JP3362089B2 - Propylene resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene resin composition which is particularly suitable for injection molded articles such as automobile exterior materials because it has an improved balance between rigidity and impact resistance, good injection moldability and excellent molding appearance. Regarding

[0002]

2. Description of the Related Art Crystalline polypropylene has excellent properties such as rigidity, heat resistance and luster and is used for various purposes, but on the other hand, it has the drawback of being poor in impact resistance. In order to improve this drawback, a method of compounding a rubber component such as ethylene / propylene copolymer rubber has been proposed. However, since the rigidity is lowered, talc and the like are further added in order to obtain a good rigidity-impact resistance balance. There has been proposed a method in which the above inorganic filler is used in combination.

For example, in Japanese Patent Publication No. 60-3420, a propylene / ethylene copolymer having a room temperature paraxylene-soluble component in a specific range is blended with an ethylene / propylene copolymer rubber having a specific intrinsic viscosity and talc. And a propylene resin composition described in JP-B-63-429.
No. 29 and Japanese Patent Publication No. 4-28749 disclose a propylene resin composition in which an ethylene / α-olefin copolymer is used instead of the ethylene / propylene copolymer rubber for the purpose of improving impact resistance. . However, these methods cannot satisfy the advanced quality requirements in recent years. Besides, JP-A-4-15934
In JP-A No. 5-35, an ethylene / α-olefin copolymer having a melt property such as a melting peak or a heat of fusion in a specific range is used, but it is not always satisfactory in impact resistance. Thus, especially in applications requiring a high degree of rigidity-impact resistance balance, such as automobile interior materials,
Further improvements are required.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a propylene resin composition having improved rigidity-impact resistance balance and good injection moldability and molding appearance.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a propylene / ethylene block copolymer having specific physical properties and ethylene / α
The present invention has been completed by finding that the above object can be achieved by selecting an olefin copolymer and further adding a filler thereto.

That is, the present invention provides the following (A) to (C).
A propylene resin composition, characterized in that the total amount of each component is 100 parts by weight. (A) Contains 5 to 30% by weight of an ethylene / propylene random copolymerization portion represented as a component eluted at 50 ° C. in fractionation with o-dichlorobenzene, and has a melt flow rate (230 ° C., 2.16 kg load). Propylene / ethylene block copolymer having 20 to 200 g / 10 min .... 50 to 80 parts by weight (B) Melt flow rate (230 ° C., 2.16 kg load) 0.1 to 20 g / 10 min, density Is from 0.869 to 0.872 g / cm ³ and the comonomer is an α-olefin having 8 or more carbon atoms, an ethylene / α-olefin copolymer: 15 to 37 parts by weight (C) average aspect ratio Inorganic filler with a ratio of 4 or more ... 5 to less than 13 parts by weight

Here, the component (B) is composed of ethylene 3 chain fraction of 60% or more and an α-olefin comonomer content of 10 to 1.
A propylene resin composition, which is an ethylene / α-olefin copolymer having 7 mol% and a density of 0.860 to 0.880 g / cm ³ , is preferable.

Further, here, the propylene resin composition in which the component (B) is a copolymer polymerized by a metallocene catalyst is preferable.

Further, here, the propylene resin composition is
A propylene resin composition, which is a composition having the following physical properties, is preferable. Melt flow rate: more than 10 to less than 80 g / 10 minutes Flexural modulus: more than 11,000 to 20,000 kg / cm ² IZOD impact strength (−30 ° C.): more than 5 kg · cm / cm ² Rockwell hardness: more than 50 Less than 80

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A): Propylene / ethylene block copolymer The above-mentioned propylene / ethylene block copolymer used in the present invention is a component which elutes at 50 ° C. in fractionation with o-dichlorobenzene. It contains 5 to 30% by weight, preferably 5.5 to 22% by weight of the ethylene / propylene random copolymerization portion represented, and has an MFR (230 ° C, 2.1%).
6 kg load) is 20 to 200 g / 10 minutes, preferably 25
~ 150 g / 10 min, particularly preferably 30-100 g /
It is a 10-minute propylene / ethylene block copolymer.

If the amount of the ethylene / propylene random copolymer portion is too small, the impact resistance is inferior, and if it is too large, the rigidity is lowered, which is not preferable. On the other hand, if the MFR is too low, injection moldability such as flow mark, weld appearance and fluidity will be poor, while if it is too high, impact resistance will be poor. The component that does not elute at 50 ° C. in the fractionation with o-dichlorobenzene is the portion represented as the crystalline propylene homopolymerization portion. The propylene / ethylene block copolymer as the component (A) can be produced by slurry polymerization, gas phase polymerization or liquid phase bulk polymerization using a highly stereoregular polymerization catalyst. Specific examples of the polymerization include, for example, magnesium chloride and titanium tetrachloride,
Homopolymerization of propylene is carried out using a catalyst in which an organic aluminum compound component is combined with a solid component formed by bringing an organic halide and an organic silicon compound into contact with each other, and then a random copolymerization of propylene and ethylene is carried out to obtain a target polymer. The method of manufacturing can be mentioned. The MF of this propylene / ethylene block copolymer
R may be adjusted during the polymerization, or may be adjusted with an organic peroxide such as diacyl peroxide or dialkyl peroxide after the polymerization.

Further, this propylene / ethylene block copolymer is similar to other unsaturated compounds, for example, α-olefins such as 1-butene and 1-hexene and vinyl acetate within a range that does not significantly impair the effects of the present invention. May be a terpolymer or more containing a vinyl ester or acrylic acid, acrylic acid such as methyl acrylate, or a derivative thereof, and may be used in combination with two or more propylene / ethylene block copolymers. It doesn't matter.

Component (B): Ethylene / α-olefin Copolymer The above ethylene / α-olefin copolymer used in the present invention has an MFR (230 ° C., 2.16 kg load) of 0.
1 to 20 g / 10 minutes, preferably 0.2 to 15 g / 10
It is an ethylene / α-olefin copolymer of α-olefin having a density of 0.869 to 0.872 g / cm ³ and a comonomer of 8 or more carbon atoms. Suitable content of α-olefin is 10 to 17 mol%, especially 12 to 17 mol%.
Is preferred. Further, the ethylene / α-olefin copolymer having an ethylene 3 chain fraction of 60% or more is preferable from the viewpoint of Rockwell hardness and the like. Therefore, ethylene 3 chain fraction 60% or more, α-olefin comonomer content 10 to 17 mol%, MFR (230 ° C, 2.16).
(kg load) 0.2 to 15 g / 10 minutes and density 0.869
Particularly preferred is an ethylene / α-olefin copolymer of about 0.872 g / cm ³ .

When the MFR is out of the above range, the impact resistance is inferior, which is not preferable. On the other hand, if the density is too low, the production becomes difficult, while if it is too high, the impact resistance becomes poor, which is not preferable. When the α-olefin has a carbon number of 7 or less, a remarkable effect of improving impact resistance cannot be expected. Examples of the α-olefin having 8 or more carbon atoms include 1-octene, 1-nonene, 1-decene, 1-undecene and 1-octene.
Dodecene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene and the like can be mentioned. ethylene·
For the purpose of improving the physical properties by including a small amount of a high molecular weight component in the α-olefin copolymer, a small amount of a diene component, for example,
Ethylidene norbornene, 1,4-hexadiene, 1,
It is also possible to copolymerize 9-decadiene, vinyl norbornene and the like.

Examples of catalysts for producing such ethylene / α-olefin copolymers include titanium compounds such as titanium halides, vanadium compounds, alkylaluminum-magnesium complexes, and alkylalkoxyaluminum-magnesium complexes. Organic Aluminum-
Mention may be made of magnesium complexes and so-called Ziegler-type catalysts such as alkylaluminum or alkylaluminum chloride, and among others, WO-91 / 0.
When polymerized with a metallocene catalyst using a metallocene compound as a catalyst as disclosed in Japanese Patent No. 4257, a copolymer exhibiting a more remarkable effect is obtained, which is preferable.

As the polymerization method, for example, a gas phase fluidized bed method,
Examples thereof include a solution method, a slurry method, and a method of copolymerizing ethylene and α-olefin by applying a manufacturing process such as a high pressure ionic polymerization method at a pressure of 200 kg / cm ² or more and a temperature of 180 ° C. or more.

Component (C): Inorganic Filler The inorganic filler used in the present invention is an inorganic filler having an average aspect ratio of 4 or more, preferably 5 or more, and particularly preferably 5.5 or more. If the average aspect ratio is too small, the elastic modulus of the molded product becomes poor, which is not preferable.

Specific examples of suitable fillers include, for example, a length of 15 μm or less and an average particle diameter of 1 to 10.
Examples include talc having an average aspect ratio of 4 or more and μm, mica having an average particle size of 8 to 100 μm and an average aspect ratio of 10 or more, and fibrous filler having an average diameter of 13 μm or less and an average aspect ratio of 5 or more. . Of these, talc is particularly preferable. As the filler, the smaller the average particle size and the larger the average aspect ratio, the higher the effect of the present invention can be exhibited.

For talc, for example, raw talc is crushed by an impact type crusher or a micron type crusher, further finely crushed by a micron mill type crusher, a jet mill type crusher, etc., and then a cyclone or a micron separator is used. It can be manufactured by classifying and adjusting. As a rough stone, it is generally preferable that it is produced in China, which has less metal impurities.

As the mica, there are white mica, gold mica, black mica and the like having different types and production methods, and they are not particularly limited, but white mica and gold mica are preferable from the viewpoint of performance. Further, it is particularly preferable that these mica are produced by a wet pulverization or a wet classification method.

Examples of the fibrous filler include glass fiber, carbon fiber, aluminum borate fiber, potassium titanate fiber, basic magnesium sulfate fiber, carbon calcium fiber and the like. Among these, particularly preferable are those having an average diameter of 0.2 to 10 μm and an average aspect ratio of 10 or more. Here, as the measurement of the average particle diameter, there is LA-500 type manufactured by Horiba Ltd. The diameter, length, and aspect ratio are values measured with a microscope or the like. The above fillers are
It may be one treated with a surface treatment agent such as a coupling agent.

Optional Components In the propylene resin composition of the present invention, optional components other than the above-mentioned essential components can be added to the propylene resin composition so long as the effects of the present invention are not significantly impaired in order to impart further functions. As this optional component, those known or used as usual polyolefin additives and compounding agents, for example, antioxidants, neutralizing agents, weather resistance improvers, antifoam agents,
Dispersants, antistatic agents, lubricants, molecular weight modifiers (peroxides, etc.), heat stabilizers, light stabilizers, UV absorbers, lubricants, antifogging agents, antiblocking agents, flame retardants, conductivity imparting agents,
Cross-linking agent, cross-linking aid, metal deactivator, bactericide, anti-mold agent,
Optical brighteners, colorants, mold release agents, foaming agents, clarifying agents, processing aids, crystal nucleating agents, softening agents or hardness modifiers (oils, waxes, etc.), gloss imparting agents, grain-sharpening agents, physical properties Examples include regulators (other resins and rubbers), other fillers,
These may be appropriately combined and compounded at any stage from the production of a molding raw material to a molded product.

Mixing Ratio of Each Component The mixing ratio of the above-mentioned essential components is as follows:
The ethylene block copolymer is in excess of 50 to 80 parts by weight, preferably 55 to 72 parts by weight, the component (B) of ethylene / α-
Olefin copolymer 15 to 37 parts by weight, preferably 20
~ 33 parts by weight, and inorganic filler 5-1 of component (C)
It is less than 3 parts by weight, preferably 8 to 12 parts by weight. However, the total amount of the components (A) to (C) is blended so as to be 100 parts by weight.

If the amount of component (A) is too small, the rigidity will be poor, while if it is too large, the impact resistance will be poor. On the other hand, if the amount of component (B) is too small, the impact resistance is poor, while if it is too large, the rigidity is poor. On the other hand, if the amount of component (C) is too small, the rigidity is poor. On the other hand, if it is too large, flow marks and welds tend to be conspicuous and the appearance tends to deteriorate, which is not preferable. The propylene resin composition of the present invention is particularly suitable for an injection-molded article for automobile exterior materials, but it is preferable to prepare an optimum blending ratio within the above range depending on the intended use.

Manufacture of Resin Composition The above-mentioned essential components and, if desired, optional components can be directly charged into a molding machine for molding, but generally, these components are blended in advance with a mixer or the like, and then a uniaxial extruder is used. ,
Melt kneading with a normal kneading machine such as a twin-screw extruder, a Banbury mixer, a roll mixer, a kneader blender, a Brabender plastograph, and granulate into pellets to form a resin composition, that is, a molding material, which is injected. It is desirable to perform equal molding. In this case, since it is important for the resin composition to disperse each component as uniformly and finely as possible,
It is preferable to knead and granulate using a twin-screw extruder. At the time of granulation, the compounds may be kneaded all at once, or may be divided and kneaded in order to improve the performance.

The resin composition of the present invention, which is a composition having the following physical properties, is particularly suitable for industrial parts material applications. Melt flow rate: more than 10 to less than 80 g / 10 minutes,
Particularly preferably, the elastic modulus in bending is from 11 to 50 g / 10 min: more than 11,000 to 20,000 kg / c.
m ² , particularly preferably over 11,000 to 18,000 k
g / cm ² IZOD impact strength (-30 ° C): over 5 kg · cm / cm ² ,
Particularly preferably 5.5 kg · cm / cm ² or more Rockwell hardness: more than 50 to less than 80, preferably 5
5-75

Molding and Use The resin composition thus obtained, that is, a molding material, is
It is molded into various shaped articles by various molding methods such as injection molding, injection compression molding, compression molding, extrusion molding (sheet molding, film molding, blow molding, pipe molding, etc.). Among these molding methods, the effect of the present invention is greatly exerted when the molding is performed by the injection molding method or the injection compression molding method. The resin composition of the present invention has improved rigidity-impact resistance balance and good injection moldability, and therefore, for example, automobile exteriors such as bumpers, corner bumpers, cowl louvers, door protectors, and side moldings. It is suitable for use as a member, a TV case, a VTR case, a washing machine cover, a vacuum cleaner case and other home electric appliance parts, or a stereo case and other audio equipment parts.

[0028]

The present invention will be further described below with reference to specific examples. In the examples, the physical properties of raw materials and molded products were evaluated by the following methods. ○ MFR: JIS K7210 compliant (230 ° C, 2.16
kg load). ○ Density: According to JIS K7112 (measured without annealing). Amount of comonomer: ¹³ C-NMR measurement method (Macromolecules
1982, Vol. 15, pp. 353-360 and 1402-1406).

Ethylene 3-chain fraction: Using the ¹³ C-NMR signal area, methylene in an alkyl chain having 6 carbon atoms, as described in Journal of Japan Rubber Association, Volume 600 No. 1 (1987), page 38. The numerical value obtained by calculating the ratio of the structural portion in which 6 chains are connected is shown. Bending elastic modulus: JIS K7203 compliant (230
C). ○ IZOD impact strength: JIS K7110 compliant (-30
℃, with cutting notch). ○ Rockwell hardness: JIS K6758 compliant (measured on the R scale).

Flow mark: 170 tons of mold clamping pressure 350 mm × 100 mm × at a molding temperature of 220 ° C. with an injection molding machine
A 3mmt sheet is molded, and its appearance is visually judged according to the following criteria. ○ Good with no flow mark. △ There is some flow mark. × The flow mark is very noticeable.

○ Weld appearance: 170 tons of mold clamping pressure 350mm × 100mm × at injection molding machine with molding temperature set at 220 ° C
A 3mmt sheet is molded with a two-point pin gate, and the appearance of the weld line in the center is visually judged based on the following criteria. ○ Good with no weld line. △ Weld line somewhat. × Weld line is very noticeable.

Examples 1 to 11 and Comparative Examples 1 to 17 The components (A), (B) and (C) shown in Tables 1, 2 and 3 were blended in the proportions shown in Tables 4 and 5. Furthermore, 0.1 parts by weight of tetrakis [methylene-3- (3 ′, 5′-di-t-based on 100 parts by weight of these components in total.
-Butyl-4'-hydroxyphenyl) propionate] methane was mixed and mixed in a Kawada Seisakusho super mixer for 5 minutes, and then a twin-screw kneader "FC" manufactured by Kobe Steel, Ltd.
The composition was obtained by kneading and granulating with “M” at 210 ° C. The obtained pellets were molded with an injection molding machine having a mold clamping pressure of 100 tons at a molding temperature of 220 ° C. to obtain test pieces for measuring various physical properties, and the physical properties were measured. The results are shown in Tables 4 and 5. However, regarding the evaluation of the flow mark and the weld appearance, 0.5 parts by weight of carbon black was added to 100 parts by weight of the total of the components (A), (B) and (C) in addition to the above composition. The obtained pellets were used for evaluation.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

[0038]

EFFECTS OF THE INVENTION According to the present invention, since the balance between rigidity and impact resistance is improved, the injection moldability is good and the molding appearance is excellent, a propylene resin composition suitable for injection molded articles such as automobile exterior materials is particularly suitable. There is a remarkable effect that is obtained.

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Claims (4)

(57) [Claims] 1. The total amount of each of the following components (A) to (C) is 1
A propylene resin composition, characterized in that the propylene resin composition is blended in an amount of 100 parts by weight. (A) Contains 5 to 30% by weight of an ethylene / propylene random copolymerization portion represented as a component eluted at 50 ° C. in fractionation with o-dichlorobenzene, and has a melt flow rate (230 ° C., 2.16 kg load). Propylene / ethylene block copolymer having 20 to 200 g / 10 min .... 50 to 80 parts by weight (B) Melt flow rate (230 ° C., 2.16 kg load) 0.1 to 20 g / 10 min, density Is from 0.869 to 0.872 g / cm ³ and the comonomer is an α-olefin having 8 or more carbon atoms, an ethylene / α-olefin copolymer: 15 to 37 parts by weight (C) average aspect ratio Inorganic filler with a ratio of 4 or more ... 5 to less than 13 parts by weight 2. The component (B) is an ethylene 3-chain fraction 60.
% Or more and the α-olefin comonomer content is 10 to 17 mol% , the propylene resin composition according to claim 1. 3. The propylene resin composition according to claim 1, wherein the component (B) is a copolymer polymerized by a metallocene catalyst. 4. The propylene resin composition according to claim 1, wherein the propylene resin composition is a composition having the following physical properties. Melt flow rate: Exceeding 10 to less than 80 g / 10 minutes Flexural modulus: Exceeding 1,000, to 20,000
kg / cm ² IZOD impact strength: 5 kg · cm / cm ² exceeding Rockwell hardness: 50 to less than 80