JP3380281B2 - Propylene resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based resin composition which is significantly improved in impact resistance and is suitable for materials such as interior and exterior parts of automobiles and exterior parts of electric equipment. It is about. [0002] Polypropylene resin has high rigidity,
In recent years, demand has been accelerating in application fields such as interior and exterior parts of automobiles, such as bumpers, moldings, front grilles, instrument panels, etc., and exterior parts of electric equipment, because of good moldability and low cost. Is growing. However, even such a polypropylene resin has a problem that its impact resistance is insufficient depending on its use. Conventionally, in order to improve such problems, ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), ethylene-propylene-diene copolymer rubber (EPDM) have been used for polypropylene resin. )) Has been used, but when used for automotive parts, especially bumpers, etc., the impact resistance is regarded as very important, and the impact resistance is even higher than that of current products. The development of a material having good properties has been desired. SUMMARY OF THE INVENTION An object of the present invention is to improve the impact resistance of a polypropylene resin and to provide a polypropylene resin composition having a remarkably excellent impact resistance. [Summary of the Invention] The present invention has been intensively studied in view of the above problems, and as a result, a propylene / α-olefin block copolymer having a specific property and a metallocene Using a catalyst combining a compound and alumoxane, ethylene and carbon number 4 to
A propylene-based resin composition obtained by blending with an ethylene / α-olefin copolymer having specific properties obtained by copolymerizing α-olefin of No. 18 can achieve the above object. The inventor has obtained the knowledge and completed the present invention. That is, the propylene resin composition of the present invention is characterized by comprising the following components (A) and (B). Component (A) 50-97% by weight of a propylene / α-olefin block copolymer comprising the following polymer part (a) and polymer part (b) and having an overall MFR of 5 to 200 g / 10 minutes. Polymer part (a): A propylene homopolymer part having an MFR of 20 to 200 g / 10 minutes and a density of 0.9070 g / cm ³ or more 80 to 95% by weight Polymer part (b): α-olefin other than propylene Α-olefin / propylene random copolymer part having a content of 20 to 50% by weight and an MFR of 0.01 to 1 g / 10 minutes 20 to 5% by weight The component (B) was produced by a slurry method using a metallocene catalyst. A copolymer of ethylene having the following properties (a ') to (c') and an α-olefin having 4 to 18 carbon atoms: 50 to 3% by weight (a ') MFR is 0.01 to 20 g / 10 min (b ') a density (D) is 0.913 g / cm ³ or less (c') alpha-I [Specific description of the invention] [I] Constituent component (1) Component (A) [Propylene / α-olefin block copolymer] Propylene resin composition of the present invention The propylene / α-olefin block copolymer of component (A) has a MFR of the whole block copolymer of 5 to 200 g / 10 min, and propylene homopolymer is contained in the block copolymer. A polymer part [polymer part (a)] and a random copolymer part of propylene and a small amount of α-olefin [polymer part (b)
Wherein the polymer part (a) accounts for 80 to 95% by weight of the block copolymer and has an MFR of 20 to 95% by weight.
The polymer part (b) occupies 20 to 5% by weight in the block copolymer and has an α-olefin content of 200 g / 10 min at a density of 0.9070 g / cm ³ or more. MFR of 0.01 to 1 g / 1 at 〜50% by weight
It indicates 0 minutes. The method for producing such a propylene / α-olefin block copolymer is not particularly limited, and generally a so-called Ziegler-Natta type catalyst, particularly, titanium, magnesium and halogen are essential. Component, a solid component containing an electron-donating compound as an optional component or a combination catalyst using titanium trichloride as a transition metal component and an organoaluminum compound as an organometallic component, slurry polymerization, gas phase polymerization, bulk polymerization, solution In a polymerization method or a combination thereof, a propylene homopolymer obtained by homopolymerizing propylene, and propylene, an α-olefin, preferably an α-olefin having 2 or 4 to 12 carbon atoms, particularly preferably Propylene α-ole obtained by random copolymerization of ethylene and A block copolymer comprising a Inrandamu copolymer, propylene · alpha-olefin block copolymer obtained by copolymerizing at least two stages. (A) propylene homopolymer part [polymer part
ratio of (a)] a propylene homopolymer portion of the propylene · alpha-olefin block copolymer of the components constituting the propylene resin composition of the proportion present invention (A) [the polymer unit (a)], the component
It is important that (A) accounts for 80 to 95% by weight, preferably 85 to 93% by weight. If the proportion of the propylene homopolymer part [polymer part (a)] is less than the above range, the rigidity becomes insufficient, and if it is too large, the impact strength becomes insufficient. MFR MF of propylene homopolymer part [polymer part (a)]
R is 20 to 200 g / 10 min, preferably 30 to 10 g.
It is important that it is 0 g / 10 minutes. If the MFR of the propylene homopolymer portion [polymer portion (a)] is smaller than the above range, molding becomes difficult. If the MFR is too large, the impact strength is lowered and the polymer cannot be used practically. Density The density of the propylene homopolymer part [polymer part (a)] is 0.9070 g / cm ³ or more, preferably 0.90 g / cm ³ or more.
It is important that it is 74 or more. If the density of the propylene homopolymer portion [polymer portion (a)] is too low than the above range, the rigidity will be insufficient and a practical problem will occur. [0008] (b) alpha-olefin-propylene random copolymer portion [polymer unit (b)] a propylene-alpha-olefin block interpolymer components constituting the propylene resin composition of the proportion present invention (A) Weight Α- in coalescence
Olefin / propylene random copolymer part [Polymer part
It is important that the proportion of (b)] accounts for 20 to 5% by weight, preferably 15 to 7% by weight, in the component (A). If the proportion of the α-olefin / propylene random copolymer part (b) is less than the above range, the impact strength becomes insufficient, and if it is too large, the rigidity becomes insufficient. MFR , α-olefin / propylene random copolymer part
It is important that the MFR of (b) is 0.01 to 1 g / 10 min, preferably 0.05 to 0.5 g / 10 min.
If the MFR of the α-olefin / propylene random copolymer part [polymer part (b)] is less than the above range, poor dispersion may cause gel components, and if it is too large, impact strength may be reduced or sticky. I do. α-olefin content The α-olefin content in the α-olefin / propylene random copolymer part [polymer part (b)] is 20 to 50.
It is important that the amount is from 30% to 45% by weight. If the α-olefin content of the α-olefin / propylene random copolymer part (b) is too low, the low-temperature impact strength becomes insufficient. If the α-olefin content is too high, it becomes sticky and practically difficult to use. (C) Propylene / α-olefin block copolymer [Component (A)] ratio The above propylene homopolymer part [Polymer part (a)] and α-olefin / propylene random copolymer part [Polymer United part
(b)], the proportion of the propylene / α-olefin block copolymer [component (A)] in the propylene resin composition of the present invention is 50 to 97% by weight, preferably 7% by weight.
It is important to account for 0-93% by weight. The propylene / α-olefin block copolymer [component (A)]
If the proportion of the propylene-based resin composition in the propylene-based resin composition is too small, the low-temperature impact strength will be insufficient, and if it is too large, the rigidity will be insufficient and practical use will be difficult. MFR The propylene / α-olefin block copolymer [component (A)] has an MFR of 5 to 200 g / 10
It is important that the amount is 10 minutes, preferably 7 to 150 g / 10 minutes, particularly preferably 10 to 100 g / 10 minutes. The propylene / α-olefin block copolymer [component (A)
] Is too low below the above range, the moldability (particularly injection molding) becomes difficult. On the other hand, if the MFR is higher than the above range, the impact strength decreases. Further, such a propylene / α-olefin block copolymer [component
It is important to select and use (A)] from the viewpoint of highly improving the impact resistance, which is the object of the present invention. (2) Component (B) The copolymer of ethylene and the α-olefin having 4 to 18 carbon atoms as the component (B) used in the propylene resin composition of the present invention contains a metallocene catalyst. MFR 0.01 to 20 g produced by slurry polymerization method
/ 10 min, density (D) of 0.913 g / cm ³ or less, α
-A copolymer of ethylene having properties of 10 to 90% by weight and an α-olefin having 4 to 18 carbon atoms, and occupying 50 to 3% by weight in the propylene resin composition. (a) Metallocene Catalyst The metallocene catalyst is preferably a catalyst obtained by combining a metallocene compound and an alumoxane, a so-called Kaminski catalyst, for example, JP-A-58-193.
09, JP-A-59-95292, JP-A-60-35
005, JP-A-60-35006, JP-A-60-3
No. 5007, JP-A-60-35008, JP-A-60-
No. 35009, more preferably JP-A-3-1630088
The catalysts described in the above-mentioned publications, EP-A-420436, U.S. Pat. No. 5,055,428, and particularly preferably WO 91/04257 are described. [0011] Specifically, the following specific example [I] will be described.
And the catalyst shown in the specific example [II]. Specific Example [I] A catalyst comprising a combination of a transition metal compound component and an alumoxane component shown below. Transition metal compound component General formula (I) of a transition metal compound represented by the following general formula: (Wherein M is a transition metal selected from the group consisting of titanium, zirconium and hafnium, and two R ^{1 s} may be the same or different and have 1 carbon atom.
To 6 hydrocarbon residues or hydrocarbon residues containing silicon, and two R ^{2 s} may be the same or different,
A divalent hydrocarbon residue having 4 to 20 carbon atoms bonded to two adjacent carbon atoms of the five-membered ring ligand or a hydrocarbon residue containing silicon or germanium, wherein X and Y are each Independently hydrogen or halogen, or carbon number 1
20, monovalent hydrocarbon residues or hydrocarbon residues containing nitrogen, oxygen or silicon. However, the two five-membered ligands having substituents R ¹ and R ² are asymmetric with respect to the plane containing M in terms of relative position via the group R ³ . Alumoxane component alumoxane general formula (II) represented by the following general formulas (II) and (III): General formula (III) (Where m is a number from 4 to 30, R ⁴
Represents a monovalent hydrocarbon residue. ). Specific Example [II] A catalyst comprising a combination of a transition metal compound component and an alumoxane component shown below. Transition metal compound component General formula (IV) of a transition metal compound represented by the following general formula: (Wherein Q is halogen, hydroxyl, substituted or unsaturated hydrocarbon group having 1 to 20 carbon atoms, C ₅ H ₅ -such as alkoxy, allyloxy, amide, allylamide, phosphite, allyl phosphite) _yx may be a ligand of a monovalent ion different from _Rx , L is diethyl ether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, tetramethylphosphine, n
-A neutral Lewis group such as butylamine. W is 0-3
Is the number of L is Q and Q ', a second transition metal compound that bridges metals M and M'. R ¹ and R ² are independent hydrocarbon radicals having 1 to 20 carbon atoms, including those in which one or more hydrogen atoms have been replaced by halogen atoms. R '
Is a radical selected from the group consisting of hydrocarbon radicals having 1 to 20 carbon atoms. Alumoxane component Alumoxane general formula (V) represented by the following general formulas (V) and (VI) (R ³ -Al-O) m ₁ general formula (VI) Wherein, in ^{R 3, R 4, R 5} , R 6 are independently alkyl radicals having 1 to 5 carbon atoms, for example, those such as methyl, ethyl, propyl, butyl or pentyl, m ₁ is 1 to about 5
It is an integer of 0. Usually, R ³ , R ⁴ , R ⁵ , R ⁶ are each a methyl group and m ₂ is at least 4. When alkylaluminum chloride is used as a preparation of alumoxane, one or more of R ³ ,
R ⁴ , R ⁵ and R ⁶ may be halogen. ) Among these catalysts, it is preferable to use the catalyst shown in the specific example [II]. (B) Slurry polymerization method The ethylene / α-olefin copolymer is produced by a slurry polymerization method. The slurry polymerization method is a method in which polymerization is carried out using a solid catalyst in an inert hydrocarbon solvent such as pentane, hexane, heptane, octane, decane, etc., and the resulting polymer is obtained in a slurry state. Olefin Copolymer of ethylene and α-olefin having 4 to 18 carbon atoms used in the propylene resin composition of the present invention [Component (B)] Monomer constituting ethylene / α-olefin copolymer of component (B) Having 4 carbon atoms copolymerized with ethylene
1 to 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene,
4-methyl-pentene-1,4-methyl-hexene-
1,4,4-dimethylpentene-1 and the like can be mentioned. Among these preferred α-olefins,
Α having 6 to 12 carbon atoms, particularly preferably 6 to 10 carbon atoms
-An olefin. One or more of these α-olefins can be copolymerized with ethylene. The content of the α-olefin having 4 to 18 carbon atoms in the ethylene / C 4-18 α-olefin copolymer [component (B)] is 10 to 90% by weight, preferably 20% by weight, in component (B). It is preferably from 80 to 80% by weight, particularly preferably from 30 to 70% by weight. If the content of the α-olefin is too high, the amount of the non-crystalline component increases and the molded product becomes “sticky”, which is not preferable. On the other hand, if the content of the α-olefin is too small, the effect of improving the impact resistance is undesirably reduced. (C) MFR The MFR of the ethylene / α-olefin copolymer used in the present invention is from 0.01 to 20 g / 10 min, preferably from 0.01 to 10 g / 10 min, more preferably from 0.0 to 10 g / 10 min.
1 to 5 g / 10 min, most preferably 0.01 to 2 g / 1
0 minutes. If the MFR is too low, poor dispersion in the propylene polymer tends to occur. On the other hand, if the MFR is too high, it is difficult to obtain a sufficient impact strength. (D) Density The density of the ethylene / α-olefin copolymer used in the present invention is 0.913 g / cm ³ or less, preferably 0.853 to 0.900 g / cm ³ , more preferably 0. It has a value of 0.853 to 0.890 g / cm ³ , particularly preferably 0.853 to 0.880 g / cm ³ , and most preferably 0.853 to 0.870 g / cm ³ . If the density is too high, it becomes difficult to obtain sufficient impact strength. Also, with current industrial technology, 0.850 g / cm ³
Although it is difficult to produce a product having a density lower than the value of, it is considered that the effect of the present invention can be exerted even if the value is lower than this value. (3) Other Components [Component (C)] The propylene-based resin composition of the present invention contains auxiliary additives generally used in a method for producing a resin composition, such as an antioxidant, Stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, colorants, lubricants, antistatic agents and the like can be added. In addition, fillers such as calcium carbonate, kaolin, talc, mica, hollow glass spheres, titanium oxide, silica, carbon black, asbestos, glass fibers, potassium titanate fibers, etc., and olefins other than the above-mentioned component (B) used in the present invention Resins and rubbers such as copolymers, polystyrene resins, acrylonitrile-butadiene-styrene copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-propylene rubbers (EPR, EPDM), styrene-butadiene rubbers, polybutadiene, etc. Can also be blended. [II] Composition ratio The mixing ratio of each of the above components (A) and (B) used in the propylene resin composition of the present invention is generally 50 (component (A): component (B)). 97% by weight: 50: 3% by weight, preferably component (A): component (B) = 60 to 95% by weight: 40 to 5% by weight, particularly preferably component (A): component
(B) = 70 to 90% by weight: 30 to 10% by weight. If the mixing ratio of the component (B) is more than the above range, the rigidity is impaired. If the amount is too small, the effect of improving the impact resistance decreases. [III] Production of resin composition (1) Melting and kneading The propylene-based resin composition of the present invention is prepared in the same manner as in the usual production method of a resin composition except that the above components are blended in the above proportions. Can be manufactured. For example, the components (A) and (B) are melted using an extruder, a Brabender plastograph, a Banbury mixer, a kneader blender, etc.
It is common to knead and form pellets by a commonly used method. (2) Molding The pellets can be molded into various molded products. Among them, it is preferable to use the composition of the present invention for injection molding because the effects of the present invention can be exhibited most. The present invention will be described more specifically with reference to experimental examples of the present invention. (1) Evaluation method The evaluation and measurement methods of the physical properties in Examples and Comparative Examples are as follows. (a) MFR: according to JIS K7210 (b) Density: according to JIS K7112 (c) α-olefin content: “Macromolecules” (1982) 1
5,353-360, "Macromolecules" (1982) 15,1402-1406 compliant measuring method according to C ¹³ -MNR listed in (Measurement Conditions) Device: JEOL-GSX270 (manufactured by Nippon Denshi Co.) Solvent: o-Dichlorobenzene (70) / ds-benzene (30) (v / v)% Measurement concentration: 10 (Wt / V)% Temperature: 130 ° C. Spectral width: 11,000 Hz Number of data points: 16 k Number of pulses: 16 μs ( (60 ° C.) Pulse interval: 4 s Accumulated times: 3,000 times (d) Izod impact machine strength: Performed in accordance with JIS K7110 (measuring temperature: −20 ° C., −40 ° C.). (2) Experimental Example Example 1 (1) Synthesis of Propylene / α-Olefin Block Copolymer (Component (A)) Using a Ziegler / Natta catalyst, a known slurry polymerization process was carried out in the first stage. A homopropylene polymer having a MFR of 60 g / 10 min and a density of 0.9075 g / cm ³ was produced, and then, in a second stage, an ethylene content of 25% and a MFR of 25% were prepared.
An ethylene / propylene random copolymer of 0.06 g / 10 min was produced at 10% with respect to the product, and the product MFR was polymerized so that the finished product MFR was 30 g / 10 min. [0030] (2) alpha-olefin copolymer ethylene having 4 to 18 carbon atoms (component (B)) Synthesis Polymerization synthesis catalyst components International Publication Publication WO 91/04257
This was performed in the manner described in the specification. To 2.0 mmol of the complex dimethylsilylene (tetramethylcyclopentadienyl) (cyclododecylaminotitanium dichloride) obtained by the above method, methylalumoxane was added 5,000 mol times with respect to the above complex, and the mixture was reduced to 10 liters with toluene. And then a catalyst solution was prepared, and polymerization was carried out by the following method. 400 ml of toluene and 100 ml of 1-hexene were charged into a continuous autoclave-type continuous reactor having an internal volume of 1.5 liters, and ethylene was separated at a partial pressure of 3 to 5 kg / cm.
^The mixture was fed at ² · G and polymerized at 45 ° C. for 1 hour. After the reaction, M
FR 0.3g / 10min, density 0.860g / c
An ethylene / α-olefin copolymer [component (B)] having m ³ and an α-olefin content of 78.4% by weight was obtained. (3) Production of the composition The propylene polymer having the physical properties shown in Table 1 obtained by the synthesis of the above (1) propylene / α-olefin block copolymer (component (A)) and the above (2) Ethylene, carbon number 4 ~
The ethylene / α-olefin copolymer obtained by synthesizing the α-olefin copolymer (component (B)) of No. 18 was mixed with a Toyo Seiki Labo Plastomill at the compounding ratio shown in Table 1,
Kneading was performed at a temperature of 200 ° C. for 5 minutes. The obtained propylene-based resin composition was press-molded at a temperature of 190 ° C. to a thickness of 4 mm. (4) Evaluation Impact resistance was evaluated using the obtained press sheet. The evaluation results are as shown in Table 1. Example 2 Evaluation was carried out in the same manner as in Example 1 except that dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride was used for the complex in the preparation of the above catalyst component. Table 1 shows the results. Example 3 Evaluation was carried out in the same manner as in Example 1 except that dimethylsilylenebis (tetramethylcyclopentadienyl) (t-butylaminotitanium dichloride) was used for the preparation of the catalyst. Table 1 shows the results. Examples 4-6 and Comparative Examples 2-4 Evaluations were made in the same manner as in Example 1 except that the ethylene / α-olefin copolymer having the physical properties shown in Tables 1 and 2 was used. The results are shown in Tables 1 and 2. Comparative Example 1 The procedure of Example 1 was repeated except that ethylene-propylene copolymer rubber EP-O7P manufactured by Nippon Synthetic Rubber Co., Ltd. was used as the component (B) instead of the ethylene / α-olefin random copolymer. It was molded and evaluated in the same manner. Table 2 shows the results. [Table 1] [Table 2] As described above, the propylene resin composition of the present invention has a significantly improved impact resistance as compared with conventional rubber-like elastic material-mixed materials. It is a very useful material in various fields such as interior and exterior parts of automobiles such as bumpers and instrument panels, and exterior parts of electric equipment.

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Claims (1)

(57) [Claims] (1) A propylene-based resin composition comprising the following components (A) and (B). Component (A) 50 to 97% by weight of a propylene / α-olefin block copolymer comprising the following polymer part (a) and polymer part (b) and having an overall MFR of 5 to 200 g / 10 min. Polymer part (a): A propylene homopolymer part having an MFR of 20 to 200 g / 10 minutes and a density of 0.9070 g / cm ³ or more 80 to 95% by weight Polymer part (b): α-olefin other than propylene Α-olefin / propylene random copolymer part having a content of 20 to 50% by weight and an MFR of 0.01 to 1 g / 10 minutes 20 to 5% by weight The component (B) was produced by a slurry method using a metallocene catalyst. A copolymer of ethylene having the following properties (a ') to (c') and an α-olefin having 4 to 18 carbon atoms: 50 to 3% by weight (a ') MFR is 0.01 to 20 g / 10 min (b ') a density (D) is 0.913 g / cm ³ or less (c') alpha-I Fin content of 10 to 90 weight%