JPH09143317A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene resin composition excellent in rigidity and heat resistance by blending a resin component containing a specified homopolypropylene part with a specified phosphate compound and/or a metal benzoate and a fatty acid amide. SOLUTION: This composition comprises 100 pts.wt. resin component (A) comprising a homopolypropylene part (a) which has a melt flow rate(MFR), measured according to JIS K 7210, of 0.01-1,000g/10min and of which the heat of fusion (ΔHm ) determined by differential scanning calorimetry and the MFR satisfy the relation of formula I, or consisting of 70-95wt.% of the part (a) and 5-30wt.% propylene/ethylene copolymer part (b) having an ethylene content of 30-80wt.% and an intrinsic viscosity of 2-6dl/g; 0.001-5 pts.wt. component (B) comprising a phosphate compound of formula II (wherein R<1> is a direct bond, S, a 1-9C alkylene or alkylidene; R<2> and R<3> are each H or a 1-8C alkyl, and n is the valence of M<1> ) and/or metal benzoate; and 0.01-1 pt.wt. fatty acid amide (C).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene resin composition, and more particularly to a polypropylene resin composition having excellent 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 electric part, an automobile part, etc., the rigidity and heat resistance were insufficient.

Regarding the improvement of rigidity and heat resistance, a method of adding a phosphate compound to a polypropylene resin has been disclosed (for example, JP-A-62-209151).
No. 243635, JP-A-63-37148,
Ibid-210152, ibid-243150, ibid-284
No. 242, JP-A-2-49047, and JP-A-102242.
No.). However, these techniques alone are not sufficient in terms of slipperiness and heat resistance.

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

[0005]

As a result of earnest research in view of the above object, the present inventors have found that a polypropylene resin composition comprising a homopolypropylene portion or a polypropylene resin composition comprising a homopolypropylene portion and a propylene-ethylene copolymerization portion. In, while ensuring that a predetermined relationship is established between the heat of fusion of the homopolypropylene portion and the melt flow rate, the intrinsic viscosity and ethylene content of the propylene-ethylene copolymer portion are adjusted, and the nucleating agent and the lubricant are mixed. The present invention has been found out that when added at the same time, a polypropylene resin composition having excellent rigidity and heat resistance can be obtained by the synergistic action of a nucleating agent and a lubricant, and the present invention has been conceived.

That is, the polypropylene resin composition of the present invention has (A) a melt flow rate (MFR) measured according to JIS K7210 of 0.01 to 1000 g / 1.
100 parts by weight of a resin component consisting of a homopolypropylene portion satisfying a relational expression of ΔH _m ≧ 24.50 + 1.583 log MFR, where the heat of fusion (ΔH _m ) and MFR obtained by differential scanning calorimetry are in the range of 0 minutes or ( A) (a) The melt flow rate (MFR) measured according to JIS K7210 is in the range of 0.01 to 1000 g / 10 minutes, and the heat of fusion (ΔH _m ) and MFR obtained from differential scanning calorimetry are ΔH _m ≧ 24.50 + 1.583 log MFR Homopolypropylene part 70-95 satisfying the relational expression
% 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)

Embedded image (where R ¹ is a direct bond, sulfur or C 1
To 9 are alkylene groups or alkylidene groups, R ² and R ³ are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, M ¹ is a metal atom having a valence of ¹ to 3, and n is a valence of M ¹ . Is a number. ) 0.01 to 5 parts by weight of a phosphate compound and / or metal benzoate represented by the formula (C) and 0.01 to 1 part by weight of (C) a fatty acid amide.

[0007]

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 comprises a resin component substantially consisting of (A) homopolypropylene portion or (A) (a) homopolypropylene portion, and (b) propylene-ethylene copolymer. A resin component consisting of a polymerized portion, (B) a phosphate compound and / or a metal salt of benzoic acid as a nucleating agent, (C)
The lubricant is composed of fatty acid amide, and the parts (a) and (b) in the resin component may be present 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 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. If the ethylene content is less than 30% by weight, the ductility and impact resistance will decrease, while 80% by weight
If it exceeds, the rigidity becomes low. 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) Nucleating agent The nucleating agent is (a) a phosphate compound and / or (b)
Selected from metal salts of benzoic acid.

(A) Phosphate Compound The phosphate compound used in the present invention has the following general formula:
(I):

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

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.

Among these phosphate compounds, sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate is particularly preferable.

(B) Benzoic acid metal salt The benzoic acid metal salt used in the present invention is preferably a benzoic acid metal salt of a metal of Group I of the periodic table, and particularly preferred specific examples thereof are lithium benzoate, sodium benzoate and benzoic acid. Barium acid may be mentioned.

(4) Lubricant The fatty acid amide used as a lubricant in the present invention is represented by the following general formula (I
I):

Embedded image (wherein R ⁴ is an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and R ⁵ is a hydrogen atom or a carbon atom of 1).
To 21 alkyl groups or alkenyl groups, each of which may have an —OH group. ).

Specific examples thereof include monoamides such as oleic acid amide, erucic acid amide, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and ricinoleic acid amide, and N-methylolstearic acid. Amide, methylolamide such as N-methylolbehenamide, N-
Stearyl erucic acid amide, N-oleyl stearic acid amide, N-dodecyl stearic acid amide, N-dodecyl oleic acid amide, N-octadecyl erucic acid amide, N, N-dioctadecyl stearic acid amide, N-
Octadecyl oleic acid amide, N, N-dioctadecyl behenic acid amide, N-docosyl erucic acid amide, N-
Docosyl oleic acid amide, N-oleyl oleic acid amide, N-oleyl erucic acid amide, N, N-dioleyl oleic acid amide, N, N-dioleyl erucic acid amide, N, N-dioleyl stearic acid amide, N -Erucyl oleic acid amide, N-erucyl erucic acid amide,
Examples thereof include N-substituted amides such as N-erucyllauric acid amide, N-erucylstearic acid amide, N-erucylbehenic acid amide, N-octadecylbenzoic acid amide, and N, N-dioctadecylbenzoic acid amide. Of these, oleic acid amide, erucic acid amide, N-
Methylol stearamide and the like are preferable.

(5) 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 proportion of the nucleating agent (B) is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin component having the above constitution. If the amount of the nucleating agent is less than 0.05 part by weight, the nucleating action is insufficient and the composition has low rigidity. On the other hand, even if it exceeds 1 part by weight, further improvement of the effect cannot be obtained. Preferably, the nucleating agent is 0.05 to 1 part by weight. More preferably, the nucleating agent is 0.05 to 0.2 parts by weight.

The lubricant (C) is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the resin component having the above constitution. If the lubricant content is less than 0.01 parts by weight, the improvement in rigidity is insufficient,
On the other hand, even if the amount exceeds 1 part by weight, further improvement of the effect cannot be obtained. Preferably, the lubricant is 0.1-0.4 parts 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 nucleating agent and the lubricant 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 an ordinary single-screw extruder, twin-screw extruder, It is melt-kneaded in a temperature range of 170 to 300 ° C. with a Brabender or a roll.

(1) Production of Homopolypropylene Portion The homopolypropylene portion is not particularly limited in its production method as long as it satisfies the above physical properties, but it 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 ⁶ R ⁷ . R ⁶ and R ⁷ represent the same or different hydrocarbon groups, OR ⁸ groups (R ⁸ is a hydrocarbon group) or halogen atoms. More specifically, the hydrocarbon group for R ⁶ and R ⁷ has 1 carbon atom.
~ 20 alkyl groups, cycloalkyl groups, aryl groups,
Examples of the aralkyl group include an OR ⁸ group, and R ⁸ includes an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. 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,
Magnesium metal, halogenated hydrocarbon and general formula: X ¹ _n M ² (OR ⁹ ) _m-n (In the formula, X ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M ² is a boron, carbon, aluminum, silicon or phosphorus atom, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M ² , and m> n ≧ 0.) The method of contacting the alkoxy group-containing compound of 1 is mentioned.

X ^{1 in} the general formula of the alkoxy group-containing compound
Examples of the hydrocarbon group for R ⁹ and R ⁹ 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 and C (OP) when M ² 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 2} 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 ² is boron, B (OEt) ₃ ,
B (OBu) ₃ , B (OHe) ₃ , B (OPh) _{3 and the} like are included, and when M ² is aluminum, Al
(OMe) ₃ , Al (OEt) ₃ , Al (OHe) ₃ ,
Al (OPh) _{3 and the} like. Further, when M ² is phosphorus, P (OMe) ₃ , P (OEt) ₃ , P (OH
e) ₃ , P (OPh) _{3 and the} like.

As the magnesium compound, a metal (M ') of Group II or IIIa of the periodic table represented by the general formula: MgR ⁶ R ⁷ · p (M'R ¹⁰ _q )
Complexes with organic compounds of the formula (1) can also be used. The metal M ′ is aluminum, zinc, calcium or the like, and R ¹⁰ has 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 ¹⁰ _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 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 carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, malonic acid, succinic acid, adipic acid, 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, 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, Triemellitate 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 ¹¹ OH. In the general formula, R ¹¹ 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 ¹² OR ¹³ . In the general formula, R ¹² and R ¹³ are alkyl groups having 1 to 12 carbon atoms, alkenyl groups, cycloalkyl groups, aryl groups or aralkyl groups, which may be the same or 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 1 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 halogenated silicon 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) Magnesium compound, (b) Titanium compound, (c) Electron-donating compound, and optionally (d) 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
^A magnesium-containing solid obtained by contacting a compound of ² (OR ⁹ ) _mn (which may be the same as the above-mentioned alkoxy group-containing compound) is contacted with a halogen-containing alcohol, and then with an electron-donating compound and a titanium compound. In the method (JP-A-63-264607), a magnesium dialkoxide and a silicon halide compound having a hydrogen-silicon bond are brought into contact with each other, then a titanium halide compound is brought into contact therewith, and then with an electron donating compound (if necessary). According to the method (contact with a titanium halide compound) (JP-A-62-146904), a magnesium dialkoxide is contacted with a silicon halide compound having a hydrogen-silicon bond, and then with an electron-donating compound. And then contacting with a titanium compound (JP-A-58-198503). ) Can be prepared by, etc., but in particular the process 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 ¹⁴ _r AlX ² _3-r (wherein R ¹⁴ 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 to each other via an oxygen atom or a nitrogen atom. Such compounds include, for example,

Embedded image Etc. can be exemplified.

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

Embedded image (However, R ¹⁵ is a cyclic substituent having an ether bond or a thioether bond in the ring, an oxy group having an cyclic ether bond-containing cyclic substituent, an cyclic 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 ¹⁸ O—,
R ¹⁹ ₃ Si- or R ²⁰ ₃ SiO- (provided that R ¹⁸
Is a hydrocarbon group having 3 to 10 carbon atoms, R ¹⁹ and R ²⁰
Are each a hydrocarbon group having 1 to 10 carbon atoms and may be the same or different. ), R ¹⁵ 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 ¹⁵ include the following (each R ¹⁵ group is represented by RA, RB, etc.).

Embedded image

R ¹⁶ in the above general formula of the component (C),
Examples of the hydrocarbon group in R ¹⁸ , R ¹⁹ and R ²⁰ 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 ¹⁵ 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 organosilicon 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.

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 solid component (component (A)) is brought into contact with the olefin in the presence of the organoaluminum compound (component (B)) and the organosilicon compound (component (C)) to give the olefin. 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 system may be either a batch system or a continuous system, or may be performed in two or more stages. 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 organic metal 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) used when 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 a gas phase or a liquid phase. When the polymerization is carried out in a 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. Even if it is prepared separately from the homopolypropylene part, it is continuously prepared after the homopolypropylene part is prepared. May be.

(3) Preparation of Polypropylene Resin Composition When the homopolypropylene portion and the copolymerization portion are prepared separately, they can be used as the resin component by the mechanical blending method, or can be 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 above resin components are mixed with a nucleating agent and a lubricant using a Henschel mixer, a super mixer, a ribbon blender, a Banbury mixer, etc., and the mixture is mixed with a conventional single screw extruder, twin screw extruder, Brabender or roll to 170 ~
A polypropylene resin composition can be obtained by melt-kneading in a temperature range of 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.

[0069]

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.

(I) Is the resin component a homopolypropylene part?
A 1 liter reaction vessel equipped with a prepared reflux condenser Ranaru when Example 1 (1) generation component of the homopolypropylene part (A), under a nitrogen gas atmosphere, chip-like 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 metal 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 TEAL n-heptane solution (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 prepolymerized catalyst into the reaction system, 7.5 liters of hydrogen gas (same as at room temperature and normal pressure) and 3 liters of liquid propylene as a molecular weight controlling agent were injected under pressure, and then the reaction system was charged. The temperature was raised to 70 ° C., 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.

A small amount of polymer was collected 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 20 g / 10 minutes and the ΔH _m was 28 ca.
1 / g. This ΔH _m is (24.50 + 1.5
83 log MFR) calculated value ΔH _m '(2
It was larger than 6.5).

(2) Preparation of polypropylene resin composition 0.05 part as a nucleating agent is added to 100 parts by weight of the resin component.
Parts by weight of sodium-2,2'-methylenebis (4,6
-Di-t-butylphenyl) phosphate (trade name "NA-11UF", manufactured by Asahi Denka Co., Ltd.), 0.2 parts by weight of oleic acid amide (Shin Nippon Rika Co., Ltd.) as a lubricant.
50m after adding) and mixing with a super mixer
8 at 210 ° C with mφ single screw extruder (L / D = 28)
Melt-kneading was performed at a screw rotation speed of 0 rpm to obtain polypropylene resin composition pellets. 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. Table 2 shows the measurement results. Flexural modulus (kgf / cm ² ): Measured at 23 ° C. using a test piece of 110 mm × 10 mm × 4 mm according to JIS K7203. Izod impact strength (kgf · cm / cm ² ): JI
Measurement was carried out at 23 ° C. by using a notched test piece of 80 mm × 10 mm × 4 mm according to SK7110. 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 4.6 kgf / cm < ² > load.

Examples 2 to 8 and Comparative Examples 1 to 11 In the homopolypropylene portion prepared under the conditions shown in Table 1,
A nucleating agent and a lubricant were added under the conditions shown in Table 1 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.

Table 1 Examples Item 1 2 3 4 5 6 Polymerization conditions Homogeneous polypropylene part hydrogen gas amount (L) 7.5 7.5 7.5 7.5 4.0 1.8 Composition and physical properties Homopolypropylene part MFR (g / 10 min) 20 20 20 20 20 3 ΔH _m ⁽¹⁾ 28 28 28 28 23 26 ΔH _m ' ⁽²⁾ 26.5 26.5 26.5 26.5 26.5 25.2 Additive ⁽³⁾ NA-11UF ⁽⁴⁾ 0.05 0.2 0.2 0.2 0.2 0.2 Sodium benzoate ⁽⁵⁾ Gelol MD ⁽⁶⁾ Shell nucleating agent ⁽⁷⁾ OA ⁽⁸⁾ 0.2 0.2 0.2 0.2 EA ⁽⁹⁾ 0.2 MSA ⁽¹⁰⁾ 0.1 Composition MFR (g / 10 min) 20 20 20 20 20 3.0 Note (1) Measured value (cal / g). (2) Calculated value of heat of fusion (cal / g). (3) Unit: parts by weight (resin component is 100 parts by weight). (4) Nucleating agent: sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate (manufactured by Asahi Denka Co., Ltd.). (5) Nucleating agent: sodium benzoate (Fushimi Pharmaceutical Co., Ltd.). (6) Nucleating agent: 1,3,2,4-di (p-methylbenzylidene) sorbitol (manufactured by Mitsui Toatsu Chemicals, Inc.). (7) Nucleating agent: pt-butyl benzoic acid aluminum salt (manufactured by Dainippon Ink and Chemicals, Inc.). (8) Lubricant: oleic acid amide (manufactured by Shin Nippon Rika Co., Ltd.). (9) Lubricant: erucic acid amide (manufactured by Lion Corporation). (10) Lubricant: N-methylol stearic acid amide (manufactured by NOF CORPORATION).

[0083]

Table 1 (continued) Comparative Example Item 1 2 3 4 5 6 Polymerization conditions Amount of hydrogen gas produced in homopolypropylene part (L) 7.5 7.5 1.8 12.6 4.0 7.5 Composition and physical properties Homopolypropylene part MFR (g / 10 min) 20 20 3 40 20 20 ΔH _m ⁽¹⁾ 28 28 26 29 23 28 ΔH _m ' ⁽²⁾ 26.5 26.5 25.2 27.0 26.5 26.5 Additive ⁽³⁾ NA-11UF ⁽⁴⁾ 0.05 0.2 0.2 0.2 0.2 Sodium benzoate ⁽⁵⁾ 0.2 Gelol MD ⁽⁶⁾ Shell nucleating agent ⁽⁷⁾ OA ⁽⁸⁾ EA ⁽⁹⁾ MSA ⁽¹⁰⁾ Whole composition MFR (g / 10 min) 20 20 3.0 40 20 20 Note (1) to (10) Same as above.

Table 1 (continued) Comparative Example Item 7 8 9 10 11 Polymerization conditions Amount of hydrogen gas produced in homopolypropylene part (L) 7.5 7.5 7.5 7.5 7.5 Composition and properties Homopolypropylene part MFR (g / 10 min) 20 20 20 20 20 ΔH _m ⁽¹⁾ 28 28 28 28 28 ΔH _m ' ⁽²⁾ 26.5 26.5 26.5 26.5 26.5 Additive ⁽³⁾ NA-11UF ⁽⁴⁾ Sodium benzoate ⁽⁵⁾ Gelol MD ⁽⁶⁾ 0.2 Shell nucleating agent ^{( 7)} 0.2 OA ⁽⁸⁾ 0.1 0.2 0.4 0.2 0.2 EA ⁽⁹⁾ MSA ⁽¹⁰⁾ Whole composition MFR (g / 10 min) 20 20 20 20 20 Note (1) to (10) Same as above.

Table 2 Examples Mechanical properties 1 2 3 4 5 6 Flexural modulus (kgf / cm ² ) 23,000 23,300 22,800 23,300 21,200 23,200 Izod impact strength ⁽¹⁾ 2.0 2.0 2.0 2.0 2.1 2.1 HDT (° C) 139 140 139 141 132 136 Note (1) Unit: kgf ・ cm / cm ²

[0087]

Table 2 (continued) Comparative Example Mechanical Properties 1 2 3 4 5 6 Flexural Modulus (kgf / cm ² ) 21,800 22,000 21,800 22,300 20,000 22,000 Izod Impact Strength ⁽¹⁾ 2.0 2.0 2.1 1.9 2.0 2.0 HDT (° C) 135 137 135 135 137 132 137 Note (1) Same as above.

Table 2 (continued) Comparative Example Mechanical Properties 7 8 9 10 11 Flexural Modulus (kgf / cm ² ) 17,500 18,000 18,500 21,000 21,000 Izod Impact Strength ⁽¹⁾ 2.3 2.3 2.1 1.9 2.0 HDT (° C) 119 119 120 135 134 Note (1) Same as above.

(Ii) The resin component is a homopolypropylene part
And a propylene-ethylene copolymerized portion Example 1 (1) Production of homopolypropylene portion A homopolypropylene portion was prepared in the same manner as in Example 1 of (i) except for the conditions shown in Table 3. A small amount of the polymer was sampled from the container in which the propylene polymerization was performed, and the MFR and the heat of fusion ΔH _m were measured. As a result, the MFR of the homopolypropylene portion was 170 g / 10 minutes and the ΔH _m was 2
It was 8.43 cal / g. This ΔH _m is (24.
50 + 1.583 log MFR), which was larger than the calculated value ΔH _m ′ (28.03).

(2) Production of Propylene-Ethylene Copolymerization Portion and Resin Component After introducing 0.2 liters of hydrogen gas into the container, 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.

0.2 parts by weight of NA-11UF as a nucleating agent and 0.2 as a lubricant with respect to 100 parts by weight of the resin component.
After adding oleic acid amide by weight and mixing with a super mixer, a 50 mmφ single screw extruder (L / D = 2
In 8), the mixture was melt-kneaded at 210 ° C. at a screw rotation speed of 80 rpm to obtain polypropylene resin composition pellets. Table 3 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. Regarding each test piece (i) Example 1
Similar mechanical properties were measured. Table 4 shows the measurement results.

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 3, and the resin component thus obtained was treated with a nucleating agent or A lubricant 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 3 and 4.

Example 11 A homopolypropylene portion prepared under the conditions shown in Table 3,
A propylene-ethylene copolymerization portion separately prepared under the conditions shown in Table 3, a nucleating agent and a lubricant were mechanically blended using a super mixer, and melt-kneaded under the same conditions as in Example 1 to obtain a polypropylene resin composition. I got a thing. The MFR and mechanical properties of the polypropylene resin composition and each component were measured in the same manner as in Example 1. The results are shown in Tables 3 and 4.

Comparative Examples 1-2 The amounts of nucleating agents or lubricants shown in Table 3 were added to the resin components produced in Example 4 and melt-kneaded under the same conditions as in Example 1 to obtain polypropylene resin compositions, MFR and mechanical properties were measured as in Example 1. Tables 3 and 4 show the results.
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Comparative Examples 3 to 6 The component (A) produced in Example 1 was used as it is as a polymerization catalyst component without prepolymerization, and a resin component was produced under the conditions shown in Table 3 to obtain the resin component. A nucleating agent and / or a lubricant 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 3 and 4.

Table 3Example item 1 2 3 4 5 6 Polymerization conditions Generation of homopolypropylene part Hydrogen gas amount (L) 30 30 30 30 30 30Formation of copolymerized moieties C_Three/ C_Two ⁽¹⁾ 1.03 1.95 0.84 0.84 0.84 0.84 Pressure (kg / cm^TwoG) 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 0.1Composition 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 4Additive ⁽⁶⁾  NA-11UF⁽⁷⁾ 0.2 0.2 0.2 0.2 0.2 0.2 Sodium benzoate⁽⁸⁾ OA⁽⁹⁾ 0.2 0.2 0.2 0.2 0.1 0.4Entire 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 (resin component is 100 parts by weight). (7) Nucleating agent: sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate (manufactured by Asahi Denka Co., Ltd.). (8) Nucleating agent: sodium benzoate (manufactured by Fushimi Pharmaceutical Co., Ltd.). (9) Lubricant: oleic acid amide (manufactured by Shin Nippon Rika Co., Ltd.).

Table 3 (continued) Example item 7 8 9 10 11 Polymerization conditions Homopolypropylene part produced hydrogen gas amount (L) 30 30 30 30 2.7 Copolymerized part produced C ₃ / C ₂ ⁽¹⁾ 0.84 0.84 0.21 0.80 0.84 Pressure (kg / cm ² G) 6 6 6.4 6 6.1 Polymerization time (hr) 1.5 1.5 1 2 1.5 Hydrogen gas amount (L) 0.1 0 2.2 0.2 0.5 Composition and properties Homopolypropylene part content ⁽²⁾ 85 85 85 80 85 MFR (g / 10min) 170 170 170 170 5 ΔH _m ⁽³⁾ 28.43 28.43 28.43 28.43 26 ΔH _m ' ⁽⁴⁾ 28.03 28.03 28.03 28.03 25.61 Content of propylene-ethylene copolymerization part ⁽²⁾ 15 15 15 20 15 Ethylene content ⁽²⁾ 50 50 50 50 50 [η] (dl / g) ⁽⁵⁾ 4 4 6 3 3 Additive ⁽⁶⁾ NA-11UF ⁽⁷⁾ 0.2 0.2 0.2 Sodium benzoate ⁽⁸⁾ 0.2 OA ^{( 9)} 0.2 0.2 0.2 0.2 0.2 Whole composition MFR (g / 10 min) 49.8 49.8 35.3 29.2 3.8 Note (1) to (9) Same as above.

Table 3 (continued) Comparative Example Item 1 2 3 4 5 6 Polymerization conditions Homopolypropylene part produced hydrogen gas amount (L) 30 30 30 30 30 30 Copolymerized part produced C ₃ / C ₂ ⁽¹⁾ 0.84 0.84 0.84 0.84 0.84 0.84 Pressure (kg / cm ² G) 6 6 6 6 6 6 Polymerization time (hr) 1.5 1.5 1.5 1.5 1.5 1.5 Hydrogen gas amount (L) 0.1 0.1 0.1 0.1 0.1 0.1 Composition and physical properties Homopolypropylene content ⁽²⁾ 85 85 85 85 80 85 MFR (g / 10min) 170 170 170 170 170 170 170 ΔH _m ⁽³⁾ 28.43 28.43 27.3 27.3 28.43 28.43 ΔH _m ' ⁽⁴⁾ 28.03 28.03 28.03 28.03 28.03 28.03 Propylene-ethylene copolymerization Partial content ⁽²⁾ 15 15 15 15 20 15 Ethylene content ⁽²⁾ 50 50 50 50 50 50 [η] (dl / g) ⁽⁵⁾ 4 4 4 4 4 4 Additive ⁽⁶⁾ NA-11UF ^{(7 )} 0.2 0.2 0.2 0.2 Sodium benzoate ⁽⁸⁾ OA ⁽⁹⁾ 0.2 0.2 0.2 Whole composition MFR (g / 10 min) 49.8 49.8 49.8 49.8 49.8 49.8 Note (1) to (9) Same as above.

Table 4 Examples Mechanical properties 1 2 3 4 5 6 Flexural modulus (kgf / cm ² ) 18,900 16,200 17,600 17,000 16,800 17,300 Izod impact strength ⁽¹⁾ 5.5 6.5 6.2 7.5 7.5 7.3 HDT (° C) 126 124 120 123 122 123 Note (1) Unit: kgf ・ cm / cm ²

Table 4 (continued) Example Mechanical Properties 7 8 9 10 11 Flexural Modulus (kgf / cm ² ) 16,500 17,200 16,400 15,600 16,400 Izod Impact Strength ⁽¹⁾ 7.6 7.5 8.5 9.5 8.5 HDT (° C) 120 122 121 119 114 Note (1) Same as above.

Table 4 (continued) Comparative Example Mechanical Properties 1 2 3 4 5 6 Flexural Modulus (kgf / cm ² ) 13,500 16,000 13,500 13,800 14,800 13,600 Izod Impact Strength ⁽¹⁾ 7.3 7.5 8 7.8 8.7 7.2 HDT (° C) 107 121 112 115 116 108 Note (1) Same as above.

As is clear from Tables 2 and 4, the polypropylene resin composition of the present invention comprises (i) a resin component consisting of a homopolypropylene portion and (ii) a resin component consisting of a homopolypropylene portion and a propylene-ethylene copolymer. In either case of being composed of parts, the rigidity and heat resistance are excellent. From the comparison between the example and the comparative example, the heat of fusion was [2
It can be seen that the rigidity and heat resistance are poor when a homopolypropylene portion smaller than 4.50 + 1.583 log MFR] is used. Further, H _m ≧ [24.50 + 1.
583 log MFR], even if a homopolypropylene portion satisfying the following conditions is used, if a nucleating agent and a lubricant are not added,
Very good rigidity and heat resistance cannot be obtained.

[0105]

The polypropylene resin composition of the present invention has
A resin component comprising a homopolypropylene portion having a MFR of 0.01 to 1000 g / 10 minutes and having a constant relationship between the heat of fusion (ΔH _m ) determined by differential scanning calorimetry and the MFR, or a homopolypropylene portion thereof. Since a nucleating agent and a lubricant are added to a resin component consisting of a propylene-ethylene copolymerized part having a predetermined property, it has excellent rigidity and heat resistance. Such a polypropylene resin composition can be widely used for applications such as electric parts and automobile parts.

Claims (4)

[Claims] 1. A melt flow rate (MFR) measured according to (A) JIS K7210 is 0.01 to 1000 g.
/ 10 minutes range, and 100 parts by weight of a resin component consisting of a homopolypropylene portion in which the heat of fusion (ΔH _m ) determined by differential scanning calorimetry and MFR satisfy the relational expression ΔH _m ≧ 24.50 + 1.583 log MFR. , (B) The following general formula (I): (However, R ¹ is a direct bond, sulfur or an alkylene group or an alkylidene group having 1 to 9 carbon atoms, R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and M ¹ is 1 to It is a trivalent metal atom, and n is a valence of M ^1. )
A polypropylene resin composition comprising 0.01 to 5 parts by weight of a phosphate compound and / or a metal salt of benzoic acid represented by and 0.01 to 1 part by weight of (C) a fatty acid amide. (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,
Intrinsic viscosity of propylene is 2~6dl / g - a resin component 100 parts by weight of an ethylene copolymer portion 5 to 30% by weight, (B) the following general formula (I) ## STR1 ## (wherein, R ¹ is Direct bond, sulfur or carbon number 1
To 9 are alkylene groups or alkylidene groups, R ² and R ³ are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, M ¹ is a metal atom having a valence of ¹ to 3, and n is a valence of M ¹ . Is a number. ) A polypropylene resin composition comprising 0.01 to 5 parts by weight of a phosphate compound and / or a metal benzoate represented by the formula (1) and 0.01 to 1 part by weight of (C) a fatty acid amide. 3. The polypropylene resin composition according to claim 1, wherein the metal salt of benzoic acid is an alkali metal salt of benzoic acid. 4. The fatty acid amide is represented by the following general formula (II): (However, R ⁴ is an alkyl group or an alkenyl group having 7 to 21 carbon atoms, R ⁵ is a hydrogen atom or an alkyl group or alkenyl group having 1 to 21 carbon atoms, and both are alkyl groups or alkenyl groups. May have an -OH group).
The polypropylene resin composition according to any one of 1.