with the solid fraction (a) thus obtained are also added to the catalyst system of the gas phase one-stage polymerization method.
Each of the compounds mentioned in series can be used. Regarding the usage amount of each component constituting the catalyst system (1), the solid fraction (a) is usually determined by the reaction volume 1 in terms of titanium atoms.
The alkoxy group-containing aromatic compound (b) is used in an amount of 0.0005 to 1 mole per sentence, and the molar ratio of the alkoxy group-containing aromatic compound (b) to the titanium atom of the solid fraction (b) is usually 0.01 to 500 (preferably 1 to 300). ). If this molar ratio is less than 0.01, the physical properties of the earthen polymer will decrease,
If it exceeds 500, the catalytic activity decreases, which is not preferable. Also. The organoaluminum compound (c) usually has an aluminum/titanium atomic ratio of 1 to 3 ooo (preferably 4
0 to 800). If this amount exceeds the above range, the catalyst activity will be insufficient. Next, to explain the catalyst system (2), the solid catalyst (A) in this catalyst system (2) is composed of the solid catalyst (A) of the catalyst system (1) and an alkoxy group-containing aromatic compound. It can be prepared by reacting (b) with the organoaluminum compound (c) in the presence or absence of the organoaluminum compound (c). For this preparation, a hydrocarbon solvent (for example, the hydrocarbon solvent used in the preparation of the catalyst system (1)) is generally used. The reaction temperature is usually 0 to 150°C (preferably 10 to 50°C).
``C), and if this temperature is less than 0°C, the reaction will not proceed sufficiently, and if it exceeds 150°C, side reactions will occur and the activity will decrease.The reaction time varies depending on the reaction temperature, but usually is from 1 minute to 20 hours, preferably from 10 to 60 minutes. When preparing the solid catalyst fraction (A) in the presence of the organoaluminum compound (c), the concentration of the aluminum compound (c) is usually 0.05 to 100 mmol/Jl (preferably 1 to 10 mmol/Jl).
．． If the amount is less than 0.5 mmol/mole, the effect of conducting the reaction in the presence of the organoaluminum compound (c) will not be sufficient, and if it exceeds 100 mmol/mimole, the solid content (b) will not be obtained.
As the reduction of titanium inside progresses, the catalytic activity decreases. On the other hand, when preparing the solid catalyst fraction (A) by reacting the solid fraction (a) with the alkoxy group-containing aromatic compound (b) in the absence of the organoaluminum compound (c), the alkoxy group The containing compound (b) is used in such a proportion that the molar ratio to the titanium atoms in the solid fraction (a) is usually 0.1 to 200 (preferably 1 to 50), and The concentration of b) is usually selected in the range of 0.01 to 10 mmol/ml (preferably 0.1 to 2 mmol/!l). If the molar ratio to titanium atoms is outside the above range, it will be difficult to obtain a catalyst with the desired activity. Further, if the concentration is less than 0.01 mmol/l, the volumetric efficiency is low and it is not practical, and if it exceeds 10 mmol/l, overreaction tends to occur and the catalytic activity decreases. As the organoaluminum compound (B) in the catalyst system (2), the organoaluminum compounds exemplified in connection with the catalyst for the one-stage gas phase method can be used. Regarding the amount of each component used in the catalyst system (2), the solid catalyst component (A) is equivalent to the reaction volume 1 in terms of titanium atoms.
The organoaluminum compound (
B) has an aluminum/titanium atomic ratio of usually 1 to 30.
00 (preferably 40 to 800). If this atomic ratio exceeds the above range, the catalyst activity will be insufficient. In the slurry one-stage polymerization method of the present invention, when brobylene is homopolymerized, the polypropylene polymer (a
) can be obtained, and brobylene and α having 4 to 30 carbon atoms can be obtained.
By carrying out copolymerization with polyolefin, the above-mentioned random copolymer (b) can be obtained. In the case of slurry one-stage polymerization, the polymerization temperature is usually 0 to 200°C.
(preferably in the range of 60 to Zooo°C), and more particularly, the brobylene pressure is usually selected in the range of 1 to 50 Kg/cm''. Polymerization time of about 5 minutes to 10 hours is sufficient; The molecular weight of the TA section can be determined by known means 2, for example, by adjusting the hydrogen concentration in the polymerization vessel.Next, among the soft polypropylenes used in the present invention, propylene-based composition (d) composition of polymer (a) and ethylene-propylene copolymer (C) or ethylene-propylene-boriene copolymer (C')} and propylene-based composition (e) {the random copolymer (b) and an ethylene-propylene copolymer (C) or an ethylene-propylene-boriene copolymer (C')} can be produced, for example, by the following gas phase multi-stage method, slurry multi-stage method or blending 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. The first polymerization (first stage polymerization) is the same as the gas phase one stage polymerization described above.Therefore, the molecular weight can be adjusted by known means (for example, mffi of hydrogen concentration).The polymerization temperature is generally 40°C. -90°C (preferably 60-75°C), the polymerization pressure is 10-45 Kg/cm" (preferably 20-30 Kg/cm"), and the polymerization time is 5 minutes to 10 hours.

The second to final polymerization (nth stage polymerization) is ethylene-brobylene copolymerization or ethylene-brobylene-boriene copolymerization. Examples of non-conjugated polyenes that can be used in the copolymer include dicyclobentadiene, tricyclobentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene. norbornene, 5-isopropylidene-2-norbornene,
5-Imbrobenyl-2-norbornene, 5-(1-butenine)-2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5.9-cyclotodecatriene, 6-methyl-4.7,8.9-tetrahydro Indene, 2-2゜-dicyclobentenyl, trans-1.2
-divinylcyclobutane, 1,4-hexadiene, 4-
Methyl-1,4-hexadiene, L,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1.9
-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 1,4
．． Examples include 7-octatriene, 5-methyl-1.8-nonadiene, norbornadiene, and vinylnorbornene. Among these nonconjugated polyenes, cyclobentadiene, 5-ethylidene-2-norbornene, and 21,7-octadiene are particularly preferred. At each polymerization step, the molecular weight WW1 can be determined by known means (for example, hydrogen concentration in mm). In the case of ethylene-propylene copolymers, the ethylene unit content can be controlled by adjusting the feed gas composition. Also, in the case of an ethylene-propylene-boriene copolymer, the adjustment to contain polyene units can be made by changing the amount of the polyene compound charged. The polymerization temperature is 20
to 90°C (preferably 40 to 50°C), and the polymerization pressure is 5 to 30 Kg/am” (preferably 10 to 20
Kg/am").The polymerization time is 5 minutes to 10 hours. Also in the slurry one-stage polymerization method and the slurry multi-stage polymerization method, the catalyst system (1) or (2 ) can be used.The polymerization order and the number of polymerization stages in the slurry multistage polymerization method are not particularly limited and can be selected arbitrarily.For example, in the first and third stage polymerization, propylene homopolymerization or It is possible to perform copolymerization of brobylene and an α-olefin having 4 to 30 carbon atoms, and perform ethylene-brobylene copolymerization or ethylene-propylene-boriene polymerization in the second and fourth stage polymerization.Number of polymerization stages As with the gas phase multi-stage method, the number of stages (n) can be determined by selecting the optimal number of stages to obtain the desired raw material, and the polymerization method can be either continuous polymerization method or non-j!! In the case of propylene homopolymerization or copolymerization of brobylene and an α-olefin having 4 to 30 carbon atoms, the polymerization temperature is usually O~
In the range of 200°C (preferably 60 to 100°C), the brobylene pressure is usually selected in the range of 1 to 50 Kg/c@”. In the case of -borien copolymerization,
Polymerization temperature is usually 0 to 200°C (preferably 40 to 80°C)
C) range, and the olefin pressure is usually 1 to 50 κg/
In all 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, such as adjusting the hydrogen concentration in the polymerization vessel. The ethylene unit content I!1 in the case of ethylene-propylene copolymer can be carried out by the two charge gas compositions, and the polyene unit content in the case of ethylene-propylene-polyene copolymer. The content can be adjusted by changing the amount charged. As the polyene monomer, the polyene monomer described in the gas phase multi-stage method can be used. (e) is a polypropylene polymer (a) or a random copolymer (b) and an ethylene-brobylene copolymer (C) or an ethylene-brobylene-boriene copolymer (C゛). The polypropylene polymer (a) and the random copolymer (b) can be prepared by blending by a method (for example, dry blending or cross-mixing). - It can be obtained by a one-stage polymerization method, and the ethylene-brobylene copolymer (C) or the ethylene-brobylene-boriene copolymer (C') can each be obtained by a known method. Note that the post-treatment after the ffi synthesis can be carried out by a conventional method.In other words, in the gas phase one-stage polymerization method or the gas phase multi-stage polymerization method, after the polymerization, this In order to remove unreacted olefins contained therein, a stream of nitrogen or the like may be passed through the catalyst.Also, if desired, it may be pelletized using an extruder.In order to completely deactivate the catalyst, In addition, in the slurry one-stage polymerization method or the slurry multi-stage polymerization method, after polymerization, the monomer is completely separated from the polymer that is taken out from the polymerization vessel, and then pelletized. (Hereinafter V-margin) The above-mentioned flexible polypropylene includes homopolypropylene and block polypropylene, and homopolypropylene has a two-sea-island structure and is an atactic polymer with an island fraction of Mw=40,000 or more. Particle size composed of polypropylene 1.
Refers to soft polypropylene with a thickness of 2 μm or less. In addition, block polypropylene has a seabird structure, and the island component is Mw =
A soft polypropylene with a particle size of 2 mm or less that is composed of atactic polypropylene having a molecular weight of 40,000 or more, ethylene propylene rubber, and polyethylene surrounded by ethylene propylene rubber. Atactic polypropylene for homopolypropylene, atactic polypropylene for block. Ethylene propylene rubber has a polyethylene component and is easily soluble in low polar solvents. The above-mentioned soft polypropylene has a breaking point of the tensile SSdll wire greater than the yield point or does not exhibit yield. As the water-soluble organic filler, water-soluble organic fillers that have an average particle size of 30 μm or less, are in the form of fine powder particles or short mta, and are soluble in water are mainly used. Organic fillers that are easily soluble in water include low molecular weight gelatin, low molecular weight collagen, starch, and agar. If the mixing ratio of filler-1 is 60% by weight or more, heat generation during kneading increases,
The organic filler deteriorates easily, and when a molded product is made with the filler, the surface becomes extremely rough. Examples of water-insoluble organic fillers include leather powder. Silk powder. Cellulose, bamboo powder, gelatin, 6-nylon. 6.6-Boria resins such as nylon: Fluorine resins such as polytetrafluoroethylene, tetrafluoroethylene hexafluoropropylene copolymers: polyamides; silicone resins; phenolic resins; benzoguanamine resins; or styrene , acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, etc., and a methyl crosslinking agent such as divinylbenzene. When extracting the filler, the blending ratio of the soft polypropylene and filler is 90 to 90%.
40% by weight, preferably 70-40% by weight, and 10-60% by weight, preferably 30-60% by weight of filler.
It is. When the percentage of filler is less than the lower limit,
The resulting microporous film has insufficient pore formation, making it impossible to obtain the desired porosity. On the other hand, if the proportion of filler added exceeds the above upper limit, the formability of the sheet or film tends to deteriorate, or the sheet or film cannot be stretched sufficiently, making it impossible to impart sufficient porosity, which is undesirable. Examples of inorganic fillers include Group IIA of the periodic table, f
Oxide, hydroxide, carbonate of one metal selected from the group consisting of group 5mA and group rVB, f! Acid acid. Carbide or silica fillers are preferably used. For example, metals in group IIA of the periodic table include alkaline earth metals such as calcium, magnasium, and barium; metals in group fnmA include boron and aluminum; and metals in group ffB include metals such as boron and aluminum. , titanium, zirconium. Metals such as hafnium are preferred. Oxides and hydroxides of these metals. Carbonates or sulfates can be used without particular limitation. In particular, more specific examples of S* fillers that are preferably used include calcium oxide, magnesium oxide, and barium oxide. Aluminum oxide. Oxidation of boron oxide, titanium oxide, zirconium oxide, etc.? k: Calcium carbonate. Magnesium carbonate. Carbonates such as barium carbonate: Magnesium hydroxide. Hydroxides such as calcium hydroxide and aluminum hydroxide: calcium sulfate. These include sulfates such as barium sulfate and aluminum sulfate. It is preferable for the filler to have a particle size of 173 or less of the thickness. In the case of ism miscellaneous, it is preferable that the major axis is 1/2 or less of the thickness. If the particle size is 173 or more and the major axis is 1/2 or more, the film is The surface of the sheet becomes rough, which is not desirable. Fillers include known additives such as antioxidants, heat stabilizers, and lubricants. Antistatic agent. Anti-blocking agents or flame retardants may also be added. Examples of films and sheets manufactured by mixing, molding, and extracting these materials are as follows. ■Film made of soft polypropylene. A sheet having micropores with a pore diameter of 0.1 to 100 μm covering 2 to 85% of the surface area at least on the surface of the sheet. (2) A film or sheet made of soft polypropylene having micropores with a pore diameter of 3 to 30 μm covering 3 to 60% of the surface area at least on the surface. This porous film. The sheet is made of high-molecular atactic polypropylene, which is smooth and has a pore size and a pore size distribution that depend on the diameter C of the water-soluble organic filler and inorganic filler. The amount of high molecular weight atactic polypropylene is 8 to 63f% by weight.
■Film made of soft polypropylene. At least on the surface of the sheet, over 5 to 50% of its surface area, the maximum pore diameter is 1.2 m or less and the average pore diameter is 0.6 to 0.9 #L.
It has micropores of m. This porous film/sheet is! After the ethylene propylene rubber (containing polyethylene), which is the island component produced in the first step, is selectively released, it has a smooth and sharp distribution, and is a high-molecular atactic polypropylene. The amount of polymeric atactic polypropylene is 10-47.5f% by weight. ■At least on the surface of a film or sheet made of 90-40% soft polypropylene and 10-60% by weight organic filler with a pore size of 3-30 Bm, the maximum pore size is 1.2 μm or less over 2-45% of the surface area. The average pore size is 0.6-0.
It has micropores of 9JLm. This porous film or sheet has a smooth and sharp distribution after the polymerized ethylene propylene rubber (including polyethylene) is selectively released, and is made of high molecular weight atactic polypropylene. ．． Furthermore, if it contains a natural water-insoluble organic filler, it has moisture absorption and desorption properties. The amount of high molecular weight atactic polypropylene is 1 to 42.8f% by weight. ■At least on the surface of the film or sheet, the maximum pore size is 1.2p over 2 to 45% of the surface area. micropores with an average pore diameter of 0.6 to 0.9 μm, and micropores with a pore diameter of 3 to 30 Bm over 10 to 60% of the surface area. This porous film or sheet has a smooth and sharp distribution after selectively releasing the ethylene propylene rubber (containing polyethylene) produced by water-insoluble organic filler polymerization. There is atactic polypropylene. Furthermore, it has a relatively large and mild distribution after the water-soluble organic puller is removed. The amount of polymeric atactic polypropylene is 1~
It is 42.8fii%.

■99-40% by weight of soft polypropylene and pore size of 0.
1 to 307 Lm of inorganic filler in an amount of 1 to 60% by weight on at least the surface thereof. One with a pore diameter of 1 to 30 μm. This porous film. The sheet is made of high-molecular atactic polypropylene, which is smooth and has a pore size and pore size distribution that depend on the diameters of the water-soluble organic filler and inorganic filler. The amount of high molecular weight atactic polypropylene is I to 33.
2f% by weight. Ethylene propylene rubber (containing polyethylene) is 2 to 35% by weight. Next, porous film. We will explain the manufacturing method of the sheet. The manufacturing method of the present invention is to knead 1% by weight of soft homopolypropylene 90 to 40Tf and 10 to 60% organic filler with a particle size of 3 to 30 μm, and then form a film or sheet by T-die or inflation molding. The method is designed to extract at least the organic filler on the surface of the film or sheet. If necessary, after kneading the soft block polypropylene, a film or sheet is formed by T-die or inflated molding, and then the ethylene propylene rubber (containing polyethylene) on at least the surface of the film or sheet is extracted with a solvent. There is. In addition, if necessary, soft block polypropylene 90~
40% by weight and 10 to 10% organic filler with a particle size of 3 to 30 μm
After kneading 60% by weight, a film or sheet is formed using a Y die or inflation molding, and then a film is formed using a solvent. Ethylene propylene rubber on at least the surface of the sheet (
It is designed to extract the polyethylene contained therein. Also, if necessary. ! ! : Ka block polypropylene 9
Organic filler 1 with a content of 0 to 40% by weight and a particle size of 3 to 30 μm
After kneading 0 to 60% by weight, a film or sheet is formed by Y-die or inflation molding, and then the organic filler and ethylene propylene rubber (containing polyethylene) on at least the surface of the film or sheet are extracted with a solvent. In addition, if necessary, soft block polypropylene 90~
40% by weight and organic filler 10 with a particle size of 3 to 30jLm
After kneading ~60% by weight, a film or sheet is formed by Y-die or inflation molding, and then the organic filler on at least the surface of the film or sheet is extracted with a solvent. In addition, if necessary, soft homobolypropylene 90 to 40
Weight% and 2 Inorganic filler with particle size 0.1-30 μm 10-
After kneading 60% by weight, a film or sheet is formed by T-die or inflation molding, and then the inorganic filler on at least the surface of the film or sheet is extracted with a solvent. In addition, if necessary, soft block polypropylene 99~
40% by weight and inorganic filler 1 with a particle size of 0.1 to 30 μm
After kneading ~60% by weight, a film or sheet is formed by T-die or inflation molding, and then a film is formed using a solvent. The ethylene propylene rubber (containing polyethylene) on at least the surface of the sheet is extracted. In addition, if necessary, soft block polypropylene 99~
40% by weight and inorganic filler 1 with a particle size of 0.1-30←m
After kneading ~60% by weight, a film or sheet is formed by Y-die or inflation molding, and then the inorganic filler and ethylene propylene rubber (containing polyethylene) on at least the surface of the film or sheet are extracted with a solvent. In addition, if necessary, soft block polypropylene 90~
40% by weight and inorganic filler 1 with a particle size of 0.1 to 30 μm
After kneading 0 to 60% by weight, a film or sheet is formed by T-die or inflation molding, and then the inorganic filler on at least the surface of the film or sheet is extracted with a solvent. Specifically, this manufacturing method consists of a drying process for two fillers, a kneading process, a molding process, and an extraction process. Drying process Organic fillers or composites containing organic fillers are dried at 100 to 120°C for 1 to 24 hours before molding, and the moisture content is kept below 2% to prevent foaming due to moisture and to prevent deterioration and decomposition of the organic filler. Therefore, it is preferable to keep it at 0.5% or less. In addition, in the case of soft polypropylene alone,
The drying process can also be omitted. An l-screw extruder is used as a kneading device for the mixing process. Multi-screw extruder, Banbury mixer. Use a kneader, Niki roll, etc. The crosstalk temperature is 170℃~ for soft polypropylene alone.
The temperature is 320°C, preferably 190-280°C. If the temperature is low, the soft polypropylene will not melt properly, and if the temperature is high, it will easily deteriorate due to heat. In the case of soft polypropylene and organic filler, the kneading temperature is 170°C to 220°C, preferably 190 to 210°C. If the temperature is low, the organic filler deteriorates due to poor melting of the soft polypropylene and high shear during crosstalk. At high temperatures, organic fillers tend to undergo thermal deterioration and decomposition. Uraseiou I Select the appropriate molding machine and molding method depending on the molded product and its intended use. Usually, this is done by inflation molding or Y-die molding. The molding temperature is 170℃ for single soft polypropylene.
320°C, the combination of soft polypropylene and organic filler is 170°C to 220°C, preferably 190 to 21°C
The temperature is 0°C. At low temperatures, the organic filler deteriorates due to poor melting of the soft polypropylene and high shear during molding. In addition, if the temperature is high, the organic filler is likely to undergo thermal deterioration and decomposition. In this process, the organic filler is extracted from the formed film to make the film or sheet porous. a) In the case of block polypropylene molded products (ethylene propylene rubber (polyethylene included) extraction) Extract with a low polar solvent (boiling diethyl ether, boiling dimethyl ether, boiling methyl ethyl ether) for 3 to 30 minutes. If the extraction time is less than 3 minutes, the extraction will be poor, and if the extraction time is longer than 30 minutes, a large amount of the high molecular weight atactic polypropylene will be extracted, resulting in a decrease in 2-thermal adhesion. Preferably the extraction time is 3
In ~10 minutes, a heat-adhesive porous film is formed. It becomes a sheet. b) For film (homoblock) molded products, extract with boiling water at 0°C for at least 5 minutes. If the extraction time is less than 5 minutes, the extraction will be poor, and even if the extraction is made for more than 5 minutes, only the water-soluble organic filler will selectively remain. What is extracted is homopolypropylene, block polypropylene, and atactic polypropylene. It is made of ethylene propylene rubber and has adhesive properties. The water-soluble organic filler is 30 to 60jII amount%. Particle size is 3-30 μm. C) In the case of block polypropylene + insoluble organic filler molded products, ethylene propylene rubber and polyethylene are extracted, and at the same time some atactic polypropylene is extracted. Extract with a low polar solvent (boiling diethyl ether, boiling dimethyl ether, boiling methyl ethyl ether) for 3 to 30 minutes. If the extraction time is less than 3 minutes, the extraction will be insufficient, and if the extraction time is longer than 30 minutes, a large amount of high molecular weight atactic polypropylene will be extracted, resulting in a decrease in thermal adhesiveness. Preferably the extraction time is 3
If you do this in ~10 minutes...! 8 Adhesive porous film. It becomes a sheet.

Natural water-insoluble organic fillers have moisture absorbing and desorbing properties.

d) In the case of block polypropylene + water-soluble organic filler molded products (ethylene propylene rubber. Polyethylene is extracted, and at the same time some of the attenuated polypropylene is extracted.Furthermore, it is extracted with boiling water from 0℃) Low polarity Extract with a solvent (boiling diethyl ether, boiling dimethyl ether, boiling methyl ethyl ether) for 3 to 30 minutes. If the extraction time is less than 3 minutes, the extraction will be poor, and if the extraction time is longer than 30 minutes, a large amount of high molecular weight atactic polypropylene will be extracted, resulting in a decrease in thermal adhesiveness. Preferably the extraction time is 3
By doing this in ~10 minutes, a fully adhesive porous film or sheet is formed. Next, extract with boiling water at 0°C. If the extraction time is less than 5 minutes, the extraction will be poor, and even if the extraction time is longer than 5 minutes, only the water-soluble organic filler will be selectively extracted. What remains is two-block polypropylene, which is atactic polypropylene and has adhesive properties. The water-soluble organic filler is 10 to 60% by weight. Particle size is 3-30 μm. e) In the case of film (homoblock) molded products and block polypropylene + water-soluble inorganic filler molded products For example, when a siliceous filler is generally used, caustic soda. Extraction may be carried out with an aqueous caustic alkali solution such as caustic potash.Inorganic fillers other than siliceous fillers can be extracted with hydrochloric acid, formic acid, etc.
Extract using an acid solution with acetic acid or a mixed solution of this solution and an alcohol solution such as methanol or ethanol. [Example] Kneading process Using a Banbury mixer, the resin temperature during kneading was 200℃.
Rotate the Banbury mixer so that the temperature is a. The degree of pressurization was adjusted to rA and kneaded to obtain a compound. The initial temperature setting of the equipment was 170°C. The obtained combine was made into a sheet using a roll (temperature 140°C), and after cooling, it was made into a pellet using a sheet pelletizer. Direct gloss ((In case of single soft polypropylene) T-die molding machine (Tsukada Juki Seisakusho tATLC35-20)
The resin temperature was set at 220°C. Screw rotation speed 50r
In μm, width 170 mm, riff interval 0.
It was extruded from a 6 mm die at 1.2 Kg/Hr, brought into contact with an air knife on a 170 mm diameter cooling roll with 30°C water circulating inside, and pulled off at 5.3 m/min to obtain a film with a thickness of 30 Bm. Ta. (For soft polypropylene containing water-soluble organic filler) Using a T-die molding machine (TLC35-20 manufactured by Tsukada Juki Seisakusho), the resin temperature was set to 200°C. The screw rotation speed was 50 rμ.
m, Illg 170 m m, wAo between riffs. L from a 6mm die. It was extruded at IKg/}lr, an air knife was brought into contact with a 170 mm diameter cooling roll in which water at 30°C was circulated, and the film was pulled off at 5.0 m/min to obtain a film with a thickness of 30 μm. After the kneading process and molding process described above, the following procedure was carried out. Example 1 50% by weight of homo-soft polypropylene produced as below and gelatin (average molecular weight: SOOO, Nitta Gelatin Co., Ltd.) further dried with a ball mill to reduce the average particle size to 5 μm.
Contains 50% by weight as m. The film (40 μm thick, 10 cm square) obtained by kneading and further molding was placed in an extraction device equipped with a reflux device, and immersed in 100 m of boiling water.
Gelatin was extracted for 0 minutes to obtain a porous film. The maximum pore diameter of the porous film is 7 JLm or less. It had a network structure consisting of communicating pores with an average size of 5 μm, and the porosity was 50%. The amount of high molecular weight atactic polypropylene was 49% by weight. Note that all amounts of atactic polypropylene are based on the porous film being taken as 100%. When we examined the permeability of the liquid paraffin, we found that the communicating pores were maintained. The hole diameter is determined by scanning electronics! It was determined from the results of a observation using an i0 microscope. The porosity was determined from the weight before and after immersion in liquid paraffin.

The amount of high-molecular atactic polypropylene was determined by extraction with boiling hemobutane for 6 minutes, immediately filtered, the resulting liquid was cooled to room temperature, and the precipitated material was quantified as high-molecular atactic polypropylene. Example 2 A polypropylene film was obtained in the same manner as in Example 1, except that the homosoft polypropylene was replaced with block flexible polypropylene produced as described below. The porous film had a network structure consisting of communicating pores with a maximum pore diameter of 77 mm or less and an average size of 5 wells, and the porosity was 50%. The amount of high molecular weight atactic polypropylene was 35% by weight. The amount of ethylene propylene rubber was 28% by weight. Example 3 100% by weight of block polypropylene produced as follows was cross-wired. Sheet obtained by molding (thickness 300μ
Place a 10cm square sheet of water into an extractor equipped with a reflux device and soak it in 100mjL of boiling diethyl ether.
A porous sheet was obtained by extraction for 0 minutes. On the surface of the porous sheet, pores with a maximum pore diameter of 1.2 JLm or less and an average size of 0.6 to 0.9 μm accounted for 28% of the surface area. Scanning electron microscope lol! From the results of observing the surface of the porous sheet using an L mirror, it was observed that among the islands of soft polypropylene, high molecular weight atactic polypropylene remained and ethylene propylene rubber was extracted. Example 4 70% by weight of block polypropylene produced as described below and 30% by weight of dried leather (average particle size 5 Bm) were blended and mixed. Sheet obtained by molding (thickness 300μm, 10cm
A porous sheet was obtained by placing the cube in an extractor equipped with a reflux device, immersing it in 100 ml of boiling diethyl ether, and extracting it for 20 minutes. The maximum pore diameter of the porous sheet surface is 1.2 μm
Hereinafter, pores with an average size of 0.6 to 0.9 μm accounted for 20% of the surface area. According to the surface observation results of the pouga sheet using a scanning electron microscope, about 207 Lm from the surface of the island component of soft polypropylene, there is no ethylene propylene rubber, and some high-molecular atactic polypropylene, isotactic polypropylene, and leather powder are present. The rest had become porous. Example-5 The dried leather powder of Example-4 was mixed with gelatin (average molecular weight
o, a film (40 p-m thick) obtained by cross-wiring and molding in the same manner except that the film was changed to Nitta Gelatin Co., Ltd.
, 10 cm) into an extraction device equipped with a reflux device, and soaked in 100 mM boiling diethyl ether for 20 minutes.
The gelatin was extracted for 30 minutes and then soaked in 10ml of boiling water for 30 minutes to obtain a porous film. The porous film has pores with a pore size of 7 JLm or less, an average of 5 μm, and a pore size of 1.2 pLm or less, an average of 0.6 to 0.9 μm.
It had a network structure consisting of communicating pores with a mixture of pores. The porosity was 50%. The amount of high molecular weight atactic polypropylene was 49% by weight. Example-6 The dried leather powder of Example-4 was mixed with an inorganic filler, calcium carbonate (BF300: manufactured by I Kitafunka Kogyo Co., Ltd. with an average particle size of 8 μm).
A sheet (thickness: 300 lLm, 10 cm square) obtained by mixing and molding in the same manner except that step (m) was changed was placed in an extractor equipped with a reflux device, and immersed in 100 ml of boiling diethyl ether for 20 minutes. A porous sheet was obtained. On the surface of the porous sheet, pores with a maximum pore diameter of 1.2 μm or less and an average diameter of 0.6 to 0.9 μm accounted for 20% of the surface area. From the results of close observation of the surface of the porous sheet using a scanning electron microscope, approximately 20 μm from the surface is comprised of islands of soft polypropylene, including ethylene propylene rubber, some high-molecular atactic polypropylene, isotactic polypropylene, and calcium carbonate. remained and became porous.

(1) 20 mu of purified hebutane and Mg (O
Add 4 g of E t ) 2 and 1.2 g of di-n-butyl phthalate, keep the system at 90°C, add µml of TfCJla dropwise without stirring, and add TfCJla 4 g.
An additional 111 m of water was added and the temperature was raised to 110°C. 11
After reacting at 0°C for 2 hours, the mixture was washed with purified butane at 80°C. A TiC pattern <115m pattern was added to the obtained solid phase portion, and the reaction was further carried out at 110°C for 2 hours. After the reaction was completed, the raw material was washed several times with 100 mL of purified hebutane to obtain a solid catalyst component [corresponding to the solid catalyst component (IT) of the 9 & phase method]. (2) Preparation of solid components 1.71 g of purified hebutane and A9. Et. 0
．． 07 mol, diphenyldimethoxysilane (DPDMS
)O. OS mmol and catalyst fraction 12 of the above (・1)
Added 0g. The inside of the system was maintained at 30°C, brobylene was continuously supplied without stirring, and the internal pressure was maintained at 0.5 κg/am'. After continuing this reaction for 1 hour, purified heptane 1
Wash with fL 5 times, solid component [solid fraction (I) of gas phase method]
equivalent to] was obtained. A! LEt. 3 mmol, l
-Allyl3,4-dimethoxybenzene (ADMB)0
．． 15, Rimol, diphenyldimethoxysilane (DPD
MS) 0.23 mmol and a certain fraction of the solid (2) above (
I) A 20 mM hebutane solution containing Zoomg (0.06 fi mol in terms of Ti atoms) was added. After evacuating the system for 5 minutes, gas phase polymerization was carried out at 70°C for 1.7 hours while supplying brobylene gas until the total pressure reached 28 Kg/am2. Melt index (Ml) is 0.5g/
640 g of 10-minute soft polypropylene was obtained. The boiling butane soluble content (HSP content) of this soft polypropylene is 4
9.5% by weight, and the intrinsic viscosity was 1.99 db/g. In addition, the boiling butane insoluble content (HIP content) is 50.
5% by weight, and the intrinsic viscosity is 4. It was 13 dl/g. Furthermore, the bentad fraction by C-NMR was 34.5%, and the melting peak temperature (Tm) measured by DSC was 15%.
The enthalpy of fusion (ΔH) measured by DSC at 8°C was 58.2 J/g, and a domain structure was observed in the melt using a transmission electron microscope (vIL). Block Soft Polypropylene After preparing the solid catalyst component and solid fraction A in the same manner as in the case of the above-mentioned homo-soft polypropylene, the following procedure was carried out. (1) 5 containing 20g of vapor phase T5 1-stage polymerized polypropylene powder! 33 mmol of A I E t , 1-allyl-3,4-dimethoxybenzene (AD
MB) 0.15 mmol, diphenyldimethoxysilane (DPDMS) 0.23 mmol, and the above Production Example 1
Solid fraction (1) prepared in (1) and (2) 100 m
20 m of a hebutane solution containing 0.06 mmol (calculated as TiL'X) was added. After evacuating the system for 5 minutes, the hydrogen gas was evacuated to 0. 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) Gas phase second Stage polymerization After the reaction in (1) above is completed, the system is depressurized and exhausted, and then 0.5 Kg/cm of hydrogen gas and 10 Kg of ethylene-propylene mixed gas (molar ratio 1/4) are added. /
cm'' and gas phase polymerization was carried out at 50°C for 1.4 hours. 550 g of soft polypropylene with a melt index (MI) of 3.9 g and 710 minutes was obtained. % and 28% by weight of an ethylene-propylene copolymer, the homopolymer has an intrinsic viscosity of 1.18 du/g, a boiling hebutane soluble content (HSP content) of 48.2% by weight, and a solid viscosity of 1. .8
4 dl/g boiling to butane insoluble content (HIP content) 51.8
weight%, bentad fraction by 13C-NMR (where r r r r/1-mmmm is 3
4.5%, melting peak temperature (Tm) measured by DSC
Or 158℃. Melting enthalpy (△
H) was 62.6 J/g, and a domain structure was observed in transmission electron microscopy. On the other hand, the ethylene unit content of the copolymer was 30 mol%, and the intrinsic viscosity was 1.77 dl/g. [Method of Measuring Characteristics and Method of Evaluating Effects] Next, the measuring methods and evaluation methods related to the present invention will be summarized. (1) Average pore diameter and maximum pore diameter The long axis and single axis of the pore diameter are measured by scanning electron W4WL mirror (SEM) observation of the sample surface, and the geometric mean of the average long axis and the average single axis is taken as the average pore diameter. Similarly, the long axis of the largest pore found on the sample surface or cleavage surface is taken as the maximum pore diameter. (2) Porosity: Pr A sample (10 cmX!O cm) was immersed in liquid paraffin for 24 hours, the liquid paraffin on the surface layer was thoroughly wiped off, the weight (W2) was measured, and the weight of the sample before immersion was measured. Weight (Wl). Find the pore a (VO) using the following formula from the density (ρ) of Paraffin. VO = (W2 - Wl)
/ρ The porosity (Pr) is calculated from the apparent body yt<thickness, the value calculated from dimensions)■ and the void body fiVo. Pr=Vo/VX too (%) (3) Intrinsic viscosity ([η]) 0.1g of sample was heated to 135℃ according to ASTM D1601.
completely dissolve in 100 ml of tetralin, measure this solution with a viscometer in a constant temperature bath at 135°C, and determine the intrinsic viscosity from the specific viscosity S according to the following formula. [η] = S/(0.IX( 1+0.22XS))
(4) Isotactic index (II) and isotactic bentad fraction Dry the sample at 130°C for 2 hours. From now on, the weight W (m
Take a sample of g) and boil it in a Soxhlet extractor.
Extract with hebutane for 12 hours. Next, take out this sample, wash it thoroughly with acetone, vacuum dry it at 130°C for 6 hours, then measure the weight W' (mg) and calculate it using the following formula. I I = (W' /W)
Let the attributed peak area fraction of m m ) be the isotactic bentad fraction. In addition, the peak assignment is Hacr
Based on omelecules 8, 687 (1975).
(5) Melting point and melt crystallization temperature of polypropylene Scanning calorimeter DSC-2 type (manufactured by Perkin Elmer)
5 mg of sample was heated at a heating rate of 20% under a nitrogen stream using
It is measured from room temperature at °C/min, and the endothermic peak temperature accompanying melting is taken as the melting point. Subsequently, the temperature was raised to 280°C, held for 5 minutes, and then heated to 280°C.
In the process of lowering the temperature at a rate of 0°C/min, the latent heat peak temperature accompanying crystallization of polypropylene is defined as the melting crystallization temperature. [Effects of the Invention] As described above, according to the porous film or sheet of the present invention, a molded article having high moisture permeability and air permeability can be obtained.

Claims (16)

[Claims] (1) A porous film or sheet made of soft polypropylene, characterized in that it has micropores with a pore diameter of 0.1 to 100 μm over 2 to 85% of its surface area on at least the surface thereof. (2) A porous film or sheet made of soft polypropylene, characterized in that it has micropores with a pore diameter of 3 to 30 μm over 3 to 60% of its surface area on at least the surface thereof. (3) The porous film according to claim 2, wherein the flexible polypropylene contains ethylene propylene rubber.
sheet. (4) At least on the surface of a film or sheet made of soft polypropylene, the maximum pore size is 1.2 μm or less and the average pore size is 0.6 to 0.5 μm over 5 to 50% of the surface area.
A porous film or sheet characterized by having micropores of 9 μm. (5) At least on the surface of a film or sheet made of 90 to 40% by weight of soft polypropylene and 10 to 60% by weight of an organic filler with a pore size of 3 to 30 μm,
A porous film or sheet having ~45% of micropores with a maximum pore diameter of 1.2 μm or less and an average pore diameter of 0.6 to 0.9 μm. (6) Micropores with a maximum pore diameter of 1.2 μm or less and an average pore diameter of 0.6 to 0.9 μm are formed on at least the surface of the film or sheet over 2 to 45% of the surface area, and over 10 to 60% of the surface area. A porous film or sheet characterized by having micropores with a pore diameter of 3 to 30 μm. (7) At least on the surface of a film or sheet made of 99 to 40% by weight of soft polypropylene and 1 to 60% by weight of an inorganic filler with a pore size of 0.1 to 30 μm, the maximum pore size is 1.0 μm over 2 to 45% of the surface area. A porous film or sheet characterized by having micropores of 2 μm or less and an average pore diameter of 0.6 to 0.9 μm. (8) After kneading 90 to 40% by weight of soft homopolypropylene and 10 to 60% by weight of organic filler with a particle size of 3 to 30 μm, form a film or sheet by T-die or inflation molding, and then form the film or sheet with a solvent. A method for producing a porous film or sheet, characterized by extracting at least an organic filler on the surface. (9) After kneading the soft block polypropylene, a film or sheet is formed by T-die or inflation molding, and then the ethylene propylene rubber (containing polyethylene) on at least the surface of the film or sheet is extracted with a solvent. Film and sheet manufacturing methods. (10) Soft block polypropylene 90-40% by weight
and 10 to 60% by weight of organic filler with a particle size of 3 to 30 μm.
A porous film characterized in that after kneading, a film or sheet is formed by Y-die or inflation molding, and then the ethylene propylene rubber (containing polyethylene) on at least the surface of the film or sheet is extracted with a solvent.
Method of manufacturing sheets. (11) Soft block polypropylene 90-40% by weight
and 10 to 60% by weight of organic filler with a particle size of 3 to 30 μm.
After kneading, the film or sheet is formed by T-die or inflation molding, and then the organic filler and ethylene propylene rubber (containing polyethylene) on at least the surface of the film or sheet are extracted with a solvent. manufacturing method. (12) Soft block polypropylene 90-40% by weight
and 10 to 60% by weight of organic filler with a particle size of 3 to 30 μm.
After kneading, the film or sheet is formed by T-die or inflation molding, and then the organic filler on at least the surface of the film or sheet is extracted with a solvent. (13) 90 to 40% by weight of soft homopolypropylene;
10 to 60% by weight of inorganic filler with a particle size of 0.1 to 30 μm
After kneading, the film or sheet is formed by T-die or inflation molding, and then the inorganic filler on at least the surface of the film or sheet is extracted with a solvent. (14) Soft block polypropylene 99-40% by weight
After kneading 1 to 60% by weight of inorganic filler with a particle size of 0.1 to 30 μm, a film or sheet is formed by T-die or inflation molding. ) A method for producing porous films and sheets characterized by extracting. (15) Soft block polypropylene 99-40% by weight
After kneading 1 to 60% by weight of inorganic filler with a particle size of 0.1 to 30 μm, a film or sheet is formed by T-die or inflation molding, and then the inorganic filler and ethylene propylene rubber on at least the surface of the film or sheet are mixed with a solvent. A method for producing porous films and sheets characterized by extracting polyethylene (inherent in polyethylene). (16) Soft block polypropylene 90-40% by weight
and 10 to 60 inorganic fillers with a particle size of 0.01 to 30 μm.
A method for producing a porous film or sheet, which comprises kneading the weight percent, forming the film or sheet by T-die or inflation molding, and then extracting inorganic filler from at least the surface of the film or sheet with a solvent.