JP5076450B2 - Polypropylene resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a polypropylene resin composition, an inorganic filler-containing polypropylene resin composition, and a molded article comprising the same. More specifically, the present invention relates to a polypropylene resin composition excellent in scratch resistance, stress whitening resistance, and impact resistance, an inorganic filler-containing polypropylene resin composition, and a molded article comprising the same.

  Conventionally, polypropylene resins have been used for automobile materials and the like because they have excellent appearance and high rigidity.

  For example, in JP-A-11-293058, as a thermoplastic resin composition excellent in rigidity, impact resistance and molded appearance, two or more selected from a polypropylene resin, ethylene, propylene, and α-olefin are used. A thermoplastic resin composition comprising an olefin copolymer obtained by copolymerizing olefins having a total number of carbon atoms of 6 or more and an inorganic filler is described.

  Japanese Patent Application Laid-Open No. 2001-192509 includes, as a means for improving flexibility and heat resistance, an amorphous olefin polymer having a strength at tensile cutting of less than 2 MPa, and a crystalline olefin resin. An olefin resin composition having a Shore A hardness of 85 or less is described.

Japanese Patent Laid-Open No. 11-293058 JP 2001-192509 A

However, even in the polypropylene resin composition described in the above-mentioned publication, further improvements have been required for scratch resistance, stress whitening resistance, and impact resistance.
Under such circumstances, an object of the present invention is to provide a polypropylene resin composition excellent in scratch resistance, stress whitening property, and impact resistance, a polypropylene resin composition containing an inorganic filler, and a molded article comprising the same. .

As a result of intensive studies, the present inventor has found that the present invention can solve the above problems, and has completed the present invention.
That is, one aspect of the present invention is
40 to 90% by weight of at least one propylene polymer (A) selected from the group consisting of a propylene homopolymer (A-1) and a propylene-ethylene copolymer (A-2);
5 to 20% by weight of the following propylene-ethylene-α-olefin copolymer (B),
Containing 5 to 40% by weight of the following ethylene-α-olefin copolymer (C),
A polypropylene resin composition having a melt index of 0.5 to 40 g / 10 min at 230 ° C. and a load of 2.16 kg (provided that the total of (A), (B) and (C) is 100% by weight) It is related to.
In the propylene-ethylene-α-olefin copolymer (B), the α-olefin has 4 to 20 carbon atoms, a molecular weight distribution of 1 to 4, and an intrinsic viscosity of 0.5 to 10 dl / g. It is a propylene-ethylene-α-olefin copolymer having a heat of fusion of 30 J / g or less and an ethylene content of 60 mol% or less.
The ethylene-α-olefin copolymer (C) is an ethylene-α-olefin copolymer having an α-olefin having 4 to 20 carbon atoms and a density of 0.850 to 0.880 g / cm ^3. .

Also, one aspect of the present invention is
40 to 90% by weight of at least one propylene polymer (A) selected from the group consisting of a propylene homopolymer (A-1) and a propylene-ethylene copolymer (A-2);
5 to 20% by weight of the following propylene-ethylene-α-olefin copolymer (B),
A polypropylene resin composition containing 5 to 40% by weight of the following ethylene-α-olefin copolymer (C) (provided that the total of (A), (B) and (C) is 100% by weight) And an inorganic filler-containing polypropylene-based resin composition containing an inorganic filler (D),
The inorganic filler (D) is 0.1 to 60 parts by weight with respect to 100 parts by weight of the polypropylene resin composition,
This relates to an inorganic filler-containing polypropylene resin composition having a melt index of 0.5 to 40 g / 10 min at 230 ° C. and a load of 2.16 kg.
In the propylene-ethylene-α-olefin copolymer (B), the α-olefin has 4 to 20 carbon atoms, a molecular weight distribution of 1 to 4, and an intrinsic viscosity of 0.5 to 10 dl / g. It is a propylene-ethylene-α-olefin copolymer having a heat of fusion of 30 J / g or less and an ethylene content of 60 mol% or less.
The ethylene-α-olefin copolymer (C) is an ethylene-α-olefin copolymer having an α-olefin having 4 to 20 carbon atoms and a density of 0.850 to 0.880 g / cm ^3. .

Moreover, one aspect of the present invention relates to an injection-molded article made of the above polypropylene resin composition or an inorganic filler-containing polypropylene resin composition.
Moreover, one aspect of the present invention relates to a foamed molded article made of the above polypropylene resin composition or the inorganic filler-containing polypropylene resin composition.

According to the present invention, it is possible to obtain a polypropylene resin composition, an inorganic filler-containing polyolefin resin composition excellent in scratch resistance, stress whitening resistance, and impact resistance, and a molded article comprising the same.

In the present invention, at least one propylene polymer (A) selected from the group consisting of a propylene homopolymer (A-1) and a propylene-ethylene copolymer (A-2) is used.
Examples of the propylene-ethylene copolymer (A-2) include a propylene-ethylene random copolymer (A-2-1) and a propylene-ethylene block copolymer (A-2-2). The propylene-ethylene block copolymer (A-2-2) is a copolymer composed of a propylene homopolymer component and a propylene-ethylene random copolymer component.

  The propylene polymer (A) is preferably a propylene homopolymer or a propylene-ethylene block copolymer from the viewpoint of rigidity, heat resistance or hardness.

The isotactic pentad fraction measured by ¹³ C-NMR of the propylene homopolymer (A-1) is preferably 0.95 or more, more preferably 0.98 or more.
The isotactic pentad fraction measured by ¹³ C-NMR of the propylene homopolymer component of the propylene-ethylene block copolymer (A-2-2) is preferably 0.95 or more, more preferably 0.8. 98 or more.

The isotactic pentad fraction is defined as A.I. Zambelli et al., Macromolecules, 6, 925 (1973), that is, isotactic linkage with pentad units in a propylene polymer molecular chain measured by ¹³ C-NMR, in other words propylene monomer units. The fraction of propylene monomer units at the center of five consecutive meso-bonded chains (however, the assignment of NMR absorption peaks is determined based on subsequently published Macromolecules, 8, 687 (1975)). . Specifically, the ratio of the mmmm peak area to the absorption peak area of the methyl carbon region measured by ¹³ C-NMR spectrum is the isotactic pentad fraction. NPL reference material CRM No. of NATIONAL PHYSICAL LABORATORY measured by this method. The isotactic pentad fraction of M19-14 Polypropylene PP / MWD / 2 was 0.944.

Intrinsic viscosity ([η] _P ) measured in a tetralin solvent at 135 ° C. of the propylene homopolymer (A-1), 135 ° C. of the propylene homopolymer component of the block copolymer (A-2-2) Intrinsic viscosity ([η] _P ) measured in a tetralin solvent, and the intrinsic viscosity ([η]) measured in a 135 ° C. tetralin solvent of the random copolymer (A-2-1) is usually It is 0.7-5 dl / g, Preferably it is 0.8-4 dl / g.

  In addition, propylene homopolymer (A-1), propylene homopolymer component of block copolymer (A-2-2), and gel permeation chromatography of random copolymer (A-2-1) ( The molecular weight distribution (Q value, Mw / Mn) measured by GPC) is preferably 3 or more and 7 or less.

  The ethylene content contained in the propylene-ethylene random copolymer component of the block copolymer (A-2-2) is 20 to 65% by weight, preferably 25 to 50% by weight (provided that propylene-ethylene is used). The total amount of random copolymer components is 100% by weight).

The intrinsic viscosity ([η] _EP ) measured in a 135 ° C. tetralin solvent of the propylene-ethylene random copolymer component of the block copolymer (A-2-2) is usually 1.5 to 12 dl / g, preferably 2 to 8 dl / g.

  Content of the propylene-ethylene random copolymer component which comprises the said block copolymer (A-2-2) is 10 to 60 weight%, Preferably it is 10 to 40 weight%.

  The melt index (MI) of the propylene homopolymer (A-1) is usually 0.1 to 400 g / 10 minutes, preferably 1 to 300 g / 10 minutes. However, the measurement temperature is 230 ° C. and the load is 2.16 kg.

  The melt index (MI) of the propylene-ethylene copolymer (A-2) is usually 0.1 to 200 g / 10 minutes, preferably 1 to 150 g / 10 minutes. However, the measurement temperature is 230 ° C. and the load is 2.16 kg.

As a manufacturing method of the said propylene polymer (A), the method of manufacturing with a well-known polymerization method using a well-known polymerization catalyst is mentioned, for example.
Examples of the known polymerization catalyst used in the method for producing the propylene polymer (A) include (1) a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, and (2) organoaluminum. And a catalyst system comprising a compound and (3) an electron donor component. Examples of the method for producing this catalyst include the production methods described in JP-A-1-319508, JP-A-7-216017 and JP-A-10-212319.

  Examples of known polymerization methods used in the above production method include a bulk polymerization method, a solution polymerization method, a slurry polymerization method, and a gas phase polymerization method. These polymerization methods may be either batch type or continuous type, and these polymerization methods may be arbitrarily combined.

As a manufacturing method of said propylene-ethylene block copolymer (A-2-2), Preferably, it consists of said solid catalyst component (1), an organoaluminum compound (2), and an electron donor component (3). In the presence of a catalyst system, a polymerization tank comprising at least two tanks is arranged in series to produce a propylene homopolymer component of the propylene-ethylene block copolymer, and then the produced component is transferred to the next polymerization tank. In this polymerization tank, a propylene-ethylene random copolymer component is continuously produced to produce a (propylene)-(propylene-ethylene) block copolymer.
The amount of the solid catalyst component (1), the organoaluminum compound (2) and the electron donor component (3) used in the above production method and the method of supplying each catalyst component to the polymerization tank may be appropriately determined. .

  The polymerization temperature is usually −30 to 300 ° C., preferably 20 to 180 ° C. The polymerization pressure is usually normal pressure to 10 MPa, preferably 0.2 to 5 MPa. For example, hydrogen may be used as the molecular weight modifier.

  In the production of the propylene polymer (A), prepolymerization may be performed by a known method before carrying out the main polymerization. As a known prepolymerization method, for example, a method of supplying a small amount of propylene in the presence of the solid catalyst component (1) and the organoaluminum compound (2) and carrying out in a slurry state using a solvent can be mentioned.

Examples of the α-olefin used in the propylene-ethylene-α-olefin copolymer (B) used in the present invention include α-olefins having 4 to 20 carbon atoms.
Examples of the α-olefin having 4 to 20 carbon atoms include a linear α-olefin and a branched α-olefin, and examples of the linear α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1 -Octadecene, 1-nanodecene, 1-eicosene and the like. Examples of the branched α-olefin include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene and the like.

The propylene content contained in the copolymer (B) is 5 to 99 mol%, preferably 25 to 99 mol%, more preferably 35 to 99 mol%,
The ethylene content is 0 to 60 mol%, preferably 0 to 55 mol%,
The α-olefin content is 1 to 35 mol%, preferably 1 to 20 mol%, more preferably 1 to 10 mol%. (However, the total of the propylene content, ethylene content, and α-olefin content is 100 mol%.)

The copolymer (B) preferably satisfies the relationship of the following formula.
0.1 <[y / (x + y)] ≦ 1.0
More preferably, 0.5 <[y / (x + y)] ≦ 1.0, and still more preferably 0.8 <[y / (x + y)] ≦ 1.0.
In the above formula, x represents the molar content of ethylene in (B), and y represents the total molar content of α-olefins having 4 to 20 carbon atoms in (B).

Examples of the method for producing the copolymer (B) include a method in which a predetermined monomer is polymerized using a metallocene catalyst by a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like.
Examples of the metallocene catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008. JP, JP 61-130314, JP 3-163088, JP 4-268307, JP 9-12790, JP 9-87313, JP 11-80233. And metallocene catalysts described in JP-A-10-508055 and the like.
As a method for producing a copolymer (B) using a metallocene catalyst, a method described in EP-A-1211287 is preferably mentioned.

  The intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. of the copolymer (B) is 0.5 to 10 dl / g, more preferably 0.9 to 5 dl / g, and still more preferably. 1.2 to 3 dl / g.

  The molecular weight distribution of the copolymer (B) is 1 to 4. The molecular weight distribution is the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and is measured by gel permeation chromatography (GPC) using standard polystyrene as the molecular weight standard substance. Is done.

  The heat of fusion of the copolymer (B) is 30 J / g or less, preferably 20 J / g or less, and more preferably 10 J / g or less.

  Examples of the ethylene-α-olefin copolymer (C) used in the present invention include an ethylene-α-olefin random copolymer or a mixture thereof.

The density of the copolymer (C) is 0.850 to 0.890 g / cm ³ , preferably 0.850 to 0.880 g / cm ³ , more preferably 0.855 to 0.875 g / cm ³ . is there.

  The ethylene content contained in the copolymer (C) is 20 to 95% by weight, preferably 30 to 90% by weight, and the α-olefin content is 80 to 5% by weight, preferably 70%. -10% by weight.

  The MI (measurement temperature is 190 ° C., load is 2.16 kg) of the copolymer (C) is 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes.

  Examples of the α-olefin used in the copolymer (C) include α-olefins having 4 to 20 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, Examples include 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicocene. These α-olefins may be used alone or in combination of at least two kinds. The α-olefin is preferably an α-olefin having 4 to 12 carbon atoms such as 1-butene, 1-hexene and 1-octene.

  As a manufacturing method of a copolymer (C), the manufacturing method similar to the method used for manufacture of a copolymer (B) is mentioned. As a catalyst used for manufacture of a copolymer (C), the same metallocene catalyst as the catalyst used for manufacture of a copolymer (B) is mentioned.

  Examples of the inorganic filler (D) include carbon fiber, metal fiber, glass bead, mica, calcium carbonate, potassium titanate whisker, talc, bentonite, smectite, mica, sepiolite, wollastonite, allophane, imogolite, fibrous form. Magnesium oxysulfate barium sulfate, glass flakes and the like can be mentioned, and talc is preferable.

  As an average particle diameter of an inorganic filler (D), it is 0.01-50 micrometers normally, Preferably it is 0.1-30 micrometers, More preferably, it is 0.1-5 micrometers. Here, the average particle size of the inorganic filler (D) was determined from the integral distribution curve of the sieving method measured by suspending in a dispersion medium such as water or alcohol using a centrifugal sedimentation type particle size distribution measuring device. It means a 50% equivalent particle diameter D50.

  The inorganic filler (D) may be used as it is without treatment, in order to improve the interfacial adhesive strength with the polypropylene resin composition, or to improve the dispersibility of the inorganic filler in the polypropylene resin composition. In order to improve, the surface of the inorganic filler is treated with various known silane coupling agents, titanium coupling agents, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid salts or other surfactants. May be.

The content of the propylene polymer (A) is 40 to 90% by weight, preferably 45 to 80% by weight, and more preferably 50 to 75% by weight. The content of the propylene-ethylene-α-olefin copolymer (B) is 5 to 20% by weight, preferably 6 to 15% by weight, and more preferably 8 to 12% by weight. As content of ethylene-alpha-olefin random copolymerization (C), it is 5 to 40 weight%, Preferably, it is 5 to 30 weight%.
However, the total amount of (A), (B) and (C) is 100% by weight.

  As content of an inorganic filler (D), it is 0.1-60 weight part with respect to 100 weight part of polypropylene resin compositions containing (A), (B), and (C), Preferably From the viewpoint of improving rigidity, it is 1 to 40 parts by weight, more preferably 5 to 30 parts by weight.

  MI (measurement temperature is 230 ° C., load is 2.16 kg) of the polypropylene resin composition of the present invention and the inorganic filler-containing polypropylene resin composition is 0.5 to 40 g / 10 min, preferably 1 to The amount is 40 g / 10 minutes, more preferably 5 to 40 g / 10 minutes.

  Examples of the method for producing the polypropylene resin composition and the inorganic filler-containing polypropylene resin composition of the present invention include a method of kneading each component, and the apparatus used for kneading includes a single screw extruder, a twin screw extruder, A Banbury mixer, a heat roll, etc. are mentioned. The kneading temperature is usually 170 to 250 ° C., and the time is usually 1 to 20 minutes. In addition, the kneading of each component may be performed at the same time or may be performed separately.

  The polypropylene resin composition of the present invention and the inorganic filler-containing polypropylene resin composition may contain additives as necessary, for example, neutralizers, antioxidants, light resistance agents, ultraviolet absorption Agents, copper damage inhibitors, lubricants, processing aids, plasticizers, dispersants, antiblocking agents, antistatic agents, nucleating agents, flame retardants, foaming agents, antifoaming agents, crosslinking agents, colorants, pigments, etc. Can be mentioned.

  The molded article of the present invention is a molded article comprising the polypropylene resin composition of the present invention or an inorganic filler-containing polypropylene resin composition, and the polypropylene resin composition of the present invention or an inorganic filler-containing polypropylene resin composition. Examples of the method for molding a product include an injection molding method, an extrusion molding method, a rotational molding method, a vacuum molding method, a foam molding method, and a blow molding method.

  Examples of the use of the molded article of the present invention include automobile interior parts or exterior parts, motorcycle parts, furniture and electrical product parts.

  Examples of automobile interior parts include instrument panels, trims, door panels, side protectors, console boxes, column covers, and the like. Examples of automobile exterior parts include bumpers, fenders, wheel covers, and the like. Examples of the parts include a cowling and a muffler cover.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
In the examples or comparative examples, the following resins and additives were used.
(1) Propylene-ethylene block copolymer (A-1)
It was prepared by a solvent polymerization method using the solid catalyst component described in JP-A-7-216017.
MI (230 ° C., 2.16 kg load): 30 g / 10 minutes Intrinsic viscosity [η] _{T of the} entire propylene-ethylene block copolymer: 1.52 dl / g
Intrinsic viscosity [η] _{P of the} propylene homopolymer portion: 1.05 dl / g
Ethylene unit content: 7.2% by weight
Weight ratio of propylene-ethylene random copolymer portion to the whole copolymer: 16% by weight
Intrinsic viscosity [η] _{EP of} propylene-ethylene random copolymer portion: 4.0 dl / g
Ethylene unit content of propylene-ethylene random copolymer portion: 45% by weight

(2) Propylene homopolymer (A-2)
It was prepared by a solvent polymerization method using the solid catalyst component described in JP-A-7-216017.
MI: 300g / 10min

(3) Propylene-ethylene copolymer (A-3)
It manufactured according to the manufacturing method of the propylene polymer (HMS-3) as described in the Example of Unexamined-Japanese-Patent No. 2005-146160. The polymer produced up to the second tank corresponds to the propylene-ethylene random copolymer component, the intrinsic viscosity [η] is 7.8 dl / g, the ethylene content is 2.8% by weight, and the first tank The ratio of the polymerization amount in the second tank and the polymerization amount in the third tank is 72:28, and the intrinsic viscosity of the propylene polymer polymerized in the third tank is 0.9 dl / g (A-3) was obtained.

(4) Propylene homopolymer (A-4)
Product name: FS2011DG3 manufactured by Sumitomo Chemical Co., Ltd.
(5) Propylene-ethylene copolymer (A-5)
Product name: S131, manufactured by Sumitomo Chemical Co., Ltd.

(6) Propylene-ethylene-1-butene copolymer (B)
(6-1) Production of transition metal complex (dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride) (polymerization catalyst component) (1) 1-bromo Production of -3-tert-butyl-5-methyl-2-phenol In a 500 ml four-necked flask equipped with a stirrer, 20.1 g (123 mmol) of 2-tert-butyl-4-methylphenol was toluene in a nitrogen atmosphere. Dissolved in 150 ml, followed by addition of 25.9 ml (18.0 g, 246 mmol) tert-butylamine. This solution was cooled to −70 ° C., and 10.5 ml (32.6 g, 204 mmol) of bromine was added thereto. This solution was kept at −70 ° C. and stirred for 2 hours. Thereafter, the temperature was raised to room temperature, and 100 ml of 10% dilute hydrochloric acid was added and washed three times. The organic layer obtained after washing was dried using anhydrous sodium sulfate, the solvent was removed using an evaporator, and then purified using a silica gel column, and 1-bromo-3-tert-butyl which was a colorless oil was obtained. 18.4 g (75.7 mmol) of -5-methyl-2-phenol was obtained. The yield was 62%.

(6-2) Production of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene Synthesized in the above (6-1) under a nitrogen atmosphere in a 100 ml four-necked flask equipped with a stirrer. 13.9 g (57.2 mmol) of 1-bromo-3-tert-butyl-5-methyl-2-phenol was dissolved in 40 ml of acetonitrile, and then 3.8 g (67.9 mmol) of potassium hydroxide was added. Further, 17.8 ml (40.6 g, 286 mmol) of methyl iodide was added and stirring was continued for 12 hours. Thereafter, the solvent was removed by an evaporator, and 40 ml of hexane was added to the residue to extract a hexane-soluble component. The extraction was repeated 3 times. The solvent was removed from the extract to obtain 13.8 g (53.7 mmol) of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene as a pale yellow oil. The yield was 94%.

(6-3) Production of (3-tert-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane 1-bromo synthesized with tetrahydrofuran (31.5 ml), hexane (139 ml) and the above (2-2) To a solution consisting of -3-tert-butyl-2-methoxy-5-methylbenzene (45 g), at −40 ° C., a 1.6 mol / liter hexane solution (115 ml) of n-butyllithium was added over 20 minutes. It was dripped. The obtained mixture was kept at −40 ° C. for 1 hour, and tetrahydrofuran (31.5 ml) was added dropwise to the mixture to obtain a mixture.

  The mixture obtained above was added dropwise at −40 ° C. to a solution consisting of dichlorodimethylsilane (131 g) and hexane (306 ml). The resulting mixture was warmed to room temperature over 2 hours and further stirred at room temperature for 12 hours.

  Distilling off the solvent and excess dichlorodimethylsilane from the reaction mixture under reduced pressure, extracting hexane solubles from the residue using hexane, distilling off the solvent from the resulting hexane solution, giving a pale yellow oil 41.9 g of (3-tert-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane was obtained. The yield was 84%.

(6-4) Production of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (3-tert-butyl-2 synthesized in (6-3) above To a solution composed of -methoxy-5-methylphenyl) chlorodimethylsilane (5.24 g) and tetrahydrofuran (50 ml), tetramethylcyclopentadienyl lithium (2.73 g) was added at -35 ° C, and 2 The temperature was raised to room temperature over time, and the mixture was further stirred at room temperature for 10 hours.

  The solvent was distilled off from the obtained reaction mixture under reduced pressure, and hexane-soluble matter was extracted from the residue using hexane, and the solvent was distilled off from the obtained hexane solution under reduced pressure to give a yellow oily product. 6.69 g of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane was obtained. The yield was 97%.

(6-5) Production of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl- 2-methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (10.04 g), toluene (100 ml) and triethylamine (6.30 g) were added to n-butyl at −70 ° C. A 1.63 mol / liter hexane solution of lithium (19.0 ml) was added dropwise, and then the mixture was warmed to room temperature over 2 hours and further kept at room temperature for 12 hours to obtain a mixture.

  The mixture obtained above was dropped into a toluene solution (50 ml) of titanium tetrachloride (4.82 g) at 0 ° C. in a nitrogen atmosphere, and then the temperature was raised to room temperature over 1 hour, followed by heating for 10 hours. Refluxed.

該化合物のスペクトルデータは次のとおりであった。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃） δ ０．５７（ｓ，６Ｈ）、１．４１（ｓ，９Ｈ）、２．１５（ｓ，６Ｈ）、２．３４（ｓ，６Ｈ）、２．３８（ｓ，３Ｈ）、７．１５（ｓ，１Ｈ）、７．１８（ｓ，１Ｈ）
¹³Ｃ−ＮＭＲ（ＣＤＣｌ₃） δ １．２５、１４．４８、１６．２８、２２．４７、３１．２５、３６．２９、１２０．２３、１３０．６２、１３１．４７、１３３．８６、１３５．５０、１３７．３７、１４０．８２、１４２．２８、１６７．７４
マススペクトル（ＣＩ、ｍ／ｅ）４５８ The reaction mixture was filtered, the solvent was distilled off from the filtrate, the residue was recrystallized from a toluene-hexane mixed solvent, and orange columnar crystals of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5- 3.46 g of methyl-2-phenoxy) titanium dichloride (the following formula) was obtained. The yield was 27%.

The spectral data of the compound was as follows.
¹ H-NMR (CDCl ₃ ) δ 0.57 (s, 6H), 1.41 (s, 9H), 2.15 (s, 6H), 2.34 (s, 6H), 2.38 (s , 3H), 7.15 (s, 1H), 7.18 (s, 1H)
¹³ C-NMR (CDCl ₃ ) δ 1.25, 14.48, 16.28, 22.47, 31.25, 36.29, 120.23, 130.62, 131.47, 133.86, 135 .50, 137.37, 140.82, 142.28, 167.74
Mass spectrum (CI, m / e) 458

(6-6) Production of propylene-1-butene copolymer (B-1) From the lower part of a 100 L-SUS polymerizer equipped with a stirrer, to which a jacket for circulating cooling water is attached, is used as a polymerization solvent. Dimethylsilyl (tetramethylcyclohexane) synthesized in the above item 1 as a polymerization catalyst component at a rate of 100 L / hour of hexane, a rate of 24.00 kg / hour of propylene and a rate of 1.81 kg / hour of 1-butene. Pentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride at a rate of 0.005 g / hr and triphenylmethyltetrakis (pentafluorophenyl) borate at a rate of 0.298 g / hr. , Triisobutylaluminum continuously at a rate of 2.315 g / hr, hydrogen as a molecular weight regulator, respectively And was continuously copolymerized at 45 ° C.

  After the polymerization reaction is stopped by adding a small amount of ethanol to the reaction mixture continuously withdrawn from the upper part of the polymerization vessel so that the reaction mixture in the polymerization vessel maintains an amount of 100 L, depolymerization and By washing with water and then removing the solvent with steam in a large amount of water, a propylene-1-butene copolymer (B-1) was obtained, which was dried under reduced pressure at 80 ° C. overnight. The production rate of the copolymer was 7.10 kg / hour. The structure of the obtained copolymer (B-1) is shown in Table 1.

(6-7) Production of Propylene-Ethylene-1-butene Polymers (B-2) and (B-3) Using the same catalyst as used in the production of (B-1), the amount of ethylene supplied during polymerization Then, the amount of propylene supplied, the amount of 1-butene supplied, the amount of hydrogen and the like were adjusted to obtain a polymer (B-2) and a polymer (B-3) having the structure shown in Table 1 below.

(7) Master batch (B ')
(7-1) Propylene-1-butene polymer masterbatch (B′-1)
A propylene-1-butene polymer masterbatch comprising 70% by weight of the propylene-1-butene polymer (B-1) obtained above and 30% by weight of a propylene homopolymer (A-4).

(7-2) Propylene-ethylene-1-butene polymer master batch (B′-2)
Propylene-ethylene-1-butene polymer master comprising 85% by weight of the propylene-ethylene-1-butene polymer (B-2) obtained above and 15% by weight of the propylene-ethylene copolymer (A-5). batch.

(7-3) Propylene-ethylene-1-butene polymer masterbatch (B′-3)
A propylene-ethylene-1-butene polymer masterbatch comprising 55% by weight of the propylene-ethylene-1-butene polymer (B-3) obtained above and 45% by weight of a propylene homopolymer (A-4).

(8) Elastomer (C)
(C-1) Ethylene-octene copolymer rubber
Product Name: Engage 8200 (Dow Chemical Co.)
Density: 0.87 (g / cm ³ )
MI (190 ° C., 2.16 kg load): 5 (g / 10 min)
(C-2) Ethylene-butene copolymer rubber
Product name: Toughmer A0250S (Mitsui Chemicals)
Density: 0.86 (g / cm ³ )
MI (190 ° C., 2.16 kg load): 0.2 (g / 10 min)
(C-3) Ethylene-octene copolymer rubber
Product Name: Engage 8842 (Dow Chemical Co.)
Density: 0.857 (g / cm ³ )
MI (190 ° C., 2.16 kg load): 1 (g / 10 min)
(C-4) Ethylene-butene copolymer rubber
Product name: GA801 (Sumitomo Chemical Co., Ltd.)
Density: 0.920 (g / cm ³ )
MI (190 ° C., 2.16 kg load): 20 (g / 10 min)

(9) Inorganic filler (D)
Talc (Made by Hayashi Kasei Co., Ltd.)
Product name: MWHST (average particle size: 2.7 μm)

[Examples 1-4, Comparative Examples 1-2]
The inorganic filler-containing polypropylene resin composition was produced according to the following method.

  A predetermined amount of each component is weighed so as to have the components shown in Table 2, and after uniformly premixing with a tumbler, using a twin-screw kneading extruder (TEX44SS 30BW-2V type manufactured by Nippon Steel) The pellets were produced by kneading and extrusion under an extrusion rate of 30 kg / hr, a screw rotation speed of 300 rpm, and vent suction.

The measuring method of the physical property of the resin component and composition used by the Example and the comparative example was shown below.
(1) Melt index (MI, unit: g / 10 minutes)
It measured according to the method prescribed | regulated to JIS-K-6758.
Unless otherwise specified, the measurement was performed at 230 ° C. and a load of 2.16 kg.

(2) Structural analysis of propylene-ethylene block copolymer (2-1) Intrinsic viscosity of propylene-ethylene block copolymer (2-1-a) Intrinsic viscosity of propylene homopolymer portion (first segment): [ η] P
The intrinsic viscosity of the propylene homopolymer portion, which is the first segment of the propylene-ethylene block copolymer: [η] P is the propylene homopolymer from the inside of the polymerization tank after the polymerization of the propylene homopolymer as the first step. The coalescence was taken out, and [η] P of the taken out propylene homopolymer was measured.

(2-1-b) Intrinsic viscosity of propylene-ethylene random copolymer portion (second segment): [η] EP
The intrinsic viscosity of the propylene-ethylene random copolymer portion, which is the second segment of the propylene-ethylene block copolymer: [η] EP is the intrinsic viscosity of the propylene homopolymer portion: [η] P and the propylene-ethylene block copolymer. Intrinsic viscosity of the entire polymer: [η] T was measured, and the weight ratio: X of the propylene-ethylene random copolymer portion to the entire propylene-ethylene block copolymer was calculated from the following formula.
[η] EP = [η] T / X− (1 / X−1) [η] P
[η] P: Intrinsic viscosity of the propylene homopolymer portion (dl / g))
[η] T: intrinsic viscosity of the entire propylene-ethylene block copolymer (dl / g)

(2-1-c) Weight ratio of propylene-ethylene random copolymer portion to the entire propylene-ethylene block copolymer: X
Weight ratio of the propylene-ethylene random copolymer portion to the entire propylene-ethylene block copolymer: X is the amount of heat of crystal melting of the propylene homopolymer portion (first segment) and the entire propylene-ethylene block copolymer. And obtained by calculation using the following equation. The heat of crystal fusion was measured by differential scanning thermal analysis (DSC).

(3) Ethylene content of propylene-ethylene random copolymer portion in propylene-ethylene block copolymer: (C2 ′) EP
Ethylene content of propylene-ethylene random copolymer portion of propylene-ethylene block copolymer: (C2 ') EP is a measure of ethylene content (C2') T of the entire propylene-ethylene block copolymer by infrared absorption spectroscopy. And obtained by calculation using the following equation.
(C2 ') EP = (C2') T / X
(C2 ′) T: Ethylene content (% by weight) of the entire propylene-ethylene block copolymer
(C2 ′) EP: ethylene content of propylene-ethylene random copolymer portion (% by weight)
X: Weight ratio of propylene-ethylene random copolymer portion to the entire propylene-ethylene block copolymer

(4) Heat of fusion of copolymer (B) Measurement was performed under the following conditions using a differential scanning calorimeter (DSC RDC220 manufactured by Seiko Denshi Kogyo Co., Ltd.).
(I) About 5 mg of a sample is heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after the temperature increase is completed.
(Ii) Next, the temperature is decreased from 200 ° C. to −100 ° C. at a temperature decreasing rate of 10 ° C./min.
(Iii) After completion of the temperature decrease, the temperature is maintained for 5 minutes, and then the temperature is increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min.
The peak observed in (iv) is the melting peak, and the heat of fusion was calculated from the peak area.

(5) Molecular weight distribution of copolymer (B) The gel permeation chromatograph (GPC) method was used for measurement under the following conditions.
From the obtained results, a weight average molecular weight (Mw) and a number average molecular weight (Mn) were calculated, and a molecular weight distribution (Mw / Mn) was calculated.
Equipment: 150C ALC / GPC manufactured by Waters
Column: Showa Denko Corporation Shodex Packed Column A-80M 2 temperature: 140 ° C
Solvent: o-dichlorobenzene Elution solvent flow rate: 1.0 ml / min
Sample concentration: 1 mg / ml
Measurement injection volume: 400 μl
Molecular weight reference material: Standard polystyrene Detector: Differential refraction

(6) Izod impact strength (Izod, unit: kJ / m ² )
It measured according to the method prescribed | regulated to JIS-K-7110. The pellets obtained by biaxial kneading with the composition shown in Table 2 were measured at 23 ° C. using a notched test piece with a thickness of 6.4 mm formed by injection molding.

(7) Scratch test Using pellets obtained by biaxial kneading with the composition shown in Table 2, injection was performed at a molding temperature of 220 ° C. and a mold cooling temperature of 50 ° C. using a SE180D injection molding machine manufactured by Sumitomo Heavy Industries. Molding was performed to obtain a flat plate test piece of 400 mm × 100 mm × 3 mm. A 100 × 100 mm square flat plate was cut out from the flat plate test piece to obtain a scratched test piece. Using a special large UF scratch tester manufactured by Ueshima Seisakusho Co., Ltd., a scratch test was conducted under the following conditions. A 0.5 kg or 1 kg load is applied to a wound test needle whose tip is a hemisphere (material SUS403) with a diameter of 1 mm, and scratches on the surface of the grid at 1 mm intervals or 2 mm intervals at a speed of 600 mm / min. Was attached.
Scratch resistance was evaluated by the color difference (ΔE) before and after the scratch test of the mirror surface flat plate. The measurement was carried out using a SM color computer (SM-5-CH model) manufactured by Suga Test Instruments Co., Ltd. under the conditions of a condensing lens: φ30 and a sample stage: φ30 using a 45 ° diffusion system. A smaller ΔE value means better scratch resistance.

(8) Stress whitening test A flat test piece molded and cut out in the same manner as in the scratch test was used. A weight made of stainless steel and a hemispherical tip having a diameter of 12 mm was placed on the test piece, and a 1 kg load was dropped from the height of 60 cm onto the weight, and the whitening area of the test piece was measured. A smaller whitening area means higher stress whitening resistance.

  It turns out that Examples 1-4 which satisfy the requirements of this invention are excellent in impact resistance, scratch resistance, and stress whitening resistance. On the other hand, Comparative Example 1 which did not use the polymer (B) which is a requirement of the present invention has insufficient stress whitening resistance and does not satisfy the density of the polymer (C) which is a requirement of the present invention. It can be seen that Comparative Example 2 using the copolymer (C-4) has insufficient impact resistance.

Claims (4)

40 to 90% by weight of at least one propylene polymer (A) selected from the group consisting of a propylene homopolymer (A-1) and a propylene-ethylene copolymer (A-2);
5 to 20% by weight of the following propylene-ethylene-α-olefin copolymer (B),
Containing 5 to 40% by weight of the following ethylene-α-olefin copolymer (C),
A polypropylene resin composition having a melt index of 0.5 to 40 g / 10 min at 230 ° C. and a load of 2.16 kg (provided that the total of (A), (B) and (C) is 100% by weight) .
In the propylene-ethylene-α-olefin copolymer (B), the α-olefin has 4 to 20 carbon atoms, a molecular weight distribution of 1 to 4, and an intrinsic viscosity of 0.5 to 10 dl / g. It is a propylene-ethylene-α-olefin copolymer having a heat of fusion of 30 J / g or less and an ethylene content of 60 mol% or less.
The ethylene-α-olefin copolymer (C) is an ethylene-α-olefin copolymer having an α-olefin having 4 to 20 carbon atoms and a density of 0.850 to 0.880 g / cm ^3. . 40 to 90% by weight of at least one propylene polymer (A) selected from the group consisting of a propylene homopolymer (A-1) and a propylene-ethylene copolymer (A-2);
5 to 20% by weight of the following propylene-ethylene-α-olefin copolymer (B),
A polypropylene resin composition containing 5 to 40% by weight of the following ethylene-α-olefin copolymer (C) (provided that the total of (A), (B) and (C) is 100% by weight) And an inorganic filler-containing polypropylene-based resin composition containing an inorganic filler (D),
The inorganic filler (D) is 0.1 to 60 parts by weight with respect to 100 parts by weight of the polypropylene resin composition,
An inorganic filler-containing polypropylene resin composition having a melt index of 0.5 to 40 g / 10 min at 230 ° C. and a load of 2.16 kg.
In the propylene-ethylene-α-olefin copolymer (B), the α-olefin has 4 to 20 carbon atoms, a molecular weight distribution of 1 to 4, and an intrinsic viscosity of 0.5 to 10 dl / g. It is a propylene-ethylene-α-olefin copolymer having a heat of fusion of 30 J / g or less and an ethylene content of 60 mol% or less.
The ethylene-α-olefin copolymer (C) is an ethylene-α-olefin copolymer having an α-olefin having 4 to 20 carbon atoms and a density of 0.850 to 0.880 g / cm ^3. .   An injection-molded article comprising the polypropylene resin composition according to claim 1 or the inorganic filler-containing polypropylene resin composition according to claim 2.   A foam molded article comprising the polypropylene resin composition according to claim 1 or the inorganic filler-containing polypropylene resin composition according to claim 2.