JPH03168232A - Soft polypropylene-based thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable as raw material of automobile, parts, industrial mechanical parts or electrical parts, etc., having sufficient elastic modulus and heat resistance and excellent impact resistance containing specific soft polypropylene and thermoplastic resin. CONSTITUTION:The aimed resin composition is composed of (A) 10-90wt.% soft polypropylene (PP) selected from A1: PP-based polymer composed of boiling heptane-soluble PP and boiling heptane-insoluble PP, A2: random copolymer of propylene and 4-30C alpha-olefin, A3: a composition composed of A1 and ethylene- propylene copolymer (EP copolymer) and/or ethylene-propylene-polyene copolymer (EPP copolymer) and A4: a composition composed of B and EP copolymer and/or EPP copolymer is mixed with (B) 90-10wt.% thermoplastic resin. Furthermore, the aimed composition is optionally containable of unsaturated cathoxylic acid (anhydride)-modified polyolefin or styrene-grafted polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic resin composition containing soft polypropylene. [Conventional technique #i] Automotive materials (A variety of resins are used depending on the part. For example, for both exterior materials such as bumpers and interior materials such as inner panels, A high degree of balance between rigidity, thermal properties and impact resistance is required.It is difficult to meet these requirements by using resins such as polypropylene, polyamide or polycarbonate alone. Therefore, various composite materials are being considered. Conventionally, blends of elastomers have been used to improve the impact properties of resins. For example, blends of polypropylene and ethylene-propylene rubber (JP-A-56
-088447, JP-A-55-151045, JP-A-51-(147946), Blend of polyamide and ethylene-propylene-dieneter polymer (E.G. Kolawote et.al, Eu
rop. Polym. J. 18,469.1982)
．． Generally, polybutadiene is added to polystyrene, or elastomer is added to polycarbonate. However, when these elastomers were added, the rigidity and heat resistance decreased significantly, which was a practical problem. [Problems to be Solved by the Invention] The present inventor conducted various studies in order to solve the conventional problems, and found that using a special soft polypropylene can suppress the decrease in elastic modulus and heat resistance. We also discovered that it was possible to obtain a thermoplastic resin composition with extremely high impact resistance. The present invention is based on this knowledge. [Means for Solving the Problems] Accordingly, the present invention provides a mature plastic resin composition comprising (A) 1lo to 90% by weight of soft polypropylene, and (B) 90 to io% by weight of 8 plastic fat. It is about things.

Furthermore, the present invention provides a soft 1JL resin containing (A) 10 to 90% by weight of soft polypropylene and CB) 90 to 10% by weight of a thermoplastic fat-free resin, and (C) unsaturated resin based on 100 parts by weight of the soft resin. It also relates to a thermoplastic resin composite characterized by containing 0.5 to 5 parts by weight of a polyolefin modified with a carboxylic acid or its anhydride, or 0.5 to 5 parts by weight of (C') a styrene-grafted polyolefin. ．． The thermoplastic resin composition of the present invention comprises soft polypropylene (
A>10~90% by weight and thermoplastic resin (B) 90~1O
% by weight. The content of soft polypropylene (A) is low! If it is less than i% by weight, the impact resistance will be low, and if it exceeds 90% by weight, the rigidity will be low, which is not preferable. [Margin below] What does "soft polypropylene" mean in this specification? The homopolymer or copolymer described in (1) to (4) below,
Furthermore, it means any composition containing these polymers. <1) (i) rl: I viscosity is 1. 2 dl/g
Butane soluble polypropylene 10-9
0% by weight and (ii) the intrinsic viscosity is O. S~9. Od/g
Hebutane-insoluble polypropylene 9o~10f
polypropylene polymer (a>, (2
) (i) α-olefin unit content is 0.1 to 5 mol%
and (ii) the boiling hexane soluble content with an intrinsic viscosity of 1.2 dl/g or more is 20 to 99.9 fii%,
and (iii) the tensile modulus is 5000 Kg/
cm” or less, propylene and α- having 4 to 30 carbon atoms
Random copolymer with olefin (b), (3)(i) the above polybrobylene polymer (a) IO~
95! lZ amount%. (ii) Ethylene unit content is 1
0-60 mol%. and the intrinsic viscosity is 0.5 to 7.0 dl/
Ethylene-brobylene copolymer (c) and/or (ii) g has an ethylene unit content of 10 to 60 mol%, a polyene unit content of 1 to 10 mol%, and an intrinsic viscosity of 0.
a brobylene-based composition (d) consisting of 90 to 5% by weight of an ethylene-propylene-boriene copolymer (c') having an ethylene-propylene-borienne copolymer (c') having an Odi/g ratio of 5 to 7-Odi/g, and (4) (i) the random copolymer Consisting of 10 to 95% by weight of the polymer (b) and (ii) 90 to 5% by weight of the ethylene-propylene copolymer (c) and/or ethylene-propylene-boriene copolymer (c'). Propylene group Xi! ．． Things (e). In addition,
The above polypropylene polymer (a) has the following property (i)
Particularly preferred are those having -(iv). (i) "In bentad fraction by C-NMR, r
rrr/1-swam is 20% or more. (ii) Melting peak temperature measured with a differential calorimeter (DSC) (
Tm) is 150°C or higher. (iii) Enthalpy of fusion measured by DSC (ΔI0 is l O O J/
g or less. (iv) A domain structure is observed in transmission electron microscopy. Among the soft polypropylenes used in the present invention, the polypropylene polymer (a) and random copolymer (b)
For example, the gas phase one-stage polymerization method described below or the slurry
It can be prepared by any one-stage polymerization method.
Below, we will explain their preparation methods in order. The catalyst system used in the gas phase one-stage polymerization method is, for example, (I)
(i) a solid component consisting of a crystalline polyolefin and (ii) a solid catalyst component consisting of magnesium, titanium, a halogen atom, and an electron-donating compound; (■) an organic alkunium compound; (m) an aromatic compound containing an alkoxy group. , and (■)?
It consists of a combination of lt child-donating compounds. The solid material (!) mentioned above is a crystalline bosolefin (i)
0.005 to 1 part by weight of solid catalyst component (portion)
30 parts by weight (preferably 0.02 to 10 parts by weight). The solid component (1) may be, for example, a solid catalyst component (ii
), an organic alkunium compound, and optionally an electron-donating compound, it can be prepared by a method of prepolymerizing an olefin (prepolymerization method). Here, solid catalyst fractionation (ii) requires magnesium, titanium, halogen atoms, and electron-donating compounds.
rF. It can be prepared by contacting a magnesium compound, a titanium compound, and an electron-donating compound. Examples of magnesium compounds include magnesium dihalides such as magnesium dichloride, magnesium oxide, magnesium hydroxide, octotalcite, magnesium carponates, alkoxymagnesiums such as diethoxymagnesium, allyloxymagnesium, alkoxymagnesium halides, and allyloxymagnesiums. Examples include alkylmagnesiums such as magnesium halide and ethylbutylmagnesium, alkylmagnesium halides, or reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, and aluminum compounds. Magnesium halides, alkoxymagnesiums, alkylmagnesiums, and alkylmagnesium halides are preferred. Also,
These magnesium compounds may be used alone or in combination of two or more. Examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-broboxytitanium, tetraisobroboxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium, etc. Tetraalkoxytitanium, titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, broboxytitanium triclosotho, n-butoxytitanium trichloride, ethoxytitanium Trihalogenated alkoxytitanium such as tribromide, dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dibroboxytitanium dichloride, di-n-broboxytitanium diclosod, diethoxytitanium dibromide, trimethoxytitanium Examples include heptanohydrogenated trialkoxytitanium such as chloride, triethoxytitanium clothodide, triproboxytitanium chloride, tri-n-butoxytitanium chloride, etc.
Among these, highly halogen-containing titanium compounds, especially titanium tetrachloride, are preferred. These titanium compounds may be used alone or in combination of 28i or more. The electron-donating compound is an organic compound containing oxygen, nitrogen, phosphorus, sulfur, silicon, etc., and can improve regularity in the polymerization of propylene.

Examples of such electron-donating compounds include esters, thioesters, amines, ketone horns, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, One can mention things like organic acid cheeks. Furthermore, for example, diphenyldimethoxysilane, diphenyldiethoxysilane,
Organosilicon compounds such as dibenzyldimethoxylane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimedoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane, penzyltrimethoxysilane, etc. 1-phthalate Aromatic dicarboxylic acid esters such as n-butyl acid and diisobutyl 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, etc. , isobrobyl methyl ether, isobrobyl ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t-butyl-n-propyl ether. t-
Butyl-n-butyl ether 5 Asymmetric ethers such as t-amylmethyl ether and t-amyl ethyl ether, 2'-azobis(2-ethylpropane), 2,2
-azobis(2-ethylbroban), 292゜-azobis(2-methylbentane〉, a.a゛-azobisisobutyronitrile, 1.1'-azobis(1-cyclohexanecarboxylic acid), (1-phenyl methyl)-azodiphenylmethane, 2-phenylazo-2,4-dimethyl-4
Examples include azo compounds in which a sterically hindering substituent is bonded to an azo bond, such as monotrixybentanenitrile, and these may be used alone or in combination. You may use a combination of 2m or more. Specifically, dimethyl phthalate, diethyl phthalate, diprobyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl isobutyl phthalate, ethyl probyl phthalate, ethyl imbutyl phthalate, probyl isobutyl phthalate dimethyl terephthalate, diethyl Terephthalate, dibrobyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl brobyl terephthalate, methyl isobutyl terephthalate 2
Ethylpropyl terephthalate, ethyl isobutyl terephthalate, probyl isobutyl terephthalate, dimethyl isophthalate, diethyl inphthalate, dibrobyl isophthalate, diisobutyl isophthalate,
Aromatic dicarboxylic acid diesters such as methyl ethyl isophthalate, methyl brobyl isophthalate, methyl isobutyl isophthalate, ethyl brobyl isophthalate, ethyl isobutyl isophthalate and probyl isobutyl 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 bivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, benzoic acid Ethyl, brobyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate, alkyl toluate, ethyl anisate, ethyl ethoxybenzoate, P-butoxybenzoic acid Monoesters such as ethyl, ethyl 0-chlorobenzoate and ethyl naphthoate, esters having 2 to 18 carbon atoms such as γ-valerolactone, coumarin diphthalide, ethylene carbonate, benzoic acid, p-oxybenzoic acid, etc. organic acids, acid anhydrides such as succinic anhydride, benzoic anhydride, p-toluic anhydride, carbon a3 such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, penzophenone, benzoquinone, etc.
~15 ketones, aldehydes with 2 to 15 carbon atoms such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthylaldehyde, a2 to 15 carbon atoms such as acetyl chlorite, penzyl chloride, 1-ruyl chloride, anisyl chloride, etc. acid halites, ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isobrobyl ether, n-phthyl ether, acryl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene gisocol butyl ether, acetic acid amide, benzoic acid Acid amides such as amide, toluic acid amide, tributylamine, N, N'
-Amines such as dimethylbiverazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediakone, acetonitrile, and penzonitrile. Examples include nitriles such as tolnitrile. Among these, esters, ethers, ketones and acid anhydrides are preferred, particularly di-n-butyl phthalate,
Suitable examples include aromatic dicarboxylic acid diesters such as diisobutyl phthalate, and alkyl esters of aromatic monocarboxylic acids having 1 to 4 carbon atoms such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid. be. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence. The above-mentioned solid catalyst component (ii) can be prepared by a known method (JP-A-53-43094, JP-A-55-13510).
Publication No. 2, JP-A-55-135103, JP-A-5
6-18606). For example, (1) a method of pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor and a 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 an 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 method of reacting the material obtained in (1) or (2) with a titanium compound; A method in which a complex compound of a magnesium compound and an electron donor is pulverized in the presence of an electron donor, a titanium compound, a grinding aid used as desired, and the like, and then treated with a halogen or a halogen compound, (6) the method described above. (
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 above-mentioned solid substance can be prepared. In addition, oxides of elements belonging to groups ■ 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 ■ to ■ of the periodic table. A substance, for example, a solid substance such as a magnesium compound supported on silica alumina, an electron donor, and a titanium compound are heated at 0 to 200°C in a solvent.
, preferably at a temperature in the range of 10 to 150°C for 2 minutes to
Solid catalyst fraction (ii) can be prepared by contacting for 24 hours. In addition, in the preparation of the solid catalyst component (it), an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, or an aromatic solvent such as benzene or toluene, is used as a solvent. It is possible to use halogenated hydrocarbons such as mono- and polyhalogenated compounds of the group hydrocarbons or saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. 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 0.1 to 1. It is in the range of 10. The above-mentioned solid component (1) can be prepared by pre-polymerizing the olefin in the presence of the thus obtained solid catalyst fraction (ii), an organoaluminum compound, and optionally an electron-donating compound. can. The aluminum compound used here has the general formula A, R, and px. -p
Examples include compounds represented by (1) (in the formula, R3 is an alkyl group having carbon atoms a1 to a10, X 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, triisobrobylaluminum, triimbutylaluminum, and trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, and diimbutylaluminum. Dialkylaluminum monohalites such as monochloride, 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 Oi) can be used. In the method for preparing solid component (I), as the olefin, for example, ethylene,
An α-olefin having 2 to 10 carbon atoms such as propylene, butene-1, 4-methylbentene-1 is used, and usually 30 to 10 carbon atoms are used.
Prepolymerization is carried out at a temperature in the range of 80"C, preferably 55 to 70"C, to form a crystalline polyolefin preferably having a melting point of 100C or higher. At this time, the aluminum/titanium atomic ratio of the catalyst system is usually o. i~100,
It is preferably selected in the range of 0.5 to 5, and the electron donating compound/titanium molar ratio is O to 50, preferably 0.1 to 5.
Selected from a range of 2. The above-mentioned solid fraction (I) is prepared by adding the solid catalyst fraction (ii), an organoaluminum compound, and an electron-donating compound (with a melting point of 100°C or more) to a crystalline powder such as polypropylene or polyethylene with a uniform particle size. The solid component (1) can also be prepared by a method of dispersing the solid component (1) (separation 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 consists of a solid component (1), an organoaluminum compound (n), an alkoxy group-containing aromatic compound (m), and an electron-donating compound (mV
), but as an organic alkunium compound (■) and an electron-donating compound Th (1'V),
Each of the compounds explained above can be used. Further, the alkoxy group-containing aromatic compound (m) can be expressed, for example, by the general formula [where R' is an alkyl group having from al to 20 carbon atoms, R2 is a hydrocarbon group having 1 to 10 carbon atoms, water/! Aj2! It is a compound represented by li or a nitro group, m is an integer of 1 to 6, and n is an integer of 6-m. Specifically, examples include m-methoxytoluene, O-methoxyphenol , m-methoxyphenol, 2-methoxy4-methylphenol, vinylanisole, p-(1-brobenyl)anisole 5p-allylanisole, 1,3-bis(p-methoxyphenyl)-1-bentene, 5-allylu2 -methoxyphenol, 4-aryl-2-methoxyphenol, 4
- Monoalkoxy compounds such as hydroxy-3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole, nitrophenetole, 0-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3.4-dimethoxytoluene, 2.6 - Dimethoxyphenol, l-allyl-3,4-dimethoxybenzene and other dialkoxy compounds and 1,3,5-trimethoxybenzene, 5-allyl-1,2,3-trimethoxybenzene, 5-allyl-1,2 .4-}rimethoxybenzene, 1,2,3-trimethoxy-5-(1-brobenyl)benzene, l,2,4-trimethoxy5-(
l-probenyl)benzene, 1,2,3-trimethoxybenzene. Examples include trialkoxy compounds such as 1,2,4-trimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferred. These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more. In the above catalyst system, the solid component (1) has an o. Use in an amount of ooos to 1 mole. Further, the amount of the alkoxy group-containing aromatic compound (m) used is 1 mole of titanium atom in the solid fraction (I). The amount is 0.01 to 500 mol, preferably 1 to 300 mol. This usage amount is o. If it is less than oi moles, the physical properties of the produced polymer will deteriorate, and if it exceeds 2,500 moles, the catalyst activity will decrease, which is not preferable. In this catalyst system, the atomic ratio of aluminum to titanium is l: 1 to 3,000 (preferably l: 40-800). If the atomic ratio falls outside of this range, sufficient catalytic activity will not be obtained. Furthermore, an alkoxy group-containing aromatic compound (m) and an electron donating compound (r
The molar ratio with V) is 1:0.01 to 100 (preferably 1:0.2 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. Molecule: im clauses can be performed by known means (eg, adjusting hydrogen concentration). jII combined temperature is generally 40~
90°C (preferably 60-75°C), and the polymerization pressure is lO-45κglcm” (preferably 20-30κg
/cm").The polymerization time is 5 minutes to 10 hours. In the slurry one-stage polymerization method, for example, either of the following two known catalyst systems can be used. That is, (1) Consists of a combination of (a) a solid whose essential components are magnesium, titanium, a halogen atom, and an electron donor, (b) an aromatic compound with an alkoxy group, and (c) an organoaluminum compound. Catalyst system, or (2) (A) obtained by reacting the above-mentioned (i) solid fraction and (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organoaluminum compound. A catalyst system is 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) is a combination of magnesium, titanium, halogen atoms and It requires an electron donor as an essential component, and can be prepared by bringing a magnesium compound, a titanium compound, and an electron donor into contact.In addition, in preparing this solid component (a), a magnesium compound is used as a solvent. , organic solvents inert towards the electron donor and the titanium compound, e.g. aliphatic hydrocarbons (
hexane, hebutane, etc.), aromatic hydrocarbons (benzene, toluene, etc.), or halogenated hydrocarbons (mono- and polyhalogens of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms) 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 one 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, solid fraction (a) can be produced as rA 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 DI (c) to be brought into contact with the solid fraction (a) thus obtained are also used in connection with the catalyst system of the gas phase one-stage polymerization method. Each compound can be used. Regarding the usage amount of each component constituting the catalyst system (1), the solid fraction (a) is usually equivalent to the reaction volume in liters converted to titanium atoms, and o. ooos to 1 mol, and the alkoxy group-containing aromatic compound (B) is the molar ratio to the titanium atoms of the solid fraction (A), or the ratio is usually 0.01 to 500 (preferably 1 to 300). If this molar ratio is less than 0.01, the physical properties of the biopolymer will deteriorate, and if it exceeds 500, the catalytic activity will decrease, which is undesirable. It is used in an amount such that the 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 (2) will be explained. Then, the solid catalyst fraction (A) in this catalyst system (2) converts the solid catalyst fraction (a) of the catalyst system (1) and the alkoxy group-containing aromatic compound (b) into the organic aluminum compound ( It can be prepared by reacting in the presence or absence of c).For this preparation, a hydrocarbon solvent (for example, the hydrocarbon solvent used in preparing the catalyst system (1) above) is generally used. The reaction temperature is usually 0 to 150°C (preferably 10 to 50°C).
℃), and if this temperature is less than 0℃, 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 1 minute to 20 hours, preferably 10 to 60 minutes. When preparing the solid catalyst component (A) in the presence of the organoaluminum compound (c), this aluminum compound 5iI
The concentration of li (c) is usually 0.05 to 100 mmol/
(preferably 1 to 10 mmol/Jl). If this concentration is less than 0.05 mmol/ml, the effect of the reaction in the presence of the organoaluminum compound (c) will not be sufficiently obtained, and if it exceeds 100 mmol/ml, the titanium in the solid fraction (b) will not be sufficiently effective. catalytic activity decreases as the reduction progresses. On the other hand, in the absence of the organoaluminum compound (c), the solid fraction (a) and the alkoxy group-containing aromatic compound (b)
When preparing the solid catalyst component (A) by reacting with
The molar ratio of the alkoxy group-containing compound (b) to the titanium atoms in the solid component (a) is usually 0.1 to 200 (
Preferably, it is used in a ratio of 1 to 50),
In addition, the concentration of the compound (b) is usually 0.01 to 1
0 mmol/day (preferably 0.1-2 mmol/day)
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. 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 usage amount of each fraction in the catalyst system (2), the solid catalyst fraction (A) is equivalent to the reaction volume 1 in terms of titanium atoms.
Literally, usually o. The aluminum compound (B) is used in an amount such that the aluminum compound (B) has an aluminum/titanium atomic ratio of usually 1 to 3.
000 (preferably 40 to 800). If this atomic ratio exceeds the above range, the catalytic activity will be insufficient. In the slurry one-stage polymerization method of the present invention, when propylene is homopolymerized, the polypropylene polymer (a
) can be obtained, and propylene and α having 4 to 30 carbon atoms can be obtained.
When copolymerized with 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℃.
(preferably 60 to 100°C) and the brobylene pressure is usually selected in the range of 1 to 50 Kg/c+s. Polymerization time of about 5 minutes to 10 hours is sufficient; The molecular weight of can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel. Polymer (
a) and an ethylene-propylene copolymer (c) or an ethylene-propylene-boriene copolymer (C)} and a brobylene composition (e) {the random copolymer (b) and an ethylene-propylene copolymer (C) or an ethylene-propylene-boriene copolymer (C゛)}, for example, by any of the following gas phase multi-stage method, slurry multi-stage method, or blending method. It can be prepared by The catalyst used in the vapor phase multi-stage polymerization method of Ibarana Moxibustion Dan Yutateushi is the same as the catalyst used in the gas phase one-stage polymerization method described above. In the gas phase multi-stage polymerization method, I&
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 (eg, adjusting the hydrogen concentration). The polymerization temperature is
Generally, the temperature is 40 to 90°C (preferably 60 to 75°C), and the polymerization pressure is 10 to 45 Kg/cm" (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, 2-tricyclobentadiene, 5-methyl-2,5-norbornadiene, and 5-methyl-2,5-norbornadiene.
Methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isobropylidene-2-norbornene, 5-isobrobenyl-2-norbornene. 5- (1
-butenine)-2-norbornene, cyclooctadine, vinylcyclohexene. 1,5.9-cyclododecatriene, 6-methyl-4.7,8.9-tetrahydroindene, 2-2°-dicyclopentenyl, trans-1
, 2-divinylcyclobutane, 1,4-hexadiene.
4-Methyl-1,4-hexadiene, 6-octadiene, 1,7-octadiene, 1.8-nonadiene, 1
．． 9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 1
, 4,7-octatriene, 5-methyl-1,8-nonadiene, norbornadiene, vinylnorbornene, and the like. Among these non-conjugated polyenes, cyclobentadiene, 5-ethylidene-2-norbornene, and 1,7-octadiene are particularly preferred. In each polymerization step, the molecular weight can be adjusted by known means (
For example, hydrogen concentration yA! ) can be done. In the case of ethylene-brobylene copolymers, the ethylene unit content can be adjusted by adjusting the feed gas composition. Further, in the case of an ethylene-brobylene-boriene copolymer, the polyene unit content tAgn can be determined by changing the amount of the polyene compound charged. The polymerization temperature is 20-90'C (preferably 40-50°C),
The polymerization pressure is 5 to 30 Kg/cm'' (preferably 10 to 20 Kg/cII2), and the polymerization time is 5 minutes to 10 hours.

Slurry multi-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, propylene homopolymerization or copolymerization of propylene and an α-olefin having 4 to 30 carbon atoms is performed, and in the second and fourth stage polymerization, ethylene-propylene copolymerization or Can perform ethylene-propylene-boriene polymerization. The number of polymerization stages (the number of n) can be selected as the optimal number to obtain the desired product, as in the gas phase multistage method, and the polymerization method can be either continuous polymerization method or discontinuous polymerization method. It can be used. In the case of propylene homopolymerization or copolymerization of propylene with an α-olefin having 4 to 30 carbon atoms, the polymerization temperature is usually 0 to 0.
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/cm. In the case of copolymerization, the polymerization temperature is usually 0 to 200°C (preferably 40 to 80°C)
range, and the olefin pressure is usually between 1 and 50 Kg/
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 to EE. In the case of an ethylene-propylene copolymer, the ethylene unit content TAm can be determined by preparing a charge gas, and in the case of an ethylene-propylene copolymer, The content of polyene units can be adjusted by adjusting the amount of charge. As the polyene monomer, the polyene monomers described in the gas phase multi-stage method can be used. d) and (e) are polypropylene polymer (a) or random copolymer (b)
It can be prepared by blending and ethylene-propylene copolymer (C) or ethylene-propylene-boriene copolymer (C゜) by a known method (for example, dry blending or kneading). ．． The polypropylene polymer (a) and random copolymer (b) are
The ethylene-brobylene copolymer (C) or the ethylene-brobylene-boriene copolymer (C°) can be obtained by the above-mentioned gas phase one-stage polymerization method or slurry one-stage polymerization method. Each can be obtained by known methods. Note that post-treatment after polymerization can be carried out by conventional methods. In other words, in the gas-phase one-stage polymerization method or the gas-phase multi-stage polymerization method, after polymerization, a stream of nitrogen or the like is applied to the polymer powder derived from the ffi combiner in order to remove unreacted olefins contained therein. It may be allowed to pass. Furthermore, if desired, the catalyst 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 polymerization, the monomer can be completely separated from the bosomer led out from the polymerization vessel, and then pelletized.

(Hereinafter T-margin) The thermoplastic resin composition of the present invention is characterized by containing the above-mentioned soft polypropylene (A). Preferred embodiments of the thermoplastic resin assembly I and article of the present invention are as follows. (1) (A) Soft polypropylene 10-90% by weight,
and (B) a composition consisting of 90 to 10% by weight polypropylene. (2) (A) 10 to 90% by weight of soft polypropylene,
and (B) a soft resin consisting of 90 to 10% by weight of polyamide, and (C) a group consisting of 0.5 to 5 parts by weight of a polyolefin modified with an unsaturated carboxylic acid or its anhydride based on 100 parts by weight of the soft resin. J & things. (:l) (A) Soft polypropylene lO~90% by weight
, and (B) a soft resin consisting of 90 to 10% by weight of polyester, and (C) 0.5 to 5 parts by weight of a polyolefin modified with an unsaturated carboxylic acid or its anhydride based on 100 parts by weight of the soft resin. A composition. (4) (A) Souga boribropylene lO ~ 90% by weight,
and (B) a soft resin consisting of 90 to io weight percent of polycarbonate, and (C) 0.5 to 5 parts by weight of a polyolefin modified with an unsaturated carboxylic acid or its anhydride based on 100 parts by weight of the soft resin. Group power. (5) (A) 10 to 90% by weight of soft polypropylene,
and (B) a soft resin consisting of 90-10% by weight of a styrene resin, and (C) a composition consisting of 0.5-5 parts by weight of a styrene-grafted polyolefin based on 100 parts by weight of the soft resin. The thermoplastic resin (
B) is not particularly limited as long as it melts and flows when heated and becomes plastic, and solidifies when cooled; for example, polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, acrylic resin. Examples include ABS resin, polyamide, polyacetal, polycarbonate, and thermoplastic polyester. In particular, polyolefins such as polyethylene, polypropylene, and polybutene are preferred. Furthermore, polypropylene is more preferred. Further, the thermoplastic resin (B) may be a homopolymer, a copolymer, or a mixture of two or more thermoplastic resins. As the polypropylene used as the thermoplastic resin CB), for example, a copolymer part consisting of an isotactic propylene homopolymer having crystallinity, an ethylene-propylene random copolymer with a small content of ethylene units, or a propylene homopolymer. A so-called brobylene block copolymer, which is composed of a homopolymerized part and a certain copolymerized part from an ethylene-propylene random copolymer with a relatively high content of ethylene units, or this block copolymer. Preferred examples include those in which each homopolymerization portion or copolymerization portion is further copolymerized with an α-olefin such as butene-1, and a substantially crystalline propylene-ethylene-α-olefin copolymer. Among these polypropylenes, the melt index (MI) is long/10 minutes or less, especially 1 to 50 g/1
A value in the range of 0 minutes is preferable. In addition, examples of the polyamide used as the thermoplastic resin (B) include hexamethylene diamine, decamethylene diamine, todecamethylene diamine, 2,2.4- or 2,4
．． 4-Trimethylhexamethylenediamine, l,3- or 1,4-bis(aminomethyl>cyclohexane), bis(p-aminocyclohexylmethane), m- or p
- Aliphatic, alicyclic, aromatic diamines such as xylylene diamine, aliphatic, alicyclic, aromatic diamines such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, diisophthalic acid, etc. Polyamides obtained by polycondensation with dicarboxylic acids; (bolyamides obtained from lactams such as monocabralactam and ω-laurolactam; alternatively, copolymer polyamides obtained from these components, mixtures of these polyamides, etc.) Specifically, for example, nylon-6, nylon-6, 6, nylon-6, 10, nylon-9, nylon-11, nylon-12, nylon-6, nylon-
6.6 copolymer, nylon-6,6, nylon-6,
Examples include 1O copolymer, nylon-6/nylon-11 copolymer, and the like. Among these widths, nylon-6 and nylon-6.6 are preferred in terms of improved heat resistance, rigidity, and the like.

In addition, the molecular weight of these polyamides is not particularly limited, but usually has a relative viscosity ηr (JISK6810 98%
(measured in sulfuric acid) is 1.0 or more.
Among these, those having a relative viscosity ηr of 2.0 or more are preferred because they have excellent mechanical strength.

Furthermore, various polyesters can be used as the thermoplastic resin (B), but for example, polyesters obtained by a polycondensation reaction of a bifunctional carboxylic acid component and an alkylene glycol component are preferred. be. Here, examples of the difunctional carboxylic acid component include dicarboxylic acids such as aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. Among these, terephthalic acid is particularly preferred. Note that other difunctional carboxylic acids may be used in combination without impairing the effects of the present invention. These are, for example, aliphatic dicarboxylic acids and their ester-forming derivatives, such as oxalic acid, malonic acid, adivic acid, suberic acid, azelaic acid, sebacic acid or decanedicarboxylic acid. The proportion of these other dicarboxylic acids should generally be within 20 mol% of the total dicarboxylic acids. Next, the alkylene glycol component is not particularly limited, but specific examples include ethylene glycol, propylene-1,2-glycol, propylene-1,3-glycol, butylene-1,4-glycol, and butylene-2,3-glycol.
Aliphatic diols having 2 to 15 carbon atoms such as -glycol, hexane-1,6-diol, octane-1,8-diol, neobentyl glycol or decane-1,10-diol can be used. Among them, ethylene glycol, butylene gellicol, etc. are preferred. Particularly suitable polyester resins include polyethylene terephthalate and polybutylene terephthalate. The polycarbonate resin used as the thermoplastic resin (B) has, for example, a general formula (wherein Z is a single bond, an ether bond, or a carbon number of 1 to
8 alkylene group, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a sulfonyl group, a thionyl group, a carbonyl group, or a C}I, CH unit. A group represented by R is a hydrogen atom, a chlorine atom, 4 bromine atoms, or an alkyl group having 1 to 8 carbon atoms, and m is O or an integer of 1 to 4). It is a polymer with This polycarbonate composition is prepared by a solvent method, i.e., by reaction of a dihydric phenol with a carbonate precursor such as phosgene, or by the reaction of a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor 2 molecular weight regulator. It can be produced by transesterification with carbonate precursors such as diphenyl carbonate. Here, dihydric phenols that can be suitably used include bisphenols, and 2,2-bis(4-hydroxyphenyl)broban (bisphenol A) is particularly preferred. Alternatively, part or all of bisphenol A may be replaced with another dihydric phenol. Examples of dihydric phenols other than bisphenol A include bis(4-hydroxyphenyl) alkanes other than bisphenol A, hytroquinone, 4.4°-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkanes, Bis(4-hydroxyphenyl) sulfide, bis(4-
compounds such as hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ether or bis(3,5-dibromo-4-hydroxyphenyl)propane, bis( 3.
Mention may be made of halogenated bisphenols such as 5-cyclo-4-hydroxyphenyl)broban. These dihydric phenols may be homobolymers or cobolymers or blends of two or more dihydric phenols. Furthermore, the polycarbonate resin used in the present invention may be a thermoplastic randomly branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and/or a carbonate precursor. The polycarbonate resin used in the present invention has a viscosity average molecular weight of io, ooo to ioo, from the viewpoint of mechanical strength and moldability.
ooo is preferable, especially 20,000 to 40,0
00 is preferable. The thermoplastic resin composition according to the present invention includes, in addition to the above-mentioned soft polypropylene (A) and the thermoplastic resin (B), a modified polyolefin CC) with an unsaturated carboxylic acid or an anhydride thereof. (A) and Iwun (
It can be contained in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the total weight of B). It is preferable to include this component (C) because it has the effect of improving the appearance of the molded product. If the content of component (C) is less than 0.5 parts by weight, the desired effect will not be obtained, and if it exceeds 5 parts by weight, impact resistance and rigidity will decrease and yellowing will occur. Examples of polyolefins used for modification include polypropylene as exemplified in the explanation of component (B) polypropylene, polyethylene, ethylene-α-olefin copolymer rubber, and ethylene-α-olefin non-conjugated diene compound copolymer (e.g., EPDM). ), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer rubber, etc. are used. Further, examples of the α-olefin include propylene, butene-1, bentene-1, hexene-1, and hexene-1.
Examples include 1,4-methylbentene-1, which may be used alone or in combination of two or more. Furthermore, examples of unsaturated carboxylic acids used for modification include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. Derivatives include acid anhydrides, esters, amides. Imides, metal salts, etc., such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, Examples include maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. When modifying the polyolefin, these unsaturated carboxylic acids and their derivatives may be used alone or in combination of two or more, and there are no particular restrictions on the modification method, and any known method may be used. Various methods can be used. For example, a method of dissolving polyolefin in a suitable organic solvent, adding an unsaturated carboxylic acid or its derivative and a radical generator, stirring and heating, or feeding each of the above components to an extruder to perform graft copolymerization. You can use the following methods. In the modified polyolefin used as component (C), the amount of unsaturated carboxylic acid or its derivative added is usually in the range of 0.2 to 15% by weight (relative to the entire component (C)); If the previous polyolefin is crystalline such as polypropylene or polyethylene. When used, the amount is usually 0.2 to 15% by weight, preferably 0.5 to 12% by weight, and more preferably 1 to 8% by weight. In cases of poor quality such as
-8% by weight, preferably 0.5-5% by weight. Further, as component (C) in the composition of the present invention, only the polyolefin modified as described above may be used, or a mixture of this modified polyolefin and an unmodified polyolefin may be used in the 1a reaction. Good too. The styrene resin used as the thermoplastic resin (B) is obtained by homopolymerizing or copolymerizing the following monomers. For example, styrene, α-alkyl substituted styrene such as α-methylstyrene, α-ethylstyrene, α-methyl-p-methylstyrene, 0-methylstyrene, m-
Nuclear alkyl-substituted styrenes such as methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, o-t-butylstyrene, pt-butylstyrene, 0-chlorostyrene, m-chlorostyrene, p- Nuclear halogenated styrenes such as chlorostyrene, p-promostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, tribromostyrene, tetrachlorostyrene, tetrabromostyrene, 2-methyl-4-chlorostyrene, and even p-hydroxy Examples include styrene, 0-methoxystyrene, vinylnaphthalene, and among these, styrene and α-methylstyrene are particularly preferred. These aromatic vinyl monomers may be used alone or in combination of two or more. If desired, copolymerizable vinyl monomers used together with the above-mentioned aromatic vinyl monomers include vinyl cyanides such as acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, α-1chloroacrylonitrile, and anhydrous vinyl monomers. Maleic acid. Examples include unsaturated dicarboxylic anhydrides such as S-water itaconic acid, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, phenylmaleimide, etc. Among these, unsaturated dicarboxylic anhydrides, especially maleic anhydride Acids are preferred. In addition, these copolymerizable vinyl monomers are 1
It may be used alone or in combination of two or more species. Furthermore, rubber-modified styrene resins can also be used.
Rubbery polymers used in these applications include, for example, cis-type, trans-type, and low-vinyl polybutadiene obtained by emulsion polymerization or solution polymerization, and butadiene-styrene copolymer rubber obtained by emulsion polymerization or solution polymerization. ,
Examples include natural rubber, polyisobrene rubber, styrene-isobrene copolymer rubber, butyl rubber, ethylene-propylene copolymer rubber, and graft copolymer rubber of these rubbers and styrene. Polybutadiene and butadiene-styrene copolymer rubbers are preferred. One type of these rubbery polymers may be used, or two types may be used.
More than one species may be used in combination. Typical examples of such rubber-modified styrenic resins include Hl-PS, }II-SMA, styrene-butadiene-methyl methacrylate copolymer, and ABS. 15% by weight and 56-84% by weight of aromatic vinyl monomers and vinyl monomers copolymerizable, especially 1-40% by weight of unsaturated dicarboxylic acid anhydrides.
It is preferable to polymerize a mixture with There are no particular restrictions on this polymerization method, and conventional methods such as emulsion polymerization may be used. A bulk polymerization method, a solution polymerization method, a suspension polymerization method, or a multistage polymerization method such as a bulk one-suspension two-stage polymerization method can be used. When using the above styrene resin as the thermoplastic resin (B), the total weight of component (A) and component (B) is 10
0 parts by weight, styrene glat polyolefin (
C) 0.5 to 5 parts by weight. Inclusion of this component (C) is preferable since it has the effect of improving the appearance of the molded product. If the content of t (c) is less than 0.5 parts by weight, the desired effect cannot be obtained,
Even if more than 5 polymerization parts are added, no further improvement in the appearance improvement effect is observed even as a compatibilizer. Examples of polyolefins to be grafted with styrene include polypropylene, polyethylene, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated diene compound copolymer (e.g., EPDM), and ethylene-aromatic monovinyl compound monoconjugated diene compound copolymer. Polymerized rubber is used. As polypropylene, for example, a certain copolymerization part from an isotactic brobylene homopolymer having crystallinity or an ethylene-brobylene random copolymer with a low content of 2 ethylene units, or a certain homopolymerization part from a propylene homopolymer. A so-called propylene block copolymer is composed of a certain copolymerized part from an ethylene-propylene random copolymer having a relatively large content of ethylene units, or each homopolymerized part or Preferred examples include those in which the copolymerization portion is further copolymerized with an α-olefin such as butene-1, and a substantially crystalline brobylene-ethylene-α-olefin copolymer. Examples of α-olefin include brobylene,
Examples include butene-12betene-1, hexene-1,4-methylbentene-1, etc., and these may be used alone or in combination of two or more. Grafting with styrene can be achieved, for example, by introducing a reactive double bond or peroxide at the end of a polystyrene oligomer in advance, and then heating and kneading the polyolefin at the same time. At this time, diene compounds and organic peroxides can also be used as reaction aids. The amount of polystyrene in the styrene grafted polyolefin is 15
~40% by weight (based on the entire component (C)) is suitable; less than 15% by weight has poor affinity with styrene;
It is technically difficult to graft more than 40% by weight. The composition of the present invention may optionally contain various additives, reinforcing materials, fillers, such as heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, pigments, dyes, glass, etc. mix. Carbon fibers, talc, calcium carbonate, calcium sulfate, etc. can be added as long as they do not impair the purpose of the present invention. There are no particular restrictions on the method for producing the composition of the present invention.
Conventional polypropylene resin assembly dt. It is possible to use the methods commonly used for the construction of objects;
The order of mixing B) and component (C) can be freely selected as desired. For example, the required amounts of the components (A) and Ibun (B). Ikebun (C) and various additives used as necessary are mixed in a kneader, roll, Banbury. It can be produced by putting it all at once into a mixing machine such as a mixer, or an l-screw or twin-screw extruder, and then kneading it. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples. (1) Fixed catalyst power XI! l! 1. Into a glass three-necked flask with an internal volume of 500 mm that was sufficiently purged with nitrogen, 20 mJL of purified heptane and Mg (OEt) were added.
24 g and di-n-butyl phthalate l. Add 2g,
Keep the inside of the system at 90℃ and do not stir TiCl<4ml.
After dropping T i C l 4 1 1 1
ml was added and the temperature was raised to 110°C.
After reacting at 80°C for 2 hours, the mixture was washed with purified butane. Tic sentence 4115m sentence 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 product was washed several times with 100 mJl of purified butane to obtain a solid catalyst component [corresponding to the solid catalyst component (ii) of the gas phase method]. (2) Preparation of solid component In a pressure-resistant three-necked glass flask with an internal volume of 2.5 cm, which was sufficiently purged with nitrogen, was added 1 liter of purified hebutane. 7Jl, AIEts0.
07 mol, diphenyldimethoxysilane (DPDMS)
O. OS mmol and the catalyst fraction of (1.) above 120
g was added. The system was maintained at 30°C, and brobylene was continuously supplied with stirring to maintain the internal pressure at 0.5 κg/cm. After continuing this reaction for 1 hour, the system was washed 5 times with 1 liter of purified hebutane. , a solid fraction [corresponding to the solid fraction (I) of the gas phase method] was obtained. x3 mmol,
l-Ali,ru-3,4-dimethoxybenzene (ADMB
>0.15 mmol diphenyldimethoxysilane (D
20 ml of a hebutane solution containing 0.23 mmol (PDMS) and 100 mg (0.06 mmol in terms of Ti atoms) of the solid component (I) in (2) above was added. 5 within the system
After evacuation for a minute, hydrogen gas was released to 0. Gas phase polymerization was carried out at 70°C for 17 hours while supplying brobylene gas until the total pressure reached 28 Kg/cm". Melt index (MI) is 8.7
640 g of soft polypropylene with a weight of 710 g was obtained. Boiling butane soluble content (HSP content) of this Souga polypropylene
was 35% by weight, and the intrinsic viscosity was 1.95 dl/g. Also. The boiling hebutane insoluble content (HIP content) was 65% by weight, and the intrinsic viscosity was 4.78 dl/g. "The bentat fraction by c-NMR is 34.5%, and the melting peak temperature (Tm) measured by DSC is 158%.
°C, the enthalpy of fusion (ΔH) measured by DSC is 6
2.6 J/g, and a domain structure was observed in transmission electron microscopy. 5! Contains 20g of vapor phase first stage polymerized polypropylene powder! 3 mmol of AffiEts, l-allyl-3,4-dimethoxybenzene (ADMB
) 0.15 mmol, diphenyldimethoxysilane (D
PDMS) 0.23 misomole, and the aforementioned Production Example 1 (
Solid component (1) prepared in 1) and (2) 1
20 mJl of a hebutane solution containing 0.0 mg (O.Oa mmol 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 κg/cm. (2) Gas phase second stage polymerization (1). After the reaction is completed, the system is depressurized and exhausted, and ethylene-propylene mixed gas (molar ratio 1/4) is added.
Gas phase polymerization was carried out at 50°C for 1.4 hours. Melt index (MI) or O. 550 g of soft polypropylene of lg/10 min was obtained. This soft polypropylene consists of 65% by weight of polypropylene homopolymer and 35% by weight of ethylene-propylene copolymer. 35% by weight and intrinsic viscosity 4.78d
l/g ms Butane insoluble content (}IIP content) 65% by weight
It consists of and. In bentad fraction by 13C-NMR, r r r r / 1-mmmm is 34.5%
, the melting peak temperature (T m ) measured by DSC was 158°C, and the enthalpy of melting (ΔH) measured by DSC was 158°C.
) was 62.6 J/g, and a tomain structure was observed under transmission electron microscopy. On the other hand, the ethylene unit content of the copolymer is 31 mol%, and the intrinsic viscosity is 4
．． It was 81 ddan/g. 1 to 11 and 1 to 7 The components shown in Tables 1 and 2 were mixed and heated at a temperature of 220 mm using an extruder m (manufactured by Nakatanie Ia: NVC50Φ).
The mixture was heated and kneaded at ~290°C and extruded into a pellet shape. Test pieces were made by injection molding the obtained pellets, and the various properties of each of these test pieces were measured according to the specifications below. The results are summarized in Tables 1 and 2. The evaluation was performed using the following method. -20°C Izod impact strength Mature deformation temperature: Compliant with JIS K7209 However, conditioning time was 96 hours. The materials used are as follows. (Please note that the numbers in the cutout are from Table 1 and 2.
(This is the abbreviation in the table). Soft polypropylene (soft PP): Production example 1 or production example 2 Polypropylene (pp) Melt index = 10 g 710 minutes Polypropylene (PA) - Manufactured by Ube Industries, Ltd., product name = Ube Nylon 6 (10
13B) Polybutylene terephthalate (PBT): Manufactured by Boliplastic Co., Ltd., product name = DURANEX 2002 Boristyrene (PS): Manufactured by Idemitsu Petrochemical Co., Ltd., product name = HT-55 Polycarbonate (PC): Idemitsu Petrochemical Co., Ltd. Manufactured by Idemitsu Petrochemical Co., Ltd., product name = A2200 Maleic anhydride-modified polypropylene (maleic anhydride PP): Manufactured by Idemitsu Petrochemical Co., Ltd., product name = Boritac H300
0P. Amount of maleic acid added = 6% by weight Styrene-grafted polybrobylene (styrene-g-pp) Manufactured by Nippon Oil & Fats Co., Ltd., trade name = Modiper Hachi 3100.
Styrene unit content = 30% by weight [blank below] [Effects of the invention] The thermoplastic resin composite of the present invention not only has sufficient elastic modulus and thermal properties. Shows extremely excellent impact resistance. The thermoplastic resin assembly of the present invention is suitably used as a material for, for example, automobile parts, industrial machine parts, electronic/electrical parts, and building materials.

Claims (3)

[Claims] (1) A thermoplastic resin composition comprising (A) 10 to 90% by weight of soft polypropylene, and (B) 90 to 10% by weight of thermoplastic resin. (2) A soft resin containing (A) 10 to 90% by weight of soft polypropylene, and (B) 90 to 10% by weight of a thermoplastic resin, and (C) an unsaturated carboxylic acid or its A thermoplastic resin composition comprising 0.5 to 5 parts by weight of an anhydride-modified polyolefin. (3) A soft resin containing (A) 10 to 90% by weight of soft polypropylene and (B) 90 to 10% by weight of thermoplastic resin, and (C) 0.5 parts by weight of styrene-grafted polyolefin per 100 parts by weight of the soft resin. 5 parts by weight.