JPH03168224A - Flexible polypropylene film and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject flexible film having low heat-seal temperatures, excellent in heat resistance, having a low brittle temperature and suitable for a wrapping film, a stretched film, gloves, etc., by carrying out T-die or inflation forming of a thermoplastic resin composed of flexible PP. CONSTITUTION:A thermoplastic resin mainly composed of flexible PP is subjected to T-die or inflation forming to obtain the objective film. In addition, PE, PS, etc., are exemplified as other thermoplastic resins.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has a heat sealing temperature lower than that of polypropylene.
It has higher heat resistance properties than linear low-density polyethylene, and is suitable for wrap films and stretch films. gloves, lk
This article relates to a flexible polypropylene film suitable for industrial films, clothing packaging, parts packaging, etc., and its manufacturing method. [Conventional technology and problems to be solved] Conventionally, oil-repellent films such as polypropylene film (block polypropylene film, homobolyfluorene film) and linear low-density polyethylene film have been used in various fields. However, these films had the following problems. That is, polypropylene film is hard, has poor stretchability, and has a relatively high embrittlement temperature. For this reason, block polypropylene films must be heat-sealed at high temperatures, and homopolypropylene itself is difficult to heat-seal. On the other hand, as a soft film, there is a linear low-vE polyethylene film, but although this film has flexibility, it has the problem of being sensitive to high temperatures. The present invention has been made in view of the above problems, and aims to provide a flexible polypropylene film that is soft, has good heat resistance, excellent low-temperature heat sealability, and has a low embrittlement temperature, and a method for producing the same. [Means for Solving the Problems] In order to achieve the above object, the inventor of the present invention has conducted intensive research, and has found that using a special soft polypropylene, it is soft and
It was discovered that a film with a low embrittlement temperature and good texture could be obtained, and the present invention was perfected. That is, the flexible polypropylene film of the present invention is mainly made of soft polypropylene. Book l again? ．． The method for producing a soft polypropylene film of the present invention mainly involves using a thermoplastic resin made of soft polypropylene containing high-molecular atactic polypropylene as T.
It is made to look like a die or inflation. Here, among the materials of the film of the present invention, soft polypropylene, which is the main component, will be explained. (Left below) In this specification, "Souga polypropylene" refers to the homopolymer or copolymer described in (1) to (4) below,
Furthermore, it means any of MlJ& products containing these polymers. (1) (i) 10 to 90% by weight of boiling hebutane-soluble polypropylene having an intrinsic viscosity of 1.2 dl/g or more
and (H) a boiling butane-insoluble polypropylene having an intrinsic viscosity of 0.5 to 9.0 dl/g and 90 to 3H amount % of a polypropylene polymer (a), (2) (i) α
- Olefin unit content is O. It is 1 to 5 mol%.
(it) 20 to 99.9% by weight of boiling hexane soluble content with an intrinsic viscosity of 1.2 d/g or more, and (i
ii) A random copolymer of propylene and an α-olefin having carbons a4 to 30 having a tensile modulus of 5000 Kg/c1 or less (b), (3)(i) the polypropylene polymer (a ) lO~
95% by weight. (ii) Ethylene unit content is IO ~
(c) an ethylene-propylene copolymer having an ethylene unit content of 60 mol% and an intrinsic viscosity of 0.5 to 7.0 dl/g and/or (ii) an ethylene unit content of 10 to 60 mol% and a polyene unit content; 1 to 10 mol%, intrinsic viscosity b<o
．． s~7. A brobylene composition (d) consisting of 90 to 5% by weight of an ethylene-propylene-boriene copolymer (c') having a ~95% by weight. (ii) The ethylene-propylene copolymer (c) and/or the ethylene-propylene-boriene copolymer (c') 90-s
A brobylene composition (e) consisting of 1%. In addition, it is particularly preferable that the polypropylene polymer (a) has the following properties (i) to (iv). (i) “In the pentad fraction by C-NMR, r
rrr/1 1 so 1 I is zO% or more. (ii) Melting peak temperature measured with a differential calorimeter (DSC) (
Tm) is 150°C or higher. (iii) Melting enthalpy (Δ!1) measured by DSC or 1 0 0 J/
g or less. (iv) Domain structure is observed in transmission electron microscopy. Among the flexible polypropylenes used in the present invention, the above polypropylene polymer (a) and random copolymer (b)
can be prepared, for example, by either the gas phase one-stage polymerization method or the slough saw one-stage polymerization method described below.
Below, we will explain their preparation methods in order. The catalyst system used in the rapid simultaneous vapor phase one-stage polymerization method, if collapsed, (1)
(i) A solid component consisting of a crystalline polyolefin and (it) a solid catalyst component consisting of magnesium, titanium, a halogen atom, and an electron-donating compound, (■) an organoaluminum compound (m) an aromatic compound containing an aloxy group , and (IV)
It consists of a combination of child-donating compounds. The solid component (1) is crystalline polyolefin (i)
The amount of solid catalyst per 1 part by weight was o. oos~
The content is 30 parts by weight (preferably 0.02 to 10 parts by weight).

The solid fraction (1) is, for example, a solid catalyst fraction (it
), an organoaluminum compound, and optionally an electron-donating compound, yJ can be produced by a method of prepolymerizing an olefin (pre-4171 polymerization method). Here, the solid catalyst (ti) has magnesium, titanium, a halogen atom, and an electron-donating compound as essential components, and is produced by bringing the magnesium compound, titanium compound, and electron-donating compound into contact with each other. It can be prepared. Examples of magnesium compounds include magnesium dihalides such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylates, alkoxymagnesiums such as diethoxymagnesium, allyloxymagnesium, alkoxymagnesium halides,
Alkylmagnesium such as allyloxymagnesium halide, ethylbutylmagnesium, alkylmagnesium halide, or reaction products of *lj&magnesium compounds with electron donors, halosilanes, alkoxysilanes, silanol, aluminum compounds, etc. However, among these, magnesium halide,
Preferred are alkoxymagnesium, alkylmagnesium, and alkylmagnesium halides. Moreover, these magnesium compounds may be used in one kind or two kinds.
More than one species may be used in combination. Examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-broboxytitanium, tetra-broboxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium, etc. Tetraalkoxytitanium. Titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, trichloride such as methoxytitanium trichloride, ethoxytitanium trichloride, broboxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide, etc. Dihalogenated dialkoxytitanium such as halogenated alkoxytitanium, dimethoxytitanium dichloride, diethoxytitanium dichloride, diproboxytitanium dichloride, di-n-proboxytitanium dichloride, diethoxytitanium dibromide, tosomethoxytitanium chloride, triethoxytitanium chloride , triproboxytitanium chloride, tri-n-butoxytitanium chloride, and other heptanohalogenated trialkoxytitanium compounds. Among these, highly halogen-containing titanium compounds, particularly titanium tetrachloride, are preferred. These titanium compounds may be used alone or in combination of 28 or more. The electron donating compound is oxygen. It is an organic compound containing nitrogen, phosphorus, sulfur, silicon, etc., and can improve regularity in the polymerization of propylene.

Examples of such electron-donating compounds include esters, thioesters, alcohols, and ketones. Nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, amides, aldehydes,
Examples include acids. Furthermore, for example, diphenyldimethoxysilane, diphenyljethoxysilane, cybenzyldimethoxylane, tetramethoxysilane,
Organosilicon compounds such as tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane, pendyltrimethoxysilane, mono-n-butyl phthalate, diisobutyl phthalate, etc. aromatic dicarboxylic acid esters, carbon a1-4 alkyl esters of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid, isobrobyl methyl ether, isopropylethyl ether , t-butyl methyl ether, t-butyl ethyl ether, t-butyl n-propyl ether, t-
Asymmetric ethers such as butyl-n-butyl ether, t-amylmethyl ether, t-amyl ethyl ether,
2,2"-azobis(2-ethylpropane), 2,2-
Azobis(2-ethylbroban), 2.2゜-azobis(2-methylbentane), a,a゛-azobisisobutyronitrile, 1.1'-azobis(l-cyclohexanecarboxylic acid), (l- phenylmethyl) monoazodiphenylmethane, 2-phenylazo-2,4-dimethyl-4-
Steric hindrance r in the azo bond such as trixybentanenitrile
Examples include azo compounds in which one substituent is bonded, and these may be used alone or in combination of 28i or more. Specifically, dimethyl phthalate 2 diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl isobutyl phthalate, ethyl brobyl phthalate, ethyl isophthyl phthalate, propyl isobutyl phthalate Terephthalate-1~, diethyl terephthalate, sibropyl terephthalate, diisophthyl terephthalate, methyl ethyl terephthalate, methyl probyl terephthalate, methyl isobutyl terephthalate, ethyl brobyl terephthalate, ethyl isophthyl terephthalate, probyl isobutyl terephthalate, dimethyl isophthalate , diethyl isophthalate, dibrobyl isophthalate, diisobutyl isophthalate,
Aromatic dicarboxylic acid diesters such as methyl ethyl isophthalate, methyl probyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and probyl isobutyl isophthalate, methyl formate, 5-ethyl acetate, vinyl acetate, acetic acid Provil, octyl acetate, cyclohexyl acetate, ethyl propionate diacetate, ethyl valerate. Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, brovyl benzoate, tutyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoic acid Monoesters such as phenyl acid, pencil benzoate, ethyl toluate, amyl toluate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, γ-valerolactone , esters with 2 to 18 carbon atoms such as coumarin, phthalito, and ethylene carbonate, organic acids such as benzoic acid and p-oxybenzoic acid, and acid anhydrides such as succinic anhydride, benzoic anhydride, and P-toluic anhydride. , acetone 2 methyl ethyl ketone, methyl isobutyl ketone, acetophenone, penzophenone, benzoquinone, etc. with 3 carbon atoms
~15 ketones, aldehyde regions with an RZ number of 2 to 15 such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthylaldehyde, acetyl chloride, penzyl chloride, toluic acid chloride,
Acid halites with 2 to 15 carbon atoms such as anisyl chloride, ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isobrobyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol butyl ether. , acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N,N'-
Dimethylbiverazine, tribenzylaton, aniline,
Examples include pyridine-2-picoline, amines such as tetramethylethylenecyamine, and nitriles such as acetonitrile, penzonitrile, and tolnitrile. Among these, esters, ethers, ketones and acid anhydrides are particularly important, especially cy-n-butyl phthalate,
Suitable examples include aromatic dicarboxylic acid diesters such as diisobutyl phthalate, and alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, P-ethoxybenzoic acid, and toluic acid. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence. The above-mentioned solid catalyst fraction (100) was prepared by a known method (JP-A-53-4:1094, JP-A-55-1:151).
02, JP-A-55-1351 [1:I, JP-A-56-18506].

For example, (1) a method in which a magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized in the presence of an electron donor and a grinding aid used as desired, and reacted with a titanium compound; 2) A method in which a liquid magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex, (3) the method described in (1) or ( 2) A method of reacting the product obtained in step (1) or (2) with a titanium compound; (4) A method of reacting the product obtained in step (1) or (2) with an electron donor and a titanium compound. (5
) A magnesium compound or 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. how to,
(6) It can be prepared by a method of treating the compounds obtained in (1) to (4) above with a halogen or a halogen compound.

Furthermore, methods other than these methods (Japanese Unexamined Patent Publication No. 56-156
No. 205, JP-A-57-1i3309, JP-A-57-190004, JP-A-57-40040
The solid catalyst component (ii) can also be prepared according to Japanese Patent Application Laid-Open No. 7, No. 58-4700: I). In addition, oxides of elements belonging to groups N to ■ of the periodic table, such as oxides of silicon oxide, magnesium oxide, aluminum oxide, etc., or composite oxides containing at least one oxide of elements belonging to groups n to ■ of the periodic table. The solid material such as the magnesium compound supported on a substance such as silica alumina, an electron donor, and a titanium compound are mixed in a solvent at a temperature of 0 to 20%.
The solid catalyst fraction (i
i) can be prepared. In preparing the solid catalyst, an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, is used as a solvent. Use of aromatic hydrocarbons such as benzene and toluene, 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 done. The thus prepared solid catalyst component (IT) usually has a magnesium/titanium atomic ratio of 2 to 100, a halogen/titanium atomic ratio of 5 to 200, and an electron donor/titanium molar ratio of 0. It is in the range of 1 to 1O. The above-mentioned solid component (1) can be produced by olefinic pre-combination with the thus obtained solid catalyst component (ii) in the presence of an organoaluminum compound and optionally an electron-donating compound. can. The aluminum compound used here has the general formula A R''pX3-p.(1)(
In the formula, R'' is an alkyl group having 1 to 10 carbon atoms, X is chlorine,
A halogen atom such as bromine, p is a number from 1 to 3). Examples of such aluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, tosoisobrobylaluminium, triisobutylaluminum, and trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, and diisobutylaluminum monochloride. Dialkylaluminum heptanohalites such as chloride, dioctylaluminum monochloride, and alkylaluminum sesquihalites such as ethylaluminum sesquichloride can be suitably used. These aluminum compounds may be used alone or in combination of two or more.

Further, as the electron-donating compound that may be optionally present, the compounds described in connection with the solid catalyst component (11) can be used.

In the method for preparing solid bokubun (I), an α-olefin having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1,4-methylbentene-1, is used as the olefin, and usually 30 to 80'C. Preferably 55-70℃
At a temperature in the range of 100 to 100° C., a preaminescence is carried out 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 selected in the range of 0.1 to ioo, preferably 0.5 to 5, and the electron donating compound/titanium molar ratio is 0 to 50, preferably 0.1. Selected in the range of ~2. The solid catalyst (I) is prepared by adding the solid catalyst (II), an aluminum compound, and an electron-donating compound (melting point 100'C or higher) to a crystalline powder such as polypropylene or polyethylene with a uniform particle size. It can also be prepared by a method of dispersing (dispersion method).

Furthermore. ii? The solid fraction (1) can also be prepared by combining the pre-418 polymerization method described in j and the dispersion method.

As mentioned above, the catalyst system used in the gas phase one-stage polymerization method is a method in which the solid component (I), the organoaluminum compound (I1), the alkoxy group-containing aromatic compound (m), and the electron-donating compound (IV) are brought into contact with each other. However, the compounds described above can be used as the aluminum compound (C) and the electronic compound (rV), respectively. Further, the alkoxy group-containing aromatic compound (III) 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 1-6! i number, n is an integer of O to (6-m)], and specifically, for example, m-methoxytoluene 2 o-methoxyphenol, m-methoxyphenol, 2-methoxy 4 - methylphenol,
Vinylanisole, p-(1-brobenyl)anisole, P-allylanisole, 1,3-bis(P-methoxyphenyl)-1-bentene, 5-asol-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4
- Monoalkoxy compounds such as hydroxybenzene 3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole, nitrophenethole 2o-dimethoxybenzene, m-dimethoxybenzene, P-dimethoxybenzene, 3.4-dimethoxytoluene 2 2.6- Dialkoxy compounds such as dimethoxyphenol, 1-allyl-3,4-dimethoxybenzene, and 1,3,5-trimethoxybenzene, 5-aryl-1,2.3-tosomethoxybenzene, 5-allyl-1,2.4 -trimethoxybenzene, 1,2.3-}-rimethoxy5-(l-
Probenyl)benzene, 1,2.4-}-rimethoxy-
Examples include trialkoxy compounds such as 5-(1-brobenyl)benzene, 1,2,3-trimethoxybenzene, and 1,2,4-trimethoxybenzene; among these, dialkoxy compounds and trialkoxy compounds is preferable. These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more. In the above catalyst system, the solid fraction (1) is used in an amount of 0.0005 to 1 mole per v111 of the reaction volume in terms of titanium atoms. In addition, an alkoxy group-containing aromatic compound (m)
The amount used is per mole of titanium atoms in solid component (1). The amount is 0.01 to 500 mol, preferably 1 to 300 mol. If the amount used is less than 0.01 mol, the physical properties of the raw wood polymer will deteriorate. Exceeding the SOO mole is undesirable because the catalytic activity decreases.In this catalyst system, the atomic ratio of aluminum and titanium is 1:1 to 3000 (
The ratio is preferably 1:40 to 800). If the atomic ratio falls outside of this range, sufficient catalytic activity will not be obtained. Furthermore, the molar ratio of the alkoxy group-containing aromatic compound Th (m) to the electron donating compound (IV) is 1:0.01 to Zoo (preferably 1:0.2 to 100). In the gas phase one-stage polymerization method, the above-mentioned polypropylene polymer (a) is obtained by homopolymerizing propylene, and the above-mentioned random copolymer is obtained by copolymerizing propylene with an α-olefin having 4 to 30 carbon atoms. Polymer (b) is obtained. The molecular weight can be adjusted by known means (for example, adjusting the hydrogen concentration). Polymerization temperature is generally 40-90℃
(preferably 60 to 75°C), and the polymerization pressure is lO to
45 Kg/cm” (preferably 20 to 30 Kg/cm”
g/cm'') .The polymerization time is 5 minutes to 10 hours.Slurry lf In the slurry one-stage polymerization method, for example, either of the following two types of catalyst systems can be used.That is, ( l〉 It is effective from the combination of (a) a solid fraction that essentially includes matanesium, titanium, a halogen atom, and an electron donor, (b) an aromatic compound containing an alkoxy group, and (c) an aluminum compound. Catalyst system, or (2) (A) obtained by reacting the above (a) solid fraction and (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organoaluminum compound. There is a catalyst system that is effective from a combination of a solid catalyst and (B) an organoaluminum compound. First, to explain the catalyst system of (1) above, the solid component (A) is a combination of magnesium, titanium, halogen atoms, and electron donating atoms. It can be prepared by bringing a magnesium compound, a titanium compound, and an electron donor into contact. Organic solvents that are inert towards the compound, electron donor and titanium compound, such as aliphatic hydrocarbons (
hexane, hebutane, etc.), aromatic hydrocarbons (benzene, toluene, etc.), or halogenated hydrocarbons (mono- and polyhydrocarbons of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms). halogen compounds, etc.) can be used alone or in combination of two or more. The magnesium compound, titanium compound, and electron-donating compound used in preparing the solid fraction (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. Solid component (a) can be prepared from these compounds 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 component (a) obtained in this way may also be used as each of the above-mentioned catalyst systems for the gas phase one-stage polymerization method. Compounds can be used. Regarding the amount of each component used in the catalyst system (1), the solid component (a) is usually calculated as 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 mol per 1 mole, and the molar ratio of the alkoxy group-containing aromatic compound (b) to the titanium atoms of the solid fraction (a) is usually 0.01 to SOO (preferably 1 to 300 > is used in a ratio of 0.01. If this molar ratio is less than 0.01, the physical properties of the raw aluminum polymer will deteriorate, and if it exceeds 500, the catalytic activity will decrease, which is not preferred.In addition, the organoaluminum compound (c) is It 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 catalyst activity will be insufficient.Next, the above catalyst system ( To explain 2), 5 the solid catalyst fraction (A) in this catalyst system (2) comprises the solid catalyst fraction (a) of the catalyst system (1) and the alkoxy group-containing aromatic compound (i), The above organoaluminum compound (c)
It can be prepared by reacting in the presence or absence of. This Xgl product generally uses a hydrocarbon solvent (for example, the hydrocarbon solvent used in the preparation of the catalyst system (1)). The reaction temperature is usually 0 to 150°C (preferably 10 to 5°C).
0°C), and if this temperature is less than 0°C, the reaction will not proceed sufficiently, and if it exceeds iso'c, side reactions will occur and the activity will decrease. The reaction time varies depending on the reaction temperature, but is usually 1 minute to 20 hours, preferably 10 to 60 minutes. When producing 7JA of solid catalyst fraction (A) in the presence of organoaluminum compound (c), the concentration of this aluminum compound (c) is usually 0.05 to 100 mmol/i (
It is preferably 1 to 10 mmol/liter). If this concentration is less than 0.05 mmol/cross, the effect of conducting the reaction in the presence of the organoaluminium compound gIIJ (c) will not be sufficiently obtained, and if it exceeds 100 mmol/cross, the reaction will not be sufficiently effective. As the reduction of titanium progresses, the catalytic activity decreases. On the other hand, in the absence of the organoaluminum compound (c), the solid component (a) and the alkoxy group-containing aromatic compound? lll(
When preparing a solid catalyst fraction (A) by reacting with (b), the alkoxy group-containing compound (i) is
The molar ratio to the titanium atoms in the
(preferably 1 to 50), and the concentration of the compound (b) is usually 0.01 to 1.
0 mmol/statement (preferably 0.1-2 mmol/statement)
Selected within the range. If the molar ratio to titanium atoms is outside the above range, it will be difficult to obtain a catalyst with the desired activity. Also, if the concentration is less than 0.01 mmol/liter, the volumetric efficiency is low and it is not practical, and if it exceeds 10 mmol/liter, 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 gas phase one-stage method can be used. Regarding the amount of each component used in the catalyst system (2), the solid catalyst fraction (A) is equivalent to the reaction volume l in terms of titanium atoms.
! ;Used in an amount that is usually in the range of 0.0005 to 1 mmol/liter, and the organoaluminum compound (B) has an aluminum/titanium atomic ratio, usually 1 to 1 mmol/L.
It is used in an amount such that the range C is 3000 (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 homopolymerization of brobylene is carried out, the polypropylene-based polymer (a
) can be obtained, and propylene and α having 4 to 30 carbon atoms can be obtained.
When copolymerized with an olefin, 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 100°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 can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel.

Next, among the soft polypropylenes used in the present invention, propylene composition (d) {the polypropylene polymer (
a) and an ethylene-propylene copolymer (C) or an ethylene-propylene-boriene copolymer (C゜)} and a propylene-based composition (e> {the random copolymer (b)) and an ethylene-propylene copolymer (C) or an ethylene-propylene-boriene copolymer (C゛), for example, by the following gas phase multistage method, slurry multistage 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.In the gas phase multi-stage polymerization method, (First stage polymerization) is the same as the gas phase IVlt polymerization described above. Therefore, the molecular weight can be adjusted by known means (for example, adjusting the hydrogen concentration). The polymerization temperature is generally 40 to 90°C (preferably (60 to 75°C), the polymerization pressure is 10 to 45 Kg/am2 (preferably 20 to 30 Kg/cm"), and the polymerization time is 5 minutes to 10 hours.

The second to final polymerization (nth stage polymerization) is ethylene-propylene copolymerization or ethylene-propylene-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. , 5-impropylidene-2-norbornene 5
5-Isofrobenyl-2-norbornene, 5-(1-
butenin)-2-norbornene, cyclooctadiene,
Vinylcyclohexene, 1,5.9-cyclododecatriene, 6-methyl-4.7,8.9-tetrahydroindene, 2-2゜dicyclobentenyl 5 trans-1
, 2-divinylcyclobutane, 1,4-hexadiene 2
4-methyl-1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1
．． 9-decacyene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene. 1
, 4,7-octatriene, 5-methyl-1,8-nonadiene, norbornadiene, vinylnorbornene, and the like. Among these non-conjugated polyenes, dicyclobentadiene, 5-ethisodene-2-norbornene, and 1,7-octadiene are particularly preferred.

In each polymerization step, the molecular weight yJ can be determined by known means (for example, adjusting the hydrogen concentration WJ). In the case of ethylene-propylene copolymers, the ethylene unit content can be adjusted by adjusting the feed gas composition. Also, in the case of an ethylene-propylene-boriene copolymer, the polyene unit content in clause 7A can be determined 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/cm” (preferably io to 50°C).
20Kg/c1). And the polymerization time is 5 minutes to 10 hours.

Slurry multi-stage polymerization method Also 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 multistage polymerization method are not particularly limited and can be arbitrarily selected. For example, in the first and third stage polymerization, brobylene homopolymerization or copolymerization of propylene and an α-olefin having 4 to 30 carbon atoms is carried out, and in the second and fourth stage polymerization, ethylene-brobylene copolymerization is carried out. Polymerization or ethylene-propylene-boriene polymerization can be carried out. As with the gas phase multistage method, the number of polymerization stages (the number of n) may be selected as the optimal number to obtain the desired product, and either continuous polymerization method or discontinuous polymerization method may be used as the polymerization method. be able to. In the case of brobylene homopolymerization or copolymerization of propylene with an α-olefin having 4 to 30 carbon atoms, the polymerization temperature is usually 0 to 30%.
The range of 200"C (preferably 60 to 100°C) and the propylene pressure are usually selected in the range of 1 to 50 Kg/am2. Also, ethylene-propylene copolymerization or ethylene-propylene-boriene copolymerization In Case of,
Polymerization temperature is usually 0 to 200°C (preferably 40 to 80°C)
) range, the fin pressure is usually between 1 and 50 kg.
/cts2 range. In each 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, by adjusting the hydrogen concentration in the polymerization vessel. ．． In the case of ethylene-propylene copolymer, the ethylene unit content vA can be determined by the charging gas composition,
In the case of an ethylene-brobylene-boriene copolymer, the content of polyene units can be adjusted by adjusting the amount charged. As the polyene monomer, the polyene monomers mentioned in the gas phase multi-stage method can be used. Blending method The above propylene compositions (d) and (e) are composed of a polypropylene polymer (a) or a random copolymer (b) and an ethylene-propylene copolymer (c) or an ethylene-propylene copolymer. It can be prepared by blending the ene copolymer (C') with the ene copolymer (C') by a known method (for example, dry blending or cross-mixing). The polypropylene polymer (a) and the random copolymer (b) are
The ethylene-propylene copolymer (C) or the ethylene-propylene-borien copolymer (C゜) can be obtained by the above-mentioned gas phase one-stage polymerization method or slurry one-stage polymerization method, respectively. It can be obtained by known methods. Note that post-treatment after polymerization can be carried out by conventional methods. That is, in the gas phase one-stage polymerization method or the gas phase multi-stage polymerization method. After polymerization, the polymer powder extracted from the polymerization vessel is
In order to remove unreacted olefins contained in this,
A stream of nitrogen or the like may be passed through. Further, if desired, it may be pelletized using an extruder, and at that time, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst. In addition, in the slurry one-stage polymerization method or the slurry multi-stage polymerization method, after the polymerization, the heptamer can be completely separated from the bosomer led out from the polymerization vessel, and then pelletized.

(V: Margin) In addition, in the soft polypropylene film of the present invention,
A water-soluble organic filler, a water-insoluble organic filler, or an inorganic filler may be added to the above-mentioned soft polypropylene, and other thermoplastic fat-retaining agents may also be added. As the water-soluble organic filler, we mainly use water-soluble organic fillers that have an average particle size of 307 zm or less, are in the form of fine powder particles or short fibers, and are soluble in water. An example of an organic filler that is easily soluble in water is low molecular weight gelatin. Low molecular weight collagen. There are starch, agar, etc. If the mixing ratio of the filler is 60% by weight or more, heat generation during crosstalk will increase, and the organic filler will easily deteriorate. When molded products are made from materials, the surface becomes extremely rough. Examples of water-insoluble organic fillers include leather powder, silk powder, cellulose, bamboo powder, and gelatin. Polyamides such as 6-nylon and 6.6-nylon; Fluorine resins such as polytetrafluoroethylene and tetrafluoroethylene hexafluoropropylene copolymers; Polyimide: Silicone resin: Phenol resin;
Benzoguanamine resin: or styrene, acrylic acid. Copolymers of methacrylic acid, methyl acrylate, methyl methacrylate, etc. and methyl crosslinking agents such as divinylbenzene are suitable. Examples of inorganic fillers include Group IIA of the periodic table. l selected from the group consisting of Group mA and Group IVB! oxide of metal i. hydroxide. Carbonates, sulfates, carbides, siliceous fillers, etc. are preferably used. For example, Periodic Law No.
Group metals include calcium. Alkaline earth metals such as magnasium and barium, metals of group mA such as boron and aluminum, and metals of group IV
As the B group metal, metals such as titanium, zirconium, and octafnium are suitable. Oxides, hydroxides, carbonates, or sulfates of these metals may be used without particular limitation.
In particular, more specific examples of inorganic fillers that are preferably used include calcium oxide, magnesium oxide. Barium oxide. Aluminum oxide. Boron oxide, titanium oxide.
Oxides such as zirconium oxide, hypoacids such as calcium carbonate, magnesium carbonate, barium carbonate, hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, sulfates such as calcium sulfate, barium sulfate, aluminum sulfate, etc. etc. Other thermoplastic resins include polyethylene and polystyrene. Also, as a known additive. For example, antioxidants and heat stabilizers. Lubricant. Wf antistatic agent. Antiblocking agents or flame retardants may also be added. A soft polypropylene film made of the above materials is manufactured through a cross-crossing process and a forming process. Single-screw extruder, multi-screw extruder as mixing equipment for kneading process 41. Use a Banbury mixer, kneader, or two rolls. Preferably, a single or multi-screw extruder is used. the material is,
Considering the subsequent process, it is preferable to make it into pellets. The crosstalk temperature of the resin is 170°C to 320°C, preferably 1
The temperature should be within the range of 90 to 280°C. If the crosstalk temperature is below 170°C, it will be difficult to crosswire due to poor melting, and the temperature will reach 320'C.
If it is more than that, thermal deterioration will be severe. Shaping process Select the appropriate molding machine and shaping method depending on the molded product and its use. Usually, this is done by inflation molding or T-die molding. Molding temperature is 170°C to 320°C, preferably 190°C to
The temperature shall be within the range of 280℃. If the molding temperature is below 170°C, it will be difficult to shape due to poor melting. If the temperature exceeds 320'C, thermal deterioration will be severe and it will be difficult to form a film.

[Example] A film was shaped under the following conditions. I Homopolypropylene and soft block polypropylene produced as follows were used.

(1) Preparation of fixed catalyst components In a three-necked glass flask with an internal volume of 500 m that was sufficiently purged with nitrogen, 20 mM of purified hebutane and Mg (OEt) were added.
* Add 4g and 1.2g of di-n-butyl phthalate, keep the system at 90°C, and stir until TiCJl<
After dropping 4 ml, add TiC. After 2 hours of reaction at 110''C, the solid phase was heated to 80℃ and washed with butane. 5ml
was added and allowed to react at 110°C for an additional 2 hours. After the reaction was completed, the product was washed several times with 100 mffi of purified hebane to obtain a solid catalyst component [corresponding to the solid catalyst component (ii) of the gas phase method].

(2) Preparation of solid hemolyte Purified hebutane 1.7JL, AJIEt3 in a pressure-resistant glass three-necked flask with contents A2.51, which has been sufficiently purged with nitrogen.
0.07 mol, diphenyldimethoxysilane (DPDM
S) 0.05 mmol and the catalyst fraction 1 of the above (1)
Added 20g. The temperature inside the system was maintained at 30°C, brobylene was continuously supplied without stirring, and the internal pressure was reduced to 0. 5 kg/
After continuing this reaction for 1 hour, it was washed 5 times with 1 liter of purified hebutane to obtain a solid component [corresponding to solid component (1) in the gas phase method]. AREt++ 3 mmol, 1
-Allyl-3,4-dimethoxybenzene (ADMB) 0
．． 15 mmol, diphenyldimethoxysilane (DPD
MS) 0.23 mmol and the solid component (2) above (
I) 20 mfL of hebutane solution containing 100 mg (0.06 mmol in terms of Ti atoms) was added. After evacuating the system for 5 minutes, hydrogen gas was introduced to 0.7Kg/cm2,
Further, gas phase polymerization was carried out at 70°C for 1.7 hours while supplying brobylene gas until the total pressure reached 28 Kg/c2. 640 g of soft polypropylene with a melt index (Ml) of Log 710 was obtained. The boiling butane soluble content (HSP content) of this soft polypropylene is 46.8
% by weight, and the intrinsic viscosity was 1.13 dJL/g. In addition, the boiling butane insoluble content (CHIP content) is 53.2i
i%, and the solid viscosity was 1.74 db/g.
Furthermore, in the bentad fraction by C-NMR, rr
r r / 1 - m m m m is 34.5%, and the melting peak temperature (Tm) measured by DSC is 1
Enthalpy of fusion (ΔH) measured by DSC at 58°C
58.2 J/g, and a tomain structure was observed in block 4 by transmission electron microscopy.
a-Polypropylene After preparing the solid catalyst component and solid A in the same manner as for the above-mentioned homo-flexible polypropylene, the following procedure was carried out. (1) AiEt, 3 mmol, 1-
Allyl-3,4-dimethoxybenzene (ADMB) 0.
15 mmol, diphenyldimethoxysilane (DPDM
S) 0.23 mmol and 100 mg of the solid component (1) prepared in Production Example 1 (1) and (2) above (Ti
A 20 mM hebutane solution containing 0.06 mmol (calculated as atoms) was added. After evacuating the system for 5 minutes, remove hydrogen gas to 0.
．． 7Kg/am” and further increase the total pressure to 28K.
Do not supply propylene gas until g/crn2.7
Gas phase polymerization was carried out at 0'C for 1.7 hours.

(2) Second-stage polymerization in gas phase After the reaction in (1) above is completed, the system is depressurized and evacuated, and then hydrogen gas is removed. 5 Kg/cm2, ethylene-propylene mixed gas (molar ratio 1/4) L O Kg/
c-, and gas phase polymerization was carried out at 50°C for 1.4 hours. 810 g of propylene elastomer with a melt index (Ml) of 4.4 g/10 min was obtained. This elastomer consists of 8l% by weight of polypropylene homopolymer and 19fflffi% of ethylene-brobylene copolymer,
The homopolymer has an intrinsic viscosity of 1.13 du/g and a boiling helibutane soluble content (HSP content) of 46.8% by weight.
- 74 dJl/g boiling hebutane insoluble content (HIP content)
It consists of 53.2% double star, and the bent fraction by C-NMR is r r r r / 1 -
m m m m is 34.5%, the melting peak temperature (Tm) measured by DSC is 158°C, the enthalpy of fusion (△H) measured by DSC is 58.2 J/g, and the melting peak temperature (Tm) measured by DSC is 58.2 J/g, and the In observation, the tomain structure is U′t
i & was done. On the other hand, the ethylene unit content of the copolymer is 3
The content was 9 mol%, and the intrinsic viscosity was 1.77 dl/g.

R kneading conditions Screw temperature: 200°C Screw rotation @: 100 rpm Beretizer: Nakatani Machinery Co., Ltd. (VC) A 20 mm T die was used to make a film with a thickness of 30 mm. Made by T-Dai Itsuki Futsukada 411 Seisakusho (TLC35-20)
Chill roll temperature: 35°C Screw rotation speed: 50 rpm Resin temperature: 200°C Take-up speed: 25 to 5.5 m/min Extrusion rate: 1.1 to 1.2 Kg/hour Air knife used [Comparative example] Other than changing the material, A film was molded under the same conditions as in the above example.

[Evaluation] Tables 1 and 2 show the heat sealing temperature, embrittlement temperature, and elastic modulus of the above examples and comparative examples.

[Leaving space] Table 1 (Example) Table 2 (Comparative example) [Effects of the invention] As described above, the soft polypropylene film of the present invention is soft, has good thermal properties, and has good low-temperature heat sealability. It is possible to obtain a film with excellent properties and a low embrittlement temperature. Further, according to the manufacturing method of the present invention, the above-mentioned soft polypropylene film can be manufactured reliably and easily.

Claims (2)

[Claims] (1) A soft polypropylene film mainly made of soft polypropylene. (2) A method for producing a soft polypropylene film, characterized in that a thermoplastic resin mainly made of soft polypropylene is T-die or inflation molded.