JPH0987451A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene resin composition excellent in impact resistance, rigidity and heat resistance, useful for e.g. automotive internal trim materials, by incorporating a specific resin component with a specified amount of a phosphate-based compound as nucleating agent. SOLUTION: This resin composition 0.5-300g/10min in MFR determined in accordance with the JIS K-7210 comprises (A) 100 pts.wt. of a resin component comprising (i) 70-90wt.% of a homopolypropylene component 0.01-1000g/10min in MFR satisfying the relationship: ΔHm >=24.50+1.583logMFR (ΔHm is heat of fusion determined by differential scanning colorimetry) and (ii) 5-30wt.% of a propylene-ethylele copolymer component 30-80wt.% in ethylene content and 2-6dl/g in intrinsic viscosity and (B) 0.05-3 pts.wt. of a phosphate-based compound of formula I or II (R<1> is a direct bond, S, a 1-9C alkylene or alkylidene: R<2> -R<4> are each H or a 1-8C alkyl; M is a mono- to trivalent metal atom; (n) is the valence number of M).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene resin composition having excellent impact resistance, rigidity and heat resistance.

[0002]

2. Description of the Related Art Polypropylene is widely used in various fields because of its light weight and excellent mechanical strength. However,
When polypropylene was used as an interior material for automobiles, the impact resistance and rigidity balance were not sufficient.

Various rubbers such as ethylene-propylene copolymer rubber (EPR) and an inorganic filler such as talc are added to a propylene-ethylene block copolymer for the purpose of improving impact resistance and rigidity balance. A polypropylene resin composition has been proposed. However, a resin composition obtained by adding a rubber component to a propylene-ethylene block copolymer is a high-impact polystyrene, AB
Compared with S resin and the like, there is a problem that impact resistance and rigidity are not sufficiently balanced, moldability is poor due to an increase in gel component, and the appearance of the molded product is poor. Further, by increasing the addition amount of the inorganic filler, the rigidity and the like can be improved, but the surface smoothness of the molded product deteriorates, and it is disadvantageous in terms of cost and recycling.

As described above, at present, a polypropylene resin composition having a good balance of impact resistance, rigidity and heat resistance has not yet been obtained. If these problems are solved, it is expected that the range of use of polypropylene-based resin materials will be expanded, the number of parts that can be covered with one material will increase, and that the development will be advantageous in terms of cost.

Therefore, it is an object of the present invention to provide impact resistance,
It is intended to provide a polypropylene resin composition having excellent rigidity and heat resistance.

[0006]

As a result of earnest research in view of the above object, the present inventors have found that in a polypropylene resin composition comprising a homopolypropylene portion and a propylene-ethylene copolymerization portion, the heat of fusion of the homopolypropylene portion and the melt While making a predetermined relationship with the flow rate, by adjusting the intrinsic viscosity and ethylene content of the propylene-ethylene copolymerization portion, and by adding a specific amount of a phosphate compound as a nucleating agent, The inventors have found that a polypropylene resin composition having excellent impact resistance, rigidity and heat resistance can be obtained, and conceived the present invention.

That is, the polypropylene resin composition of the present invention has (A) (a) a melt flow rate (MFR) measured according to JIS K7210 of 0.01 to 1000 g.
Homopolypropylene portion 70 to 95 satisfying the relational expression: ΔH _m ≧ 24.50 + 1.583 log MFR, in which the heat of fusion (ΔH _m ) obtained from differential scanning calorimetry and MFR satisfy the relation ΔH _m ≧ 24.50 + 1.583 log MFR.
% By weight, and (b) the ethylene content is 30-80% by weight,
100 parts by weight of a resin component consisting of 5 to 30% by weight of a propylene-ethylene copolymerized portion having an intrinsic viscosity of 2 to 6 dl / g, (B) the following general formula (I) or (II):

[Chemical 1]

Embedded image (wherein R ¹ is a direct bond, sulfur or C 1
To 9 are alkylene groups or alkylidene groups, R ² and R ³ and R ⁴ are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, M is a monovalent metal atom, and n is M. Is the valence. ) 0.05 to 3 parts by weight of the phosphate compound represented by the formula (1), and the MFR of the entire composition is 0.5 to 300 g / 10 minutes.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [1] Composition of polypropylene resin composition The polypropylene resin composition of the present invention is substantially (A) (a)
Homopolypropylene part, (b) a resin component consisting of a propylene-ethylene copolymerization part, and (B) a phosphate-based compound, a part in the resin component (a)
The compounds (b) and (b) may exist as a single polymer or may be in a state where they are bonded.

(1) Homopolypropylene part The homopolypropylene part is JIS K7210 (23
The melt flow rate (MFR) measured according to 0 ° C. and a load of 2.16 kg is 0.01 to 1000 g / 10 minutes. If the MFR is less than 0.01 g / 10 minutes, the moldability will decrease, while if it exceeds 1000 g / 10 minutes, the impact resistance will decrease. The preferred MFR is 0.5 to 300 g / 10 minutes.

Further, it is necessary that the heat of fusion ΔH _m and MFR obtained from the differential scanning calorimetry satisfy the relational expression ΔH _m ≧ 24.50 + 1.583 log MFR. ΔH _m <(2
4.50 + 1.583 log MFR), the polypropylene resin composition has low heat resistance and rigidity. The amount of heat of fusion ΔH _m is the amount of heat at the melting peak during the temperature rise from 85 ° C to 175 ° C during differential scanning calorimetry in which the sample is heated to 200 ° C, and the amount of heat is divided by the weight of the sample. It is calculated by
1 / g.

(2) Propylene-Ethylene Copolymerization Part The content of ethylene in the propylene-ethylene copolymerization part is 30 to 80% by weight. When the ethylene content is less than 30% by weight, the rigidity is low, while when it exceeds 80% by weight, the ductility and impact resistance are deteriorated. The preferable ethylene content is 30 to 60% by weight. The copolymerized portion is basically made of propylene and ethylene, but may contain a small amount (preferably 5% by weight or less) of other α-olefins, diene-based monomers and the like.

The intrinsic viscosity [η] of the propylene-ethylene copolymerization portion (measured in decalin at 135 ° C.) is 2 to 6
dl / g. When the intrinsic viscosity [η] is less than 2 dl / g, the effect of improving the rigidity is not sufficient, while when it exceeds 6 dl / g, the moldability decreases due to an increase in the gel component and the appearance of the molded product becomes poor. .

(3) Phosphate Compound Part The phosphate compound added as the nucleating agent is represented by the following general formula (I) or (II):

[Chemical 1]

(Wherein R ¹ is a direct bond, sulfur, an alkylene group having 1 to 9 carbon atoms or an alkylidene group, and R ^{2 is}
And R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, M is a metal atom having a valence of 1 to 3, and n is a valence of M. ).

Examples of the phosphate compound represented by the general formula (I) include sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate and sodium-2,2'-ethylidenebis. (4,6-
Di-t-butylphenyl) phosphate, lithium-
2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidenebis (4,6-di-t-butylphenyl) phosphate, sodium-2,2 '-Echidenimbisu (4-i
-Propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylenebis (4-methyl-)
6-t-butylphenyl) phosphate, lithium-
2,2'-methylenebis (4-ethyl-6-t-butylphenyl) phosphate, calcium bis [2,2 '
-Thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate], calcium bis [2,2 '] -Thiobis (4,6-
Di-t-butylphenyl) phosphate], magnesium bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium bis [2,2'-thiobis (4-t-) Octylphenyl) phosphate], sodium-2,2'-butylidenebis (4,6-dimethylphenyl) phosphate, sodium-2,2'-butylidenebis (4,6-di-t-)
Butylphenyl) phosphate, sodium-2,
2'-t-octylmethylene bis (4,6-dimethylphenyl) phosphate, sodium-2,2'-t-
Octyl methylene bis (4,6-di-t-butylphenyl) phosphate, calcium bis [2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate], magnesium bis [2,2 '] -Methylenebis (4,6-di-t-butylphenyl) phosphate], barium bis [2,2'-methylenebis (4,6)
-Di-t-butylphenyl) phosphate], sodium-2,2'-methylenebis (4-methyl-6-t-)
Butylphenyl) phosphate, sodium-2,
2'-methylenebis (4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium Bis [(4,4′-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl) phosphate], sodium-2,2′-ethylidene bis (4-s-butyl-6-) t-Butylphenyl) phosphate, sodium-2,2'-methylenebis (4,6-dimethylphenyl) phosphate, sodium-2,2'-methylenebis (4,6-diethylphenyl) phosphate, potassium-2, 2'-ethylidene bis (4,6-di-t-butylphenyl) phosphate, calcium bis [2,2'-ethylidene bis (4,6-di-t-butylphenyl) phosphate Sufeto], magnesium bis [2,2'-ethylidene-bis (4,6-di -t- butyl phenyl) phosphate], barium bis [2,2'-ethylidene-bis (4,
6-di-t-butylphenyl) phosphate], aluminum tris [2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate], aluminum tris [2,2'-ethylidenebis (4) , 6-t
-Butylphenyl) phosphate] and the like.

Examples of the phosphate compound represented by the general formula (II) include sodium bis (4-t-butylphenyl) phosphate, bis (4-t-butylphenyl) lithium phosphate, and bis (4) phosphate. -T-butylphenyl) potassium and the like.

(4) Ratio Regarding the ratio of each component in the resin component (A), (a) the homopolypropylene portion is 70 to 95% by weight, and (b) the propylene-ethylene copolymerized portion is 5 to 30% by weight. %.
When the homopolypropylene portion is less than 70% by weight, the mechanical strength is low, while when it exceeds 95% by weight, the impact resistance is lowered. Preferably, (a) the homopolypropylene portion is 80 to
95% by weight, and (b) the propylene-ethylene copolymerization portion is 5 to 20% by weight.

The amount of the (B) phosphate compound is 0.05 to 3 parts by weight based on 100 parts by weight of the resin component having the above-mentioned constitution. If the amount of the phosphate compound is less than 0.05 parts by weight, the nucleating action is insufficient and the rigidity of the composition is low. On the other hand, if the amount exceeds 3 parts by weight, further improvement of the effect cannot be obtained. Preferably, the phosphate compound is 0.0
It is 5 to 1 part by weight.

[2] Properties of Composition MFR of polypropylene resin composition (230 ° C., 2,160
g) is 0.5 to 300 g / 10 minutes. If the MFR is less than 0.5 g / 10 minutes, the moldability will be poor and 300 g / 10
If it exceeds, the mechanical properties of the composition deteriorate. The preferred MFR is 1-100 g / 10 minutes.

[3] Manufacturing Method As a manufacturing method of the resin component, there is a mechanical blending method of a homopolypropylene portion and a propylene-ethylene copolymerization portion, or a reactor blending method. In the mechanical blending method, the homopolypropylene portion and the propylene-ethylene copolymerization portion are separately prepared and then uniformly blended with a super mixer or the like. In the case of the reactor blending method, after the homopolypropylene portion is prepared, the propylene-ethylene copolymerization portion is continuously prepared in the same reactor, so that both are uniformly blended.

As a method for adding the phosphate compound to the resin component, for example, a Henschel mixer, a super mixer, a ribbon blender, a Banbury mixer or the like is used for mixing, and a conventional single screw extruder, twin screw extruder, or mixer is used. It is performed by melt-kneading with a lavender or a roll in a temperature range of 170 to 300 ° C.

(1) Formation of Homopolypropylene Portion The homopolypropylene portion is not particularly limited in its production method as long as it satisfies the above-mentioned physical properties, but is preferably produced by the following method.

(A) Preliminary Polymerization (i) Preliminary Polymerization Catalyst The prepolymerization catalyst is a solid component containing olefin (A) magnesium, titanium, halogen and an electron donating compound as essential components, (B) organoaluminum compound, It is prepared by contacting C) an organosilicon compound, and (D) an electron-donating compound if necessary. As olefins, in addition to propylene, ethylene, 1-butene, 1-hexene, 4
-Methyl-1-pentene and the like can be mentioned. Details of each of the above components of the prepolymerization catalyst are as follows.

(A) Solid Component The solid component (hereinafter referred to as component (A)) contains magnesium, titanium, a halogen and an electron donating compound as essential components, and is usually a magnesium compound, a titanium compound and an electron donating compound (the above-mentioned component). When each compound is a compound having no halogen, it can be prepared by further contacting with a halogen-containing compound.

(A) Magnesium compound The magnesium compound is represented by the general formula MgR ⁵ R ⁶ . R ⁵ and R ⁶ are the same or different hydrocarbon groups, OR ⁷ groups (R ⁷ is a hydrocarbon group) or halogen atoms. More specifically, the hydrocarbon group for R ⁵ and R ⁶ has 1 carbon atom.
~ 20 alkyl groups, cycloalkyl groups, aryl groups,
Examples of the aralkyl group include the OR ⁷ group, and R ⁷ includes an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group and an aralkyl group, and examples of the halogen atom include chlorine, bromine, iodine and fluorine. Is mentioned.

Specific examples of these compounds are shown below (however, Me: methyl, Et: ethyl, Pr: propyl,
Bu: Butyl, He: Hexyl, Oct: Octyl, P
h: phenyl, cyHe: cyclohexyl. same as below. ). _{MgMe 2, Mg (i-Pr} ) 2, MgB
u ₂ , MgOct ₂ , MgEtBu, MgPh ₂ , Mg
cyHe ₂ , Mg (OEt) ₂ , Mg (OHe) ₂ , M
g (OOct) ₂ , Mg (OPh) ₂ , EtMgCl,
HeMgCl, i-BuMgCl, PhMgCl, Ph
CH ₂ MgCl, BuMgBr, BuMgI, EtOM
gCl, PhOMgCl, EtOMgBr, EtOMg
I, MgCl ₂ , MgBr ₂ , MgI ₂ .

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when the component (A) is prepared. As an example,
Metallic magnesium, halogenated hydrocarbon and general formula: X ¹ _n M (OR ⁸ ) _mn (In the formula, X ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M is boron, carbon,
It is an aluminum, silicon or phosphorus atom, R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≧ 0. A) contacting an alkoxy group-containing compound.

X ^{1 in} the general formula of the alkoxy group-containing compound
Examples of the hydrocarbon group of R ⁸ and R ⁸ include methyl (Me), ethyl (Et), propyl (Pr), i-propyl (iP).
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (cyHe), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. And phenyl (Ph), tolyl, xylyl, and other aryl groups, phenethyl, 3-phenylpropyl, and other aralkyl groups. Of these, an alkyl group having 1 to 10 carbon atoms is particularly preferable.

Specific examples of the alkoxy group-containing compound include C (OEt) ₄ , C (OP) when M is carbon.
r) ₄ , C (OBu) ₄ , C (OOct) ₄ , HC (O
Me) ₃ , HC (OEt) ₃ , HC (OBu) ₃ , HC
(OPh) ₃ , MeC (OEt) ₃ , EtC (OM
e) ₃ , PhC (OEt) ₃ , CH ₂ ClC (OEt)
₃ , MeCHBrC (OEt) ₃ , ClC (OM
e) ₃ , ClC (Oi-Bu) ₃ , BrC (OE
t) ₃ , MeCH (OEt) ₂ , CH ₂ (OMe) ₂ ,
CH ₂ ClCH (OEt) ₂ , CHCl ₂ CH (OE
t) ₂ , CCl ₃ CH (OEt) ₂ , CH ₂ BrCH
(OEt) ₂ , PhCH (OEt) _{2 and the} like, and M
When is silicon, Si (OEt) ₄ , Si (OH
e) ₄ , HSi (OEt) ₃ , HSi (OPh) ₃ , M
eSi (OBu) ₃ , PhSi (OEt) ₃ , CHCl
₂ Si (OEt) ₃ , BrSi (OEt) ₃ , ClSi
(OBu) ₃ , CHCl ₂ SiH (OEt) ₂ , CCl
₃ SiH (OEt) ₂ , Me ₃ SiOEt, etc., and when M is boron, B (OEt) ₃ , B
(OBu) ₃ , B (OHe) ₃ , B (OPh) _{3 and the} like. When M is aluminum, Al (OM
e) ₃ , Al (OEt) ₃ , Al (OHe) ₃ , Al
(OPh) _{3 and the} like, and when M is phosphorus, P (OMe) ₃ , P (OEt) ₃ , P (OH
e) ₃ , P (OPh) _{3 and the} like.

As the magnesium compound, a group II or IIIa metal (M ') of the periodic table represented by the general formula: MgR ⁵ R ⁶ .p (M'R ⁹ _q )
Complexes with organic compounds of the formula (1) can also be used. The metal M ′ is aluminum, zinc, calcium, etc., and R ⁹ is 1 to 1 carbon atoms.
12 alkyl groups, cycloalkyl groups or aralkyl groups. Further, q represents the valence of the metal M ′, and p is 0.
The number of 1-10 is shown. Specific examples of the compound represented by M′R ⁹ _q include AlMe ₃ , AlEt ₃ , and Al (i-B).
u) ₃ , AlPh ₃ , ZnMe ₂ , ZnEt ₂ , ZnB
_{u 2, ZnPh 2, CaEt 2} , CaPh 2 , and the like.

(B) Titanium compound As the titanium compound, divalent, trivalent and tetravalent titanium compounds can be used. For example, titanium trichloride, titanium tetrachloride, titanium tetrabromide, trichloroethoxy titanium, trichlorobutoxy titanium, dichlorodiethoxy titanium, dichlorodibutoxy titanium, dichlorodiphenoxy titanium,
Examples include chlorotriethoxy titanium, chlorotributoxy titanium, tetrabutoxy titanium and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium and dichlorodiphenoxy titanium are preferable, and titanium tetrachloride is particularly preferable.

(C) Electron-donating compound Examples of the electron-donating compound include carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines and amides. , Nitriles, aldehydes, alcoholates, phosphorus bound to organic groups via carbon or oxygen,
Examples include arsenic or antimony compounds, phosphoamides, thioethers, thioesters, carbonates and the like. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, and ethers are preferred.

Specific examples of the carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, acrylic acid, methacrylic acid and crotonic acid, malonic acid, succinic acid, adipic acid and maleic acid. Aliphatic dicarboxylic acids such as, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexene monocarboxylic acid, alicyclic carboxylic acids such as cis-1,2-cyclohexanedicarboxylic acid, benzoic acid, toluic acid, anisic acid, cinnamic acid And aromatic polycarboxylic acids such as phthalic acid, naphthalic acid, trimellitic acid, trimesic acid, and mellitic acid. As the carboxylic acid anhydride, the acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, the mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, isobutyl pivalate, ethyl acrylate, methyl methacrylate and malon. Diethyl succinate, dibutyl succinate, diisobutyl adipate, diethyl maleate, diisobutyl maleate, diethyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-anisate, Ethyl cinnamate, Monomethyl phthalate, Dibutyl phthalate, Diisobutyl phthalate, Diallyl phthalate, Diphenyl phthalate, Diethyl terephthalate, Dibutyl terephthalate, Diethyl naphthalate, Dibutyl naphthalate, Trie trimellitate Le, and the like.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used,
As specific examples, acetate chloride, acetate bromide,
Acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid bromide, butyric acid iodide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid Bromide, succinic acid chloride, succinic acid bromide, adipic acid chloride, adibic acid bromide, maleic acid chloride, maleic acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, benzoyl chloride,
Examples thereof include benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid bromide, p-anisic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, and naphthalic acid dichloride. Further, a monoalkyl halide of a dicarboxylic acid such as adipic acid monomethyl chloride, maleic acid monoethyl chloride and phthalic acid butyl chloride can also be used.

Alcohols are represented by the general formula R ¹⁰ OH. In the general formula, R ¹⁰ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group. Specific examples include methanol, propanol, isobutanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, ethylphenol, n-octylphenol and the like.

The ethers are represented by the general formula R ¹¹ OR ¹² . R ¹¹ and R ¹² in the general formula the alkyl group having 1 to 12 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, may be the same also Tsu different. Specific examples include diethyl ether, diisopropyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, butyl allyl ether, diphenyl ether, anisole and the like.

(D) Halogen-containing compound Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, silicon-halide compounds having a hydrogen-silicon bond, Group IIIa, Group IVa and Va of the periodic table.
Halides of group elements (hereinafter referred to as metal halides)
And the like.

The halogenated hydrocarbon has 1 to 10 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes are mentioned. Specific examples of these compounds include, for aliphatic compounds, methyl chloride, methylene chloride, chloroform, iodoform, carbon tetrachloride, carbon tetraiodide, ethyl bromide, 1,2-dichloroethane, 1,2-diiodoethane, methyl chloroform. , 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexachloropropylene, decabromobutane, chlorinated paraffin, etc. , Chlorocyclopropane, hexachlorocyclopentadiene, hexachlorocyclohexane, etc., and aromatic compounds include chlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloro. La De, and the like. One or more of these compounds may be used.

The halogen-containing alcohol is a compound in which any one or more hydrogen atoms other than the hydroxyl groups in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are substituted with halogen atoms. As a halogen atom,
Examples thereof include chlorine, bromine, iodine and fluorine atoms, with chlorine atom being particularly preferable. Examples of these compounds include 2-chloroethanol, 1-chloro-2-propanol, 5-chloro-1-pentanol, and 3-chloro-.
1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-cresol, chlorohydroquinone, chlorophenol, 6-
Chlorothymol, 4-chlororesorcin, 2-bromoethanol, 1-bromo-2-butanol, 2-bromo-
p-cresol, 1-bromo-2-naphthol, fluorophenol, p-iodophenol, 2,2-dichloroethanol, 1,3-dichloro-2-propanol,
2,3-dibromo-1-propanol, 2,4-dibromophenol, 2,2,2-trichloroethanol,
2,3,4-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,2,2-trifluoroethanol, 2,4,6-triiodide Phenol, 2, 3, 4,
6-Tetrachlorophenol, tetrachlorobisphenol A, 2,2,3,3-tetrafluoro-1-propanol, tetrafluororesorcin and the like can be mentioned.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ and H
_{3 SiCl, H (C 2 H} 5) SiCl 2, H (t-C 4
H ₉ ) SiCl ₂ , H (C ₆ H ₅ ) SiCl ₂ , H (C
_{H 3) 2 SiCl, H (} i-C 3 H 7) 2 SiCl, H
_{2 (C 2 H 5) SiCl} , H 2 (n-C 4 H 9) SiC
1, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, H (C ₆ H ₅ ).
₂ SiCl and the like can be mentioned.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
Examples thereof include chlorides, fluorides, bromides, and iodides of i, particularly BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ ,
AlBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , T
lCl ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , Sb
F _{5 and the} like are preferable.

(A) a magnesium compound, (b) a titanium compound, (c) an electron-donating compound, and optionally (d) a halogen-containing compound are mixed and stirred in the presence or absence of an inert medium. Or by mechanical co-milling, 40
Contact at ~ 150 ° C. The inert medium, hexane, heptane, saturated aliphatic hydrocarbons such as octane, cyclopentane, saturated alicyclic hydrocarbons such as cyclohexane,
Aromatic hydrocarbons such as benzene, toluene and xylene can be used.

Specifically, the component (A) is composed of magnesium metal, halogenated hydrocarbon and the general formula: X ¹ _n M (O
R ⁸ ) _mn compound (which may be the same as the above-mentioned alkoxy group-containing compound) is contacted with a magnesium-containing solid obtained by contacting with a halogen-containing alcohol,
Then, a method of contacting with an electron donating compound and a titanium compound (JP-A-63-264607), a magnesium dialkoxide and a silicon halide compound having a hydrogen-silicon bond are brought into contact with each other, and then a titanium halide compound is brought into contact therewith, Then, a method of contacting with an electron-donating compound (and further contacting with a titanium halide compound if necessary) (JP-A-62-146904), a magnesium dialkoxide and a silicon halide compound having a hydrogen-silicon bond are contacted. And then contact with an electron-donating compound and then with a titanium compound (Japanese Patent Application Laid-Open No. Sho 5)
No. 8-198503) and the like, but a particular method is preferred. The component (A) may be washed with the above-mentioned inert medium, if necessary.

(B) Organoaluminum Compound The organoaluminum compound (component (B)) has the general formula: R ¹³ _r AlX ² _3-r (wherein R ¹³ is an alkyl group or an aryl group, X ² is a halogen atom, It is an alkoxy group or a hydrogen atom, and r is an arbitrary number within the range of 1 ≦ r ≦ 3.) Is preferable, and the number of carbon atoms is preferably 1 to 18, and more preferably 2 to 6.

Specifically, trimethylaluminum,
Trialkylaluminums such as triethylaluminum and triisobutylaluminum, dialkylaluminum monohalides such as dimethylaluminum chloride, diethylaluminum bromide and diethylaluminium iodide, monoalkylaluminums such as methylaluminum dichloride, ethylaluminum dibromide and ethylaluminium diiodide. Alkyl aluminum sesquihalides such as dihalide and ethyl aluminum sesquichloride, dialkyl aluminum monoalkoxides such as diethyl aluminum ethoxide, diethyl aluminum phenoxide and diisobutyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride Dialkylaluminum hydrides such as id and the like. Among these, trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable.

It is also possible to use an organic alnium compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such compounds include

Embedded image Etc. can be exemplified.

(C) Organosilicon Compound The organosilicon compound (component (C)) has the following general formula (III):

Embedded image (However, R ¹⁴ is a cyclic substituent having an ether bond or a thioether bond in the ring, an oxy group having an in-ring ether bond-containing cyclic substituent, an in-ring ketone bond-containing cyclic substituent, a nitrogen atom-containing heterocyclic substituent. Group, a silicon atom-containing heterocyclic substituent, or a substituent having a lactone skeleton structure, R ¹⁵ is a hydrocarbon group having 1 to 10 carbon atoms, R ¹⁷ O—,
R ¹⁸ ₃ Si- or R ¹⁹ ₃ SiO- (provided that R ¹⁷
Is a hydrocarbon group having 3 to 10 carbon atoms, R ¹⁸ and R ¹⁹
Are each a hydrocarbon group having 1 to 10 carbon atoms and may be the same or different. ), R ¹⁶ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1,
z is 2 or 3, and x + y + z = 4. ).

Specific examples of R ¹⁴ include the following (each R ¹⁴ group is represented by RA, RB, ...).

Embedded image

R ¹⁵ in the above general formula of the component (C),
Examples of the hydrocarbon group in R ¹⁷ , R ¹⁸ and R ¹⁹ include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group and an aralkyl group. As the alkyl group, ethyl, i
-Propyl, s-butyl, t-butyl, amyl, 2-ethylhexyl, decyl group and the like, and the alkenyl group includes vinyl, allyl, propenyl, 1-hexenyl, 1-octenyl, 1-methyl-1-. Examples thereof include a pentenyl group and the like, examples of the cycloalkyl group include a cyclopentyl group and a methylcyclohexyl group, examples of the cycloalkenyl group include a cyclopentenyl group and cyclohexenyl group, and examples of the cycloalkadienyl group include cyclopentadiene group. Examples of the aryl group include phenyl, tolyl, and a methylcyclopentadienyl group.
Examples thereof include a xylyl group and the like, and examples of the aralkyl group include a benzyl, phenethyl, 1-phenylpropyl group and the like.

Examples of the component (C) are shown below. [RA],
The symbols such as [RB] ... Correspond to the above symbols of R ¹⁴ in the general formula (III) of the component (C). [RA] ₂ Si
(OMe) ₂ , [RB] (i-Pr) Si (OM
e) ₂ , [RC] (t-Bu) Si (OMe) ₂ , [R
C] (Me ₃ SiO) Si (OMe) ₂ , [RA] (i
-Pr) Si (OEt) ₂ , [RA] Si (OM
e) ₃ , [RD] Si (OMe) ₃ , [RB] Si (O
Et) ₃ , [RE] MeSi (OMe) ₂ , [RF]
(I-PrO) Si (OMe) ₂ , [RG] (i-P
r) Si (OEt) ₂ , [RH] Si (OMe) ₃ ,
[RI] Si (OEt) ₃ , [RJ] Si (OSiM
e) (OMe) ₂ , [RK] Si (OEt) ₃ , [R
L] Si (OEt) ₃ , [RM] Si (OEt) ₃ ,
[RN] Si (OEt) ₃ .

(D) Electron-donating compound As the electron-donating compound (component (D)), an organic silicon compound (excluding the same as the component (C)), nitrogen, sulfur, oxygen, phosphorus, etc. Although electron donating compounds containing heteroatoms can be used, organosilicon compounds are preferred. The component (D) may be added when the organoaluminum compound is combined with the prepolymerization catalyst, or may be added after being brought into contact with the organoaluminum compound in advance.

The organosilicon compound is preferably one having a total of four alkoxy groups (which may be partially substituted with an alkyl group or an aryl group) bonded to a silicon atom. These alkyl groups and alkoxy groups may be chain or cyclic. The alkyl group or the aryl group may be substituted with a halogen element. Specific examples of the organosilicon compound include tetramethoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, and butyltriethoxy. Silane, butyltriphenoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyl Dibutoxysilane, dibutyldiphenoxylan,
Diisobutyldiethoxysilane, diphenyldimethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, chlorophenyldiethoxysilane, isopropoxycyclopentyldimethoxysilane, t-butoxycyclopentyl Examples thereof include dimethoxysilane, cyclohexylmethyldimethoxysilane, di-s-butoxy-n-propylmethoxysilane and the like.

Further, specific examples of the electron-donating compound containing a hetero atom include compounds containing a nitrogen atom:
2,6,6-tetramethylpiperidine, 2,6-diethylpiperidine, 2,6-diisobutyl-4-methylpiperidine, 2,2,5,5-tetramethylpyrrolidine, 3
-Methylpyridine, 2,6-diisobutylpyridine,
2,5-dimethylpiperidine, nicotinic acid amide, imidazole, benzoic acid amide, methyl nicotinate, 2-methylpyrrole, toluic acid amide, benzonitrile, acetonitrile, aniline, toluidine, triethylamine, tetramethylenediamine, tributylamine and the like. As a compound containing a sulfur atom, thiophenol, thiophene, ethyl 2-thiophenecarboxylate,
Methyl mercaptan, isopropyl mercaptan, diethyl thioether, diphenyl thioether, methyl benzenesulfonate, methyl sulfite and the like can be mentioned, and as a compound containing an oxygen atom, tetrahydrofuran, 2-methyltetrahydrofuran, 2,2,5,5-
Tetraethyltetrahydrofuran, 2,2,6,6-tetramethyltetrahydropyran, dioxane, diethyl ether, diphenyl ether, anisole, acetophenone, acetone, o-tolyl-t-butyl ketone, 2
-Ethyl furarate and the like can be mentioned, and as the compound containing a phosphorus atom, triphenylphosphine, triphenylphosphite, diethyl phosphate and the like can be mentioned.

(Ii) Prepolymerization Conditions The olefin is contacted with the solid component (component (A)) in the presence of the organoaluminum compound (component (B)) and the organosilicon compound (component (C)). Is prepolymerized. At that time, it is preferable to add an electron donating compound (component (D)) as necessary together with the component (B) and the component (C). The prepolymerization is carried out in the presence of an inert medium (which may be the same as that used in the preparation of the magnesium-containing solid), usually at a temperature of 100 ° C or lower, preferably -30 ° C to +.
It is carried out at a temperature of 30 ° C, more preferably -20 ° C to + 15 ° C. The polymerization method may be a batch method or a continuous method, or may be a multi-step polymerization of two or more steps. When carrying out in multiple stages, it goes without saying that the polymerization conditions can be changed in each stage.

Component (B) has a concentration of 10 to 10 in the prepolymerization system.
It is used in an amount of 500 mmol / liter, preferably 30 to 200 mmol / liter, and is 1 to 50,000 mol, preferably 2 to 1,000 mol, per 1 gram atom of titanium in the component (A). Used for. component
(C) is used so that the concentration in the prepolymerization system is 5 to 1,000 mmol / liter, preferably 10 to 200 mmol / liter. Ingredients used as needed
(D) is used so that the concentration in the prepolymerization system is 1 to 100 mmol / liter, preferably 5 to 50 mmol / liter. The olefin polymer is incorporated into the component (A) by prepolymerization, but the amount of the polymer is adjusted to the component (A).
It is preferably 0.1 to 200 g, especially 0.5 to 50 g per 1 g. The catalyst component prepared as described above is preferably washed in order to prevent deterioration of the catalyst component during storage. The catalyst component is preferably stored at the lowest possible temperature, preferably in the temperature range of -50 ° C to + 30 ° C, particularly -20 ° C to + 5 ° C.

(B) Main Polymerization The prepolymerization catalyst obtained as described above is combined with an organometallic compound and, if necessary, an electron donating compound to form a main polymerization catalyst, and homopolymerization of propylene is carried out. , To obtain the homopolypropylene part.

Examples of the organometallic compound include organic compounds of metals of groups I to III of the periodic table. lithium,
Organic compounds of magnesium, calcium, zinc or aluminum are preferable, and organic aluminum compounds are particularly preferable. The organoaluminum compound may be the same as the component (B) at the time of preparing the prepolymerization catalyst. Examples of the organic compound of a metal other than aluminum include diethyl magnesium, ethyl magnesium chloride, and diethyl zinc. Moreover, as an organic compound of aluminum and another metal,
Examples include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

The electron donating compound to be optionally combined with the prepolymerization catalyst and the organometallic compound may be the same as the electron donating compound (c) or the components (C, D). The electron donating compound may be added when the organometallic compound is combined with the prepolymerization catalyst, or may be added after being brought into contact with the organometallic compound in advance.

The amount of the organometallic compound used with respect to the prepolymerization catalyst is usually 1 to 2,000 gram moles, and preferably 20 to 500 gram moles per gram atom of titanium in the catalyst component. When an electron donating compound is used, the amount of the organometallic compound (as aluminum) is 0.1 to 40 g atom, preferably 1 to 25 g atom per mol of the electron donating compound, so that the amount of the organo metal compound is 1 to 25 g atom. Select the ratio of electron-donating compounds.

The propylene polymerization reaction may be carried out in either a gas phase or a liquid phase. When the polymerization is carried out in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, It can be carried out in an inert hydrocarbon such as xylene or in a liquid monomer. The polymerization temperature is usually -8.
The temperature range is 0 ° C to + 150 ° C, particularly 40 ° C to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atm. The molecular weight of the resulting polymer is controlled by the presence of hydrogen or other known molecular weight regulator. The polymerization reaction is carried out in a continuous or batch reaction, and the conditions may be those normally used. The polymerization reaction may be carried out in one stage or in two stages.

(2) Formation of Propylene-Ethylene Copolymerization Part The method for producing the propylene-ethylene copolymerization part is not particularly limited, and even if it is prepared separately from the homopolypropylene part, it is continuously prepared after preparation of the homopolypropylene part. May be.

(3) Preparation of Polypropylene Resin Composition When the homopolypropylene portion and the copolymerization portion are separately prepared, they can be used as the resin component by a mechanical blending method, or continuously prepared (multistage polymerization method). Also, the resin component of the present invention can be obtained. In the multi-stage polymerization method, homopolymerization of propylene is first carried out in the presence of the above catalyst to produce a homopolypropylene portion, and then the feed monomer is switched from propylene to ethylene + propylene in the same reaction vessel to continue the polymerization. Generate the ingredients.

The resin component and the phosphate compound are mixed using a Henschel mixer, a super mixer, a ribbon blender, a Banbury mixer, etc., and the mixture is mixed with an ordinary single-screw extruder, twin-screw extruder, Brabender or roll.
A polypropylene resin composition can be obtained by melt-kneading in a temperature range of 70 to 300 ° C.

[4] Additives In the polypropylene resin composition of the present invention, for the purpose of modification, for example, a heat stabilizer, an antioxidant, a light stabilizer, a flame retardant, a plasticizer, an antistatic agent, a mold release agent. Agents, foaming agents, coloring agents, crystal nucleating agents, pigments and the like can be added.

[0065]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of homopolypropylene part-forming component (A) In a 1 liter reaction vessel equipped with a reflux condenser, chip-shaped metallic magnesium (purity 99.
5%, average particle size 1.6 mm (8.3 g) and n-hexane (250 ml) were added, and the mixture was stirred at 68 ° C. for 1 hour, metallic magnesium was taken out, and dried at 65 ° C. under reduced pressure to obtain pre-activated metallic magnesium. .

Pre-activated metallic magnesium was added with n-
140 ml of butyl ether and n-butyl ether solution of n-butyl magnesium chloride (1.75 mol /
0.5 ml), and the resulting suspension is heated to 55 ° C.
Then, a solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After reacting at 70 ° C. for 4 hours with stirring,
The reaction solution was kept at 25 ° C.

HC (OC ₂ H ₅ ) ₃ 55.7 m was added to the reaction solution.
1 was added dropwise over 1 hour and kept at 60 ° C. for 15 minutes for reaction. The obtained solid was washed 6 times with 300 ml of n-hexane each time and dried under reduced pressure at room temperature for 1 hour to obtain magnesium 1
31.6 g of magnesium-containing solids containing 9.0% and 28.9% chlorine were recovered.

In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, 6.3 g of magnesium-containing solid and 50 ml of n-heptane under a nitrogen gas atmosphere.
To prepare a suspension and stir at room temperature while stirring 2,2,2-
A mixed solution of 20 ml (0.02 mmol) of trichloroethanol and 11 ml of n-heptane was added from a dropping funnel to 30
The mixture was added dropwise over a period of 1 minute and further stirred at 80 ° C. for 1 hour. The solid obtained was filtered off and 100 ml of n-hexane at room temperature was added.
Was washed 4 times with 100 ml of toluene and then twice with 2 times to obtain a solid component.

40 ml of toluene was added to the above solid component, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. After stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise, and then the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 90 ° C.
Wash twice with ml at 90 ° C. Furthermore, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C. for 2 hours, and the mixture was heated at room temperature to 100
Component (A) 5.5 g after washing 7 times with ml of n-hexane
I got

In a 500 ml reactor equipped with a prepolymerization stirrer, 3.5 g of the above component (A) and 300 m of n-heptane were placed under a nitrogen gas atmosphere.
1 was added, and the mixture was cooled to 5 ° C. with stirring. Next, a solution of triethylaluminum (TEAL) in n-heptane (2.
0 mol / l) and 2,3,4-trimethyl-3-
The concentration of TEAL and 2,3,4-trimethyl-3-azacyclopentyltrimethoxysilane in the reaction system was 10 each for azacyclopentyltrimethoxysilane.
It was added so as to be 0 mmol / liter and 10 mmol / liter, and stirred for 5 minutes.

After depressurizing the system, propylene gas was continuously introduced to polymerize propylene for 2.2 hours. After completion of the polymerization, purge propylene in the gas phase with nitrogen gas, and
The solid phase portion was washed with 00 ml of n-hexane three times at room temperature. The solid phase was dried under reduced pressure at room temperature for 1 hour to prepare a prepolymerized catalyst. As a result of measuring the amount of magnesium in the prepolymerization catalyst, the prepolymerization amount was 3. per 1 g of the component (A).
It was found to be 1 g.

Main Polymerization In a nitrogen gas atmosphere, an n-heptane solution of TEAL (0.
3 mol / liter) 4 ml and 3 ml of n-heptane solution of t-butoxycyclopentyldimethoxysilane (0.08 mol / liter) were mixed and held for 5 minutes, and then placed in a 5 liter stainless steel autoclave equipped with a stirrer. It was After charging 22.5 mg of the obtained prepolymerization catalyst into the reaction system, 36 liters of hydrogen gas (same as normal temperature and normal pressure) and 3 liters of liquid propylene as a molecular weight control agent were injected under pressure, and the reaction system was heated to 70 ° C. The temperature was raised to 1, and propylene was polymerized for 1 hour. After the completion of the polymerization, unreacted propylene and hydrogen gas were purged until the pressure in the container reached 0.2 kg / cm ² G.

Collect a small amount of polymer from the container and
R was measured at 230 ° C. and a load of 2.16 kg. In addition, according to the differential scanning calorimetry, DSC7 (7700 Dat
aStation, manufactured by Perkin Elma) at 85 ° C
The amount of heat measured at a heating rate of 10 ° C. / minute at the Atsushi Nobori to 175 ° C. according to the general calculated heat of fusion [Delta] H _m by dividing the heat quantity in weight of the sample. As a result, the MFR of the homopolypropylene portion was 170 g / 10 minutes and the ΔH _m was 28.
It was 43 cal / g. This ΔH _m is (24.50
+1.583 log MFR) calculated value ΔH
_It was larger than _m '(28.03).

(2) Production of Propylene-Ethylene Copolymerization Part and Resin Component After introducing 0.2 liters of hydrogen gas into the vessel, a mixed gas having a molar ratio of propylene and ethylene of 1.03 was supplied. The pressure in the container was kept at 6 g / cm ² G, and propylene and ethylene were copolymerized for 0.5 hour. Unreacted gas was purged to obtain 840 g of a white powdery resin component.
This resin component can also be called a propylene-ethylene block copolymer. As a result of analyzing the collected resin components, the homopolypropylene portion was 95% by weight and the propylene-ethylene copolymer portion was 5% by weight. The propylene-ethylene copolymer part had an ethylene content of 50% by weight and the intrinsic viscosity [η] (measured in decalin at 135 ° C) was 3 dl / g.

With respect to 100 parts by weight of the resin component, 0.2 parts by weight of sodium-2 as a phosphate compound,
2'-Methylenebis (4,6-di-t-butylphenyl) phosphate (trade name "NA-11", manufactured by Asahi Denka Kogyo Co., Ltd.) was added and mixed with a super mixer, and then a 50 mmφ uniaxial 21 in extruder (L / D = 28)
Melt kneading at 0 ° C. and screw rotation speed of 80 rpm,
Polypropylene resin composition pellets were obtained. Table 1 shows the production conditions of the polypropylene resin composition and the above measured values.

(3) Measurement of Mechanical Properties The pellets obtained above were injection molded at a resin temperature of 210 ° C., an injection pressure of 900 kg / cm ² and a mold temperature of 60 ° C. to prepare test pieces. The following mechanical properties were measured for each test piece. The measurement results are shown in Table 2. Flexural modulus (kgf / cm ² ): JIS K7203
With a test piece of 110 mm × 10 mm × 4 mm,
Measured in ° C. Izod impact strength (kgf · cm / cm): JIS
Measurement was carried out at 23 ° C. using a notched test piece of 80 mm × 10 mm × 4 mm according to K7110. Heat distortion temperature (HDT): 1 according to JIS K7207
It measured using the test piece of 20 mm x 12.7 mm x 4 mm at 23 degreeC and the load of 4.6 kgf / cm < ² >.

Examples 2 to 10 After producing a homopolypropylene portion under the same conditions as in Example 1, a propylene-ethylene copolymerization portion was produced under the conditions shown in Table 1, and the obtained resin component was used as a phosphate compound. Was added and melt-kneaded under the same conditions as in Example 1 to obtain a polypropylene resin composition. The polypropylene resin composition and the MFR and mechanical properties of each component were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 11 A homopolypropylene portion and a propylene-ethylene copolymerization portion were continuously produced under the conditions shown in Table 1, a phosphate compound was added, and the mixture was melt-kneaded under the same conditions as in Example 1 to obtain polypropylene. A resin composition was obtained. The polypropylene resin composition and the MFR and mechanical properties of each component were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 12 In the homopolypropylene portion produced under the conditions shown in Table 1,
The propylene-ethylene copolymerized portion produced under the conditions shown in Table 1 and the phosphate compound (“NA-11”) were melt-kneaded under the same conditions as in Example 1 to obtain a polypropylene resin composition. Polypropylene resin composition and M of each component
FR and mechanical properties were measured as in Example 1.
The results are shown in Tables 1 and 2.

Comparative Example 1 A polypropylene resin composition was prepared by adding the phosphate compound (“NA-11”) to the resin component prepared in Example 5, and the MFR and mechanical properties were the same as in Example 1. It was measured. The results are shown in Tables 1 and 2.

Comparative Examples 2 to 8 Component (A) produced in Example 1 was used as a polymerization catalyst component as it was without prepolymerization, and homopolypropylene portion and propylene-ethylene copolymerization portion were continuously added under the conditions shown in Table 1. A resin component was obtained in the same manner as in Example 1 except that the resin component was produced. A phosphate compound was melt-kneaded with the obtained resin component under the same conditions as in Example 1 to obtain a polypropylene resin composition. Polypropylene resin composition and MF of each component
R and mechanical properties were measured as in Example 1. The results are shown in Tables 1 and 2.

Comparative Example 9 A homopolypropylene portion prepared under the conditions shown in Table 1 using a catalyst not subjected to prepolymerization, a propylene-ethylene copolymerization portion prepared separately under the conditions shown in Table 1 and a phosphate compound (“ NA-11 ″) was mechanically blended using a super mixer, and melt-kneaded under the same conditions as in Example 1 to obtain a polypropylene resin composition. The MFR and mechanical properties of the polypropylene resin composition and each component were measured in the same manner as in Example 1. Tables 1 and 2 show the results.
Shown in

Table 1Example item 1 2 3 4 5 6 Polymerization conditions Generation of homopolypropylene part Hydrogen gas amount (L) 36 36 36 36 36 36Formation of copolymerized moieties C_Three/ C₂ ⁽¹⁾ 1.03 1.95 0.84 0.84 0.84 0.84 Pressure (kg / cm²G) 6 6 6.1 6 6 6 Polymerization time (hr) 0.5 1.8 1.5 1.5 1.5 1.5 Hydrogen gas amount (L) 0.2 0.1 0.5 0.1 0.1 0.1Amount of phosphate compounds added NA-11 addition amount⁽⁶⁾ 0.2 0.2 0.2 0.2 0.05 0.3Composition and physical properties Homopolypropylene part Content⁽²⁾ 95 85 85 85 85 85 MFR (g / 10min) 170 170 170 170 170 170 ΔH_m ⁽³⁾ 28.43 28.43 28.43 28.43 28.43 28.43 ΔH_m'^(Four) 28.03 28.03 28.03 28.03 28.03 28.03 Propylene-ethylene copolymer part Content⁽²⁾ 5 15 15 15 15 15 Ethylene amount⁽²⁾ 50 30 50 50 50 50 [η] (dl / g)^(Five) 3 3 2 4 4 4Entire composition MFR (g / 10 min) 123.8 63.9 76.8 49.8 49.8 49.8 Note (1) Molar ratio of propylene and ethylene. (2) Unit:% by weight. (3) Measured heat of fusion (cal / g). (4) Calculated value of heat of fusion (cal / g). (5) Measured in decalin at 135 ° C. (6) Unit: parts by weight (100 parts by weight of resin component) NA-11: sodium-methylenebis (4,6-di-t-butylphenyl) phosphate (manufactured by Asahi Denka Kogyo Co., Ltd.).

Table 1 (continued)Example item 7 8 9 10 11 12 Polymerization conditions Generation of homopolypropylene part Hydrogen gas amount (L) 36 36 36 36 21 4.5Formation of copolymerized moieties C_Three/ C₂ ⁽¹⁾ 0.84 0.84 0.21 0.80 0.84 0.84 Pressure (kg / cm²G) 6 6 6.4 6 6 6.1 Polymerization time (hr) 1.5 1.5 1 2 1.5 1.5 Hydrogen gas amount (L) 0.1 0 2.2 0.2 0.2 0.5Amount of phosphate compounds added NA-11 addition amount⁽⁶⁾ 1 0.2 0.2 0.2 0.2 0.2Composition and physical properties Homopolypropylene part Content⁽²⁾ 85 85 85 80 80 85 MFR (g / 10min) 170 170 170 170 65 5 ΔH_m ⁽³⁾ 28.43 28.43 28.43 28.43 27.87 26 ΔH_m'^(Four) 28.03 28.03 28.03 28.03 27.37 25.61 Propylene-ethylene copolymer part Content⁽²⁾ 15 15 15 20 20 15 Ethylene amount⁽²⁾ 50 50 80 50 50 50 [η] (dl / g)^(Five) 4 6 3 3 3 3Entire composition MFR (g / 10min) 49.8 35.3 65.2 45.8 29.2 3.8 Note (1) to (6) Same as above.

Table 1 (continued) Comparative Example Item 1 2 3 4 5 6 Polymerization conditions Homopolypropylene part produced hydrogen gas amount (L) 27 27 27 27 27 27 Copolymerized part produced C ₃ / C ₂ ⁽¹⁾ 0.84 1.03 1.95 0.84 0.84 0.84 Pressure (kg / cm ² G) 6 6 6.1 6 6 6 Polymerization time (hr) 1.5 0.5 1.5 1.5 1.5 1.5 Hydrogen gas amount (L) 0.1 0.1 0.1 0.1 0.1 0 Phosphate compound addition amount NA- 11 Addition amount ⁽⁶⁾ 0 0.2 0.2 0.2 0.3 0.2 Composition and properties Homopolypropylene part content ⁽²⁾ 85 95 85 85 85 85 MFR (g / 10min) 170 170 170 170 170 170 170 ΔH _m ⁽³⁾ 28.43 27.3 27.3 27.3 27.3 27.3 ΔH _m ' ⁽⁴⁾ 28.03 28.03 28.03 28.03 28.03 28.03 Propylene-ethylene copolymer content ⁽²⁾ 15 5 15 15 15 15 Ethylene content ⁽²⁾ 50 50 30 50 50 50 [η] (dl / g ) ⁽⁵⁾ 4 3 3 4 4 6 Whole composition MFR (g / 10 min) 49.8 123.8 63.9 47.9 47.9 36.8 Note (1) to (6) Same as above.

[0087] Note (1)-(6) Same as above.

Table 2 Examples Mechanical Properties 1 2 3 4 5 6 Flexural Modulus (kgf / cm ² ) 18,000 16,500 16,800 16,500 15,000 17,500 Izod Impact Strength ⁽¹⁾ 5.5 6.5 6.2 7.5 7.4 7.2 HDT (° C) 126 124 120 121 115 123 Note (1) Unit: kgf ・ cm / cm

Table 2 (continued) Example Mechanical Properties 7 8 9 10 11 12 Flexural Modulus (kgf / cm ² ) 18,000 16,000 16,800 14,000 14,800 15,500 Izod Impact Strength ⁽¹⁾ 7.6 8.5 8 10.5 9.2 8.5 HDT (° C) 124 121 123 109 119 114 Note (1) Same as above.

Table 2 (continued) Comparative Example Mechanical Properties 1 2 3 4 5 6 Flexural Modulus (kgf / cm ² ) 13,500 16,500 16,000 15,000 16,300 14,800 Izod Impact Strength ⁽¹⁾ 7.3 5.5 6.2 7 7 8.3 HDT (° C) 110 122 120 117 120 118 Note (1) Same as above.

[0091] Note (1) Same as above.

As is clear from Table 2, the polypropylene resin composition of the present invention is excellent in rigidity, impact resistance and heat resistance. Further, from the comparison between the example and the comparative example, it is understood that when the homopolypropylene portion having a heat of fusion smaller than [24.50 + 1.583 log MFR] is used, the balance of rigidity, impact strength and heat resistance is poor. Furthermore, ΔH _m ≧ [24.50 + 1.583 log MFR]
Even if the homopolypropylene portion satisfying the above condition is used, the rigidity is low when the phosphate compound is not added.

[0093]

The polypropylene resin composition of the present invention has
A homopolypropylene moiety having an MFR of 0.01 to 1000 g / 10 min and having a constant relationship between the heat of fusion (ΔH _m ) determined from differential scanning calorimetry and MFR;
Since a phosphate-based compound is added as a nucleating agent to a resin component consisting of a propylene-ethylene copolymerized portion having a predetermined property, it has excellent rigidity, impact resistance and heat resistance. Such polypropylene resin composition can be widely used for applications such as automobile interior materials.

Claims (2)

[Claims] (A) (a) Melt flow rate (MFR) measured according to JIS K7210 is 0.01 to 1000.
Homopolypropylene portion 70 to 95, which is in the range of g / 10 minutes, and in which the heat of fusion (ΔH _m ) obtained by differential scanning calorimetry and MFR satisfy the relational expression ΔH _m ≧ 24.50 + 1.583 log MFR.
% By weight, and (b) the ethylene content is 30-80% by weight,
100 parts by weight of a resin component consisting of 5 to 30% by weight of a propylene-ethylene copolymerized portion having an intrinsic viscosity of 2 to 6 dl / g, and (B) the following general formula (I) or (II): Embedded image (However, R ¹ is a direct bond, sulfur or an alkylene group having 1 to 9 carbon atoms or an alkylidene group, R ² and R ³ and R ⁴ are hydrogen atoms or an alkyl group having 1 to 8 carbon atoms, and M is A monovalent metal atom, and n is a valence of M.) 0.05
˜3 parts by weight, and the MFR of the entire composition is 0.5˜.
A polypropylene resin composition, which is 300 g / 10 minutes. 2. The polypropylene resin composition according to claim 1, wherein the amount of the phosphate compound added is 0.05 to 1 part by weight based on 100 parts by weight of the resin component.