JPH10231395A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition that is excellent in balance between its impact resistance and its stiffness as well as excellent in economy. SOLUTION: This polypropylene resin composition comprises (I) 50-95wt.% of a polyprolylene with an intrinsic viscosity ([η]) of 0.5-5.0dl/g in tetralin at 135 deg.C, and (II) 5-50wt.% of a polylefin resin component that has the main chain of methylene and methine chains including a plurality of alkane side chains different in chain length in the same polymer chains, has 20-200 methyl carbon number per 100 carbon atoms (CH3 /1,000C), satisfying the following formula in relating to its density: D (density)<0.96- 0.0156μLn(CH3 /1,000 C)+0.00016×(CH3 /1,000C) and has an intrinsic viscosity ([η]) of 0.5-5.0dl/g in tetralin at 135 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polypropylene resin composition which is excellent in balance between impact resistance and rigidity and is economically excellent.

[0002]

2. Description of the Related Art Polypropylene is widely used because of its excellent physical properties. For example, since it is excellent in rigidity, heat resistance, glossiness, and moldability and is inexpensive, it has recently been widely used especially for interior and exterior parts of automobiles and electric equipment parts. However, since polypropylene has crystallinity, it is insufficient in terms of impact resistance, and there is a problem that its use is limited. As a method of maintaining high rigidity while improving the impact resistance of such polypropylene, ethylene-propylene copolymer rubber (EP)
R), a rubber material having a high randomness and a narrow composition distribution such as ethylene-butene copolymer rubber (EBR), ethylene-propylene-diene copolymer rubber (EPDM) has been blended. . These rubbery substances are usually synthesized with a vanadium-based catalyst.
An improvement by blending an ethylene-higher α-olefin copolymer rubber (α-olefin having 4 to 8 carbon atoms) with a homogeneous catalyst typified by a metallocene catalyst is also disclosed (Japanese Patent Application Laid-Open No. Hei 6-1994). 192500, JP-A-6-192506, JP-A-6-248156
JP-A-7-102126). However, in order to synthesize such a rubber-like copolymer, it is necessary to perform copolymerization of ethylene and an α-olefin, and some rubber-like copolymers are expensive.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to provide a polypropylene resin composition which has not been achieved by the prior art and which has a good balance between impact resistance and rigidity and is economically excellent. To provide.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, completed the present invention. That is, the present invention is as follows. [1] 50-95 wt% of the following component (I) and (I)
I) A polypropylene-based resin composition comprising 5 to 50 wt%. (I) a polypropylene component having an intrinsic viscosity ([η]) of 0.5 to 5.0 dl / g measured at 135 ° C. in tetralin (II) a main chain composed of methylene and methine chains and having different chain lengths In the same polymer chain, and the number of methyl carbons per 1000 carbon atoms (C
H ₃ / 1000C) is 20 to 200 pieces, the relationship between the density satisfy the following formula, in tetralin, an intrinsic viscosity measured at 135 ℃ ([η]) is 0.5~5.0dl / g
Polyolefin resin component of the general formula: Density <0.96--0.0156 × Ln (CH ₃ /1000C)+0.000
16 × (CH ₃ / 1000C)｝ (where Ln represents a natural logarithm.) [2] The polyolefin resin component of the component (II) is
The orenfin monomer is represented by (A) MR ¹ _a R ² _b R ³ _c R ⁴ _d (M: transition metal atom of Groups IV to X of the periodic table, R ¹ _a , R ² _b , R ³ _c , R ⁴ _d :
Each independently represents a σ-binding ligand, a chelating ligand or a neutral Lewis base ligand. An essential component is a combination of a) a transition metal compound, and (B) a compound which reacts with the aluminoxane (b) transition metal compound to become a stable anion, and (c) an organoaluminum compound. The polypropylene-based resin composition according to the above [1], which is polymerized using a catalyst system contained as a component. [3] The polypropylene resin composition according to the above [1], wherein the orene fin monomer used for synthesizing the polyolefin resin component is essentially ethylene alone.

Hereinafter, the present invention will be described in detail. The polypropylene resin composition of the present invention comprises a polypropylene component (I) and a polyolefin resin component (II) having a specific structure. The polypropylene component (I) has an intrinsic viscosity ([η]) measured in tetralin at 135 ° C. in the range of 0.5 to 5.0 dl / g, preferably in the range of 0.5 to 3.0 dl / g. And
More preferably, it is in the range of 0.8 to 2.0 dl / g, and can be arbitrarily changed within the above range according to the intended use.

As the polypropylene component (I), a propylene homopolymer, a copolymer containing propylene units as a main component, for example, a propylene / ethylene random copolymer obtained by random copolymerization of propylene and ethylene , Propylene / α-olefin obtained by random copolymerization of propylene and α-olefin, preferably α-olefin having 4 to 18 carbon atoms, particularly preferably 1-butene, 1-hexene, 1-octene.
Olefin random copolymer, propylene, ethylene and α-olefin, preferably α-olefin having 4 to 18 carbon atoms, particularly preferably 1-butene, 1-hexene,
Octene, and a propylene / ethylene / α-olefin terpolymer obtained by random copolymerization with propylene, a propylene homopolymer, propylene, and ethylene or an α-olefin, preferably ethylene or a compound having 4 carbon atoms. To 18 α-olefins, particularly preferably ethylene or 1-butene, 1-hexene, 1-octene,
And a propylene / ethylene random copolymer or propylene / α- obtained by random copolymerization of
A block copolymer composed of an olefin random copolymer and a propylene / ethylene or propylene / α-olefin block copolymer obtained by copolymerization in at least two steps. The production method is not particularly limited, but generally has a Ziegler-Natta type catalyst comprising a combination of a titanium-containing solid transition metal component and an organometallic compound component, or a cyclopentadienyl ring. A metallocene catalyst comprising a combination of a transition metal compound of Group IV of the periodic table with an aluminoxane, a compound which becomes a stable anion by reacting with the transition metal compound, and at least one selected from the group consisting of organoaluminum compounds; It can be produced using a stereoregular catalyst. In particular, as a Ziegler-Natta type catalyst, titanium trichloride or titanium, magnesium and halogen as essential catalyst components,
Examples of the catalyst component include a transition metal component having an electron donor as an optional component and an organoaluminum compound as an organic metal component. Further, as the metallocene catalyst, at least two selected from the group consisting of a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group and a partially hydride thereof are used.
Condensation of one type of trialkylaluminum with titanium as a transition metal compound using titanium, zirconium and hafnium as a transition metal compound. And those obtained by condensation of two or more trialkylaluminum compounds with water, boron-containing compounds, aluminate-containing compounds, and organoaluminum compounds as compounds that react with transition metal compounds to form stable anions. One Al-C in
Examples of the compound having a bond include a trialkylaluminum compound, a dialkylaluminum compound, and a monoalkylaluminum compound having at least one Al-halogen or Al-hydrogen bond in a molecule. As the manufacturing process, either a continuous type or a batch type can be used. In addition, slurry polymerization using an inert hydrocarbon solvent such as propane, pentane, hexane, heptane, and octane, solvent polymerization, liquid phase polymerization using no solvent, gas phase polymerization, and the like, or a polymerization method in which these are combined can be used.

The polyolefin resin component (II) has a specific structure in which the main chain is composed of a methylene and methine chain, and has a plurality of alkane side chains having different chain lengths in the same polymer chain. The chain length of the alkane side chain is not particularly limited, but it is important to have a plurality (two or more kinds) of linear alkane side chains having different chain lengths in the same polymer chain. With one type (below), the effect of improving impact resistance is reduced. The polyolefin resin component (II) has 20 to 200 methyl carbon atoms per 1000 carbon atoms. Preferably 50 to 150
And can be arbitrarily changed within the above range according to the intended use. If the number of methyl carbon atoms per 1000 carbon atoms is less than 20, the effect of improving impact resistance is low. On the other hand, when the number exceeds 200, the rigidity is remarkably reduced, or the effect of improving impact resistance is low and the balance of physical properties is insufficient. Furthermore, the polyolefin-based resin component of the present invention has a methyl carbon number (CH ₃
/ 1000C) and the density satisfy the following general formula. General formula: Density <0.96--0.0156 × Ln (CH ₃ /1000C)+0.000
16 × (CH ₃ / 1000C)｝ (wherein, Ln represents a natural logarithm.) If the density does not satisfy the above general formula, the effect of improving impact resistance is low, which is not preferable. For example, low-density polyethylene (LDP) produced by a high-pressure radical polymerization method is generally used.
E), a linear low-density polyethylene (LL) produced using a Ziegler-Natta type catalyst comprising a combination of a titanium-containing solid transition metal component and an organometallic compound component.
DPE) does not often satisfy the above general formula. The polyolefin-based resin component (II) is
Intrinsic viscosity ([η]) measured at 5 ° C. is 0.5 to 5.0 d
1 / g, preferably 0.5-3.0 dl /
g, and can be arbitrarily changed within the above range according to the intended use. However, when [η] is less than 0.5 dl / g and not less than 5.0 dl / g, moldability deteriorates, which is not preferable.

The polyolefin resin component (II) used in the present invention is essentially a homopolymer of ethylene, that is, a homopolymer of ethylene or a small amount of an α-olefin such as propylene or butene-1 in ethylene. Copolymers copolymerized within a range that does not impair the object of the invention are mentioned. Polyolefin resin component (II)
Represents an olefin monomer represented by (A) MR ¹ _a R ² _b R ³ _c R ⁴ _d (M: transition metal atom of Groups IV to X of the periodic table, R ¹ _a , R ² _b , R ³ _c , R ⁴ _d :
Each independently represents a ligand such as a σ-binding ligand, a chelating ligand or a neutral Lewis base ligand. An essential component is a combination of a) a transition metal compound, and (B) a compound which reacts with the aluminoxane (b) transition metal compound to become a stable anion, and (c) an organoaluminum compound. It is obtained by polymerizing using a catalyst system containing As the monomer, ethylene alone or a mixture of ethylene and a small amount of an α-olefin such as propylene or butene-1 is used. General formula MR ¹ _a R ² _b R ³ _c , which is used as a polymerization catalyst component for olefin monomers in the production of polyolefin resin component (II)
R ⁴ d (M: transition metal atom of Periodic Tables IV to X, R ¹ _a ,
R ² _b , R ³ _c , and R ⁴ d: each independently a ligand such as a σ-binding ligand, a chelating ligand, or a neutral Lewis base ligand)
Transition metal atom (M) of the transition metal compound (A) represented by
As the metal, nickel, palladium and platinum belonging to Group X of the periodic table are preferably used. For example, nickel chloride,
Disperse an inorganic acid salt of nickel such as nickel sulfate or nickel perchlorate, an organic acid salt of nickel such as nickel acetate or nickel oxalate, an amine compound, an imine compound, an alkoxy compound or a carbonyl compound such as nickel acetylacetonate or nickel phthalocyanine. Nickel complex as a ligand, palladium chloride, palladium bromide, palladium iodide, palladium sulfate, palladium inorganic acid salts such as palladium nitrate, palladium acetate, palladium trifluoroacetate, palladium organic acid salts such as palladium cyanide,
Palladium acetylacetonate, bis (allyl) palladium, dichloro (1,5-cyclooctadiene) palladium, dichlorobis (acetonitrile) palladium,
Dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, diacetbis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ) Ethane] palladium, bis [1,2-bis (diphenylphosphino)
[Ethane] palladium, tetraamine palladium nitrate, tetrakis (acetonitrile) palladium tetrafluoroborate, and the like; palladium complexes having an amine compound, an imine compound, an alkoxy compound, or a carbonyl compound as ligands; platinum such as platinum chloride and platinum iodide; Examples thereof include inorganic acid salts, platinum complexes such as platinum acetylacetonate, and the like, and substituted products thereof. Among these, nickel and palladium complexes having a diimine compound as a ligand can be particularly preferably used. To give a concrete example, L.
K. Johnson, CM Killian, M. Brookhart, J. Am. Ch
em. Soc. 117 , 6414 (1995), LK Johnson, S. Mec
king, M. Brookhart, J. Am. Chem. Soc. 118 , 267 (19
96) (ArN = C (CH ₃ ) -C (CH ₃ ) = NAr) PdCH ₃ Cl, (ArN = C (H)
-C (H) = NAr) PdCH ₃ Cl, (ArN = C (CH ₃ ) -C (CH ₃ ) = NAr) Pd (C
H ₃ ) ₂ , (ArN = C (H) -C (H) = NAr) Pd (CH ₃ ) ₂ , (ArN = C (H) -C (H) =
_{NAr) Ni (CH 3) 2} , (ArN = C (CH 3) -C (CH 3) = NAr) Ni (CH 3) 2, [Ar
N = C (CH ₃ ) -C (CH ₃ ) = NAr) Pd (CH ₃ ) (O (C ₂ H ₅ ) ₂ )] + BAF ⁻ , [ArN =
C (H) -C (H) = NAr) Pd (CH 3) (O (C 2 H 5) 2)] + BAF -, [ArN = C (CH 3)
_{-C (CH 3) = NAr)} Ni (CH 3) (O (C 2 H 5) 2)] + BAF -, [ArN = C (H) -C
(H) = NAr) Ni (CH ₃ ) (O (C ₂ H ₅ ) ₂ )] ⁺ BAF ⁻ , (ArN = C (H) -C (H) = NA
_{r) NiBr 2, (ArN =} C (CH 3) -C (CH 3) = NAr) NiBr 2, (ArN = C (An) -
C (An) = NAr) NiBr ₂ (or more, Ar = 2,6-C ₆ H ₃ (iC ₃ H ₇ ) ₂ , BAF
_{= B (3,5-C 6 H} 3 (CF 3) 2) 4 -, An = Acenaphtenequinon
e), (ArN = C ( H) -C (H) = NAr) NiBr 2, (ArN = C (CH 3) -C (CH 3) =
Nickel and palladium compounds such as NAr) NiBr ₂ (above, Ar = 2,6-C ₆ H ₃ (CH ₃ ) ₂ ).

As the aluminoxane (B) (a), those obtained by condensing one kind of trialkylaluminum with water and those obtained by condensing two or more kinds of trialkylaluminum with water are used. Can be Specific examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Particularly, methylaluminoxane and methylisobutylaluminoxane are preferably used. The amount of aluminoxane to be used can be selected from a wide range such as 1 to 10000 mol per mol of transition metal atom. Preferably, the transition metal atom 1
The range is from 100 to 3000 moles per mole. Also,
Examples of the compound (B) (b) which becomes a stable anion by reacting with a transition metal compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N
Compounds containing tetrakis (pentafluorophenyl) borate or tetrakis (pentafluorophenyl) aluminate, such as dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (pentafluorophenyl) aluminate, and tris (pentafluorophenyl) aluminate; (Fluorophenyl) borane is preferably used. The organoaluminum compound (B) (c) used in the present invention has at least one Al-C bond in the molecule. Specific examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum,
Triisopropyl aluminum, tripentyl aluminum, trinormal hexyl aluminum, tri (2-
Methylpentyl) aluminum, trinormal octyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isobutyl aluminum sesquichloride, dimethyl aluminum chloride, diethyl aluminum chloride, dinormal propyl aluminum chloride, dinormal butyl Aluminum chloride, diisobutyl aluminum chloride, di-t-butyl aluminum chloride, diisopropyl aluminum chloride, dipentyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, t-butyl aluminum dichloride Id, isopropyl aluminum dichloride, pentyl aluminum dichloride, and the like. Of these organoaluminum compounds,
Organoaluminum is preferred. As the organic aluminum, triethyl aluminum and triisobutyl aluminum are more preferably used. The amount of the organoaluminum compound used is determined by the amount of the transition metal atom 1 in the transition metal compound (A).
It can be selected from a wide range, such as from 1 to 10,000 moles per mole. Preferably, one mole per mole of transition metal atom
１０００1000 mol.

As a method of supplying each of the catalyst components to the polymerization tank, for example, the catalyst components are supplied in an inert gas such as nitrogen, argon or the like in the absence of moisture in the presence of a monomer. The catalyst components (A) and (B) may be supplied individually or may be supplied in contact with each other in advance. The polymerization temperature is usually -30 to 300
C., but preferably from 0 to 280.degree. C., more preferably from 20 to 250.degree.
The polymerization pressure is not particularly limited, but is preferably about normal pressure to about 150 atm from the viewpoint of industrial and economical use. The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can range from 5 minutes to 40 hours.
In order to adjust the molecular weight of the polyolefin resin component (II) to be obtained, a chain transfer agent such as hydrogen may be added to the polymerization system. The polymerization process can be either continuous or batch. Slurry polymerization with an inert hydrocarbon solvent such as propane, pentane, hexane, heptane, and octane, solvent polymerization, liquid phase polymerization without solvent, or gas phase polymerization can also be performed.

In the polypropylene resin composition of the present invention, the content of the polypropylene component (I) is from 50 to 95.
wt%, the content of the polyolefin resin component (II) is 5 to 50 wt%, and can be arbitrarily changed according to the intended use. Polypropylene component (I) is 50
If the amount is less than wt%, the rigidity is significantly reduced, and
If the content exceeds wt%, the effect of improving impact resistance is low, which is not preferable.

The polypropylene-based resin composition of the present invention generally contains a heat stabilizer, an antioxidant, a weather-resistant stabilizer, and a mold release as long as the object of the present invention is not impaired in order to maintain processing stability. Various additives such as an agent, a lubricant, a colorant, and an antistatic agent may be added. Also, if necessary, a clarifying agent,
A nucleating agent or an inorganic filler such as calcium carbonate, talc, mica, and silica may be added. Further, the polypropylene-based resin composition of the present invention includes other polypropylene-based resins, various olefin-based resins such as polyethylene and polybutene, acrylonitrile-butadiene-styrene copolymer resin, styrene / ethylene-butene / styrene block copolymer. It is also possible to blend resins and rubbers such as styrene rubber.

[0013] The above-mentioned additives are added to the polypropylene resin composition of the present invention, and if necessary, blended with a filler, various resins and rubbers, and the mixture is extruded using an extruder, a Banbury mixer, a kneader blender or the like. Melt kneading to form a pellet, various molding methods, for example, injection molding, extrusion molding, various molded products by blow molding, sheet, film,
It can be formed into a bottle or the like. The polypropylene resin composition of the present invention has excellent mechanical properties such as rigidity and impact resistance, and can be used for a wide range of applications.
For example, it can be used for applications such as electric equipment parts, automobile interior and exterior parts, and detergent containers.

[0014]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples. In addition, the measurement value of each item in an Example was measured by the following method. (1) Measurement of side chain length and methyl carbon number of polyolefin resin component James. C. Randall, J. Macromol. Sci., Rev. Macromol. Chem.
¹³ described in Phs., C29 (2ε3), 29, 201-317 (1989)
Determined by C-nuclear magnetic resonance spectroscopy. The ¹³ C-NMR measurement of the polymer was performed by dissolving a solution of about 150 mg of the polymer in 3 ml of orthodichlorobenzene in a 10 mmφ sample tube at a measurement temperature of 135 ° C., a measurement frequency of 67.8 MHz, and a spectral width of The measurement was performed under the conditions of 3000 Hz, a filter width of 10000 Hz, a pulse repetition time of 10 seconds, a pulse width of 45 °, and an integration number of 5000 to 7000 times. ¹³ C-NMR of linear alkane side chain for reference
This shows the chemical shift value of the spectrum. ・ L = 0 1B ₁ Actual value (ppm) 19.95 -21.94 Calculated value (ppm) 19.63 ・ L = 1 1B ₂ 2B ₂ Actual value (ppm) 10.8 26.8 -11.3 〜27.7 Calculated value (ppm) 11.36 27.16 ・ L = 2 1B ₃ 2B ₃ 3B ₃ Calculated value (ppm) 14.35 20.21 36.91 ・ L = 3 1B ₄ 2B ₄ 3B ₄ 4B ₄ Actual value (ppm) 14.21 23.39 29.18 34.13 〜29.58-35.37 Calculated value (ppm) 13.86 22.90 29.96 34.22 ・ L = 4 1B ₅ 2B ₅ 3B ₅ 4B ₅ 5B ₅ Calculated value (ppm) 13.86 22.65 32.65 27.27 34.17 ・ L = 5 1B ₆ 2B ₆ 3B ₆ 4B ₆ 5B ₆ 6B ₆ Actual value (ppm) 14.17 22.89 32.22 29.98 27.27 34.62 Calculated Value (ppm) 13.86 22.65 32.40 29.96 27.52 34.47

(2) Weight average molecular weight (Mw) and weight average molecular weight / number average molecular weight (Mw / Mn) Measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve was prepared using standard polystyrene. Model Millipore Waters 150CV type Column Shodex M / S 80 Measurement temperature 145 ° C, solvent orthodichlorobenzene, sample concentration 5mg / 8ml In this condition, NSB (National Bureau of Standard)
s) Standard Reference Material 706 (Mw / M
As a result, a molecular weight distribution (Mw / Mn) of 2.1 was obtained.

(3) Intrinsic viscosity ([η]: dl / g) Measured at 135 ° C. in tetralin. (4) Melting point (Tm: ° C) Using a differential scanning calorimeter (manufactured by PerkinElmer, DSC), 10 mg of a specimen was previously measured under a nitrogen atmosphere under a nitrogen atmosphere.
After melting at 5 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 5 ° C./min for crystallization. Thereafter, the temperature was raised at 10 ° C./min, and the temperature of the maximum peak of the obtained melting endothermic curve was defined as the melting point. (4) Density (g / cm ³ ) Press molding and condition adjustment are in accordance with JIS K6758. Physical properties were measured after 48 hours at 23 ° C. after molding.
The measurement is based on JIS K7112. (5) Flexural modulus (Kg / cm ² ) Press molding and condition adjustment are in accordance with JIS K6758. Physical properties were measured after 48 hours at 23 ° C. after molding.
The measurement is based on JIS K7203.

(6) Izod impact (Kg · cm
/ Cm ² ) Press molding and condition adjustment are according to JIS K6758. Physical properties were measured after 48 hours at 23 ° C. after molding.
When the measurement temperature was −20 ° C., the measurement was further performed after −20 ° C. for 2 hours. The test piece with the V notch was measured using an Izod impact tester (manufactured by Toyo Seiki Co., Ltd.). (JIS K7110) (7) Melt index (MI: g / 10 min) It was measured at a measurement load of 2.16 kgf and a measurement temperature of 230 ° C. using a melt indexer manufactured by Techno Seven Co., Ltd.
(JIS K7210)

Synthesis Example 1 Synthesis of acenaphthenequinonediimine In a reaction vessel equipped with a Dean-Stark trap, 9.1 g (50 mmol) of acenaphthenequinone, 26.6 g (150 mmol) of 2,6-diisopropylaniline, and xylene 20
0 ml, BF ₃ · O (C ₂ H ₅ ) ₂ 0.13 ml
After adding (1 mmol), the mixture was refluxed at room temperature under a nitrogen atmosphere for 3 hours. After the reaction, the reaction solution was allowed to cool, the precipitated solid was separated by filtration, washed with xylene, and then recrystallized from xylene to obtain 17.4 g of brown crystals. ¹ H-NM of the crystal
The data of the R spectrum (CDCl ₃ , 250 MHz) is shown below. δ 7.89-6.63 (m, 12H, C 6 H 5), 3.
05-3.01 (P, 4H, CH ( i-C 3 H 7), 1.
24, 1.23, 0.98, 0.96 (q, 24H, C
H ₃ (i-C ₃ H ₇ ) From the results of the above ¹ H-NMR, the obtained yellow crystals were converted into (Ar
N = C (An) -C (An) = NAr) (Ar = 2,6-C ₆ H ₃ (iC ₃ H ₇ ) ₂ ). The isolation yield was 69.4%.

Example 1 (Polymerization of ethylene) A 0.3-liter glass reactor was purged with nitrogen, and 187 ml of purified toluene and Toso-
Akzo's methylaluminoxane (1.71 mmo)
1 / ml toluene solution) was charged. 200 ml of ethylene gas while raising the polymerization temperature to 30 ° C
The solution was fed at a flow rate of / min and saturated to prepare for polymerization. On the other hand, a 100 ml flask equipped with a magnetic stirrer was replaced with nitrogen, and 7 ml of purified toluene was synthesized under a nitrogen atmosphere, and then synthesized in Example 1 (ArN = C (An) -C (An) = N
56 μmol of Ar) and 28 μmol of nickel acetylacetonate manufactured by STREM were added, and mixed by stirring at room temperature for 5 minutes to dissolve. This catalyst solution was charged into a glass reaction vessel, and polymerization was performed at 30 ° C. for 3 hours. During this time, ethylene gas was continuously supplied to the gas phase at a flow rate of 200 ml / min. Thereafter, the polymerization was stopped by adding 15 ml of methanol. Unreacted monomer gas was purged, the contents of the autoclave were taken out, washed with 1 mol / l hydrochloric acid, and then washed with a large amount of water. This was poured into about 4-fold ethanol, and the precipitated polymer was separated by filtration.
Drying was performed at about 4 ° C. for about 4 hours. As a result, 13.3 g of a polyolefin resin was obtained. [Η] of the obtained polymer was 1.54 dl / g, Mw was 123600, and Mw was
/ Mn was 1.9 and the density was 0.842 g / cm ³ . ^The number of methyl carbon atoms per 1000 carbon atoms determined by ¹³ C-NMR was 136. The value on the right side of the above general formula is 0.862. ¹³ C-NMR of the same polymer
The spectrum is shown in FIG.

(Preparation of resin composition and evaluation of physical properties) As a polypropylene component, MI was 38.2 g / 10 min, [η] was 1.54 dl / g, ethylene content was 5.6 wt%, and JI was used.
Flexural modulus by SK7203 is 13200 Kg / c
m ² , the Izod impact according to JIS K7110 is 6.0 at 23 ° C. and 2.7 Kg · cm / cm at −20 ° C.
² propylene / ethylene block copolymer 85wt%
And 15 wt% of the above-mentioned polyolefin resin are dry-blended, and 100 parts by weight of the blended product is Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., 2,6-di-
0.2 parts by weight of t-butyl-p-cresol), Irganox 1010 (manufactured by Ciba Geigy Corporation, tetrakis [methylene-3- (3 ′, 5-di-t-butyl-4-hydroxyphenyl) propione) −g] methane} to 0.0
5 parts by weight and 0.15 parts by weight of calcium stearate were added, and the mixture was melt-kneaded with a small twin-screw kneader Labo Plastomill manufactured by Toyo Seiki Co., Ltd. at 180 ° C. and 100 rpm for 5 minutes, shredded and pelletized. And This is JIS
After press molding and condition adjustment according to K6758, the density was evaluated, the density was 0.892 g / cm ³ , the flexural modulus was 10500 Kg / cm ² , the Izod impact was 17.0 at 23 ° C., and 8.7 Kg · at −20 ° C. cm / cm
^{Was 2} . MI was 30.9 g / 10 minutes.

[0021]

According to the present invention, it is possible to provide a polypropylene-based resin composition which is excellent in balance between impact resistance and rigidity and economically excellent.

[Brief description of the drawings]

FIG. 1 is a ¹³ C-NMR spectrum of a polyolefin resin synthesized in Example 1.

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁶ identifications FI C08L 23:02)

Claims (3)

[Claims] 1. A polypropylene resin composition comprising the following components (I): 50 to 95 wt% and (II): 5 to 50 wt%. (I) a polypropylene component having an intrinsic viscosity ([η]) of 0.5 to 5.0 dl / g measured at 135 ° C. in tetralin (II) a main chain composed of methylene and methine chains and having different chain lengths In the same polymer chain, and the number of methyl carbons per 1000 carbon atoms (C
H ₃ / 1000C) is 20 to 200 pieces, the relationship between the density satisfy the following formula, in tetralin, an intrinsic viscosity measured at 135 ℃ ([η]) is 0.5~5.0dl / g
Polyolefin resin component of the general formula: Density <0.96--0.0156 × Ln (CH ₃ /1000C)+0.0
0016 × (CH ₃ / 1000C)｝ (where Ln represents natural logarithm) 2. The polyolefin resin component of the component (II) is an olefin monomer represented by (A) MR ¹ _a R ² _b R ³ _c R ⁴ _d (M: Group IV to X of the periodic table) Transition metal atoms, R ¹ _a , R ² _b , R ³ _c , and R ⁴ _d :
Each independently represents a σ-binding ligand, a chelating ligand or a neutral Lewis base ligand. An essential component is a combination of a) a transition metal compound, and (B) a compound which reacts with the aluminoxane (b) transition metal compound to become a stable anion, and (c) an organoaluminum compound. The polypropylene resin composition according to claim 1, wherein the composition is polymerized by using a catalyst system containing as a catalyst. 3. The polypropylene resin composition according to claim 2, wherein the olefin monomer used for synthesizing the polyolefin resin component of the component (II) is essentially ethylene alone.