JP2009242509A - Propylene-based resin composition and its molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene-based resin composition having excellent property balance, weld appearance and flow mark appearance and further having high profitability and to provide its molding. <P>SOLUTION: The propylene-based resin composition contains (A) 30 to 97 wt.% propylene-based block copolymer (I) composed of a crystalline propylene polymer component and a propylene-ethylene copolymer component polymerized by using a Ziegler catalyst and satisfying prescribed characteristics, (B) 1 to 40 wt.% elastomer, (C) 1 to 15 wt.% propylene-based block copolymer (II) polymerized by using a metallocene-based catalyst and satisfying prescribed characteristics and (D) 1 to 45 wt.% inorganic filler. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a propylene-based resin composition and a molded article thereof, and more specifically, propylene-based block copolymer (I) polymerized using a Ziegler-based catalyst, an elastomer, and propylene polymerized using a metallocene-based catalyst. The present invention relates to a propylene-based resin composition having a physical property balance, a weld appearance, and a flow mark appearance, and a molded product thereof, comprising a composition containing a system block copolymer (II) and an inorganic filler.

  Propylene-based resin compositions have excellent moldability and mechanical strength as various molded products in the field of industrial parts, such as automotive parts such as bumpers, side moldings, and instrument panels, and parts of household electrical appliances such as televisions. It has been put into practical use by taking advantage of its adaptability to environmental issues and economic characteristics. In particular, moldings in the automotive field are becoming larger, more complicated in design, and are becoming unpainted. Along with this, propylene-based resin compositions and molded articles have a high balance of physical properties (for example, high rigidity and impact). In addition to the development of balance with strength, etc., in order to further increase the product value, welded appearance (linear pattern of the resin flow-matching part) and flow mark (striped pattern along the resin flow direction) are further improved. There is a need to improve and make it less noticeable.

In order to improve the physical property balance of the propylene-based resin composition, it is necessary to improve both of the opposite characteristics of rigidity and impact strength. For example, in a propylene polymer, a propylene-ethylene block copolymer is formed by a metallocene catalyst. Many attempts have been made to improve the rigidity and impact strength in a balanced manner, and a crystalline propylene homopolymer or a copolymer of propylene and a small amount of ethylene and a propylene-ethylene copolymer are exclusively used. The method of manufacturing by two-stage polymerization is used (for example, refer patent documents 1-4).
Furthermore, using a metallocene-based catalyst, a method for producing a propylene-based resin composition having a compatibilizer component of propylene-ethylene copolymer and having an excellent balance of physical properties by at least three-stage polymerization (see, for example, Patent Document 5) ) And a specific component-containing catalyst system such as a metallocene system without blending a rubber-like copolymer with a narrow composition distribution (for example, a method for obtaining a propylene / ethylene / α-olefin copolymer having excellent physical property balance) Documents 6 and 7) have also been proposed.

On the other hand, a technique of adding an inorganic filler such as talc is often used to improve the rigidity level.
Furthermore, for improving the impact strength level, ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR), polystyrene-ethylene / butene-polystyrene triblock copolymer (SEBS), ethylene-octene rubber (EOR), etc. A technique of adding a rubber component and an elastomer is used (for example, see Patent Document 8).
In addition, a technique of adding an elastomer or an inorganic filler to a propylene polymer using a metallocene catalyst to improve the balance between rigidity and impact strength is used (see, for example, Patent Document 9).
Furthermore, a propylene-based resin composition that balances rigidity and impact strength is achieved by combining a propylene-based block copolymer with a metallocene-based catalyst with a propylene-based block copolymer with an elastomer, an inorganic filler, and a Ziegler-based catalyst. Attempts have also been made (see, for example, Patent Documents 10 and 11).

Regarding the improvement of weld appearance and flow mark (tiger mark), a composition in which an ethylene / α-olefin copolymer rubber (elastomer) and an inorganic filler are blended with a specific propylene resin is disclosed (for example, And Patent Documents 12 to 15).
Moreover, in order to improve the physical properties of the propylene-based resin composition and the appearance of molding such as a tiger mark, a composition is disclosed that is blended with a specific three types of polypropylene components together with an inorganic filler by reducing the post-addition amount of rubber components. (For example, refer to Patent Document 16).
The present inventors have combined a propylene-based block copolymer composition based on a metallocene catalyst, a propylene-based block copolymer based on a Ziegler-based catalyst and an elastomer, and a propylene-based polymer having excellent physical property balance and molding appearance (flow mark appearance). The resin composition was proposed previously (refer patent document 17).

  However, although these propylene-based resin compositions have achieved some improvement in physical property balance and some improvement in weld appearance and flow mark appearance, the size of the molded body, the complexity of the design, and the thinning of the molded body will continue to increase. As a result, it is still insufficient to develop a comprehensive balance of these performances at a high level.

JP-A-4-337308 Japanese Patent Laid-Open No. 5-202152 JP-A-6-172414 JP-A-8-67783 WO95 / 27741 JP 9-316147 A JP-A-10-158351 JP-A-11-29669 JP-A-10-1573 JP 2003-147157 A JP 2003-147158 A JP-A-9-194646 JP 2000-26697 A JP 2006-124520 A JP 2006-193643 A JP 2003-301086 A JP 2007-2111189 A

  An object of the present invention is to provide a propylene-based resin composition that is excellent in physical property balance, weld appearance, and flow mark appearance, and also has high economic efficiency, and a molded article thereof, in view of the above-described problems of the prior art. .

  In order to solve the above problems, the present inventors have made various studies, and as a result, a propylene-based block copolymer that is polymerized using a Ziegler-based catalyst, an elastomer, and a propylene-based polymerized using a metallocene-based catalyst. Propylene-based resin composition obtained by blending block copolymer and inorganic filler at a specific ratio has excellent physical property balance and has a weld appearance and flow mark appearance during injection molding and injection compression molding. It has been found that it has excellent performance and is also economical, and has completed the present invention.

That is, according to the first invention of the present invention, (A) a crystalline propylene polymer component and a propylene / ethylene copolymer component polymerized using a Ziegler-based catalyst, the following characteristics 1) to 5: The propylene-based block copolymer (I) satisfying (1) 30 to 97% by weight, (B) elastomer 1 to 40% by weight, (C) polymerized using a metallocene catalyst, the following characteristics 6) to 11) A propylene-based resin composition comprising 1 to 15% by weight of a propylene-based block copolymer (II) and (D) 1 to 45% by weight of an inorganic filler is provided.
Characteristic 1) It consists of crystalline propylene polymer component (a) 65 to 97% by weight and propylene / ethylene copolymer component (b) 3 to 35% by weight.
Characteristic 2) The MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (a) is 10 to 600 g / 10 minutes.
Characteristic 3) The ethylene content of the propylene / ethylene copolymer component (b) is 30 to 70% by weight.
Characteristic 4) The weight average molecular weight of the propylene / ethylene copolymer component (b) is 50,000 to 2,000,000.
Characteristic 5) MFR (230 ° C., 2.16 kg load) of the whole component is 5 to 300 g / 10 minutes.
Characteristic 6) It consists of 25 to 70% by weight of a crystalline propylene polymer component (c) and 30 to 75% by weight of a propylene / ethylene copolymer component (d).
Characteristic 7) The MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (c) is 40 to 350 g / 10 minutes.
Characteristic 8) The melting point obtained by differential scanning calorimetry (DSC) of the crystalline propylene polymer component (c) is 156 ° C. or higher.
Characteristic 9) The ethylene content of the propylene / ethylene copolymer component (d) is 10 to 30% by weight.
Characteristic 10) The weight average molecular weight of the propylene / ethylene copolymer component (d) is 250,000 to 1,000,000.
Characteristic 11) MFR (230 ° C., 2.16 kg load) of the whole component is 5 to 200 g / 10 minutes.

  Further, according to the second invention of the present invention, in the first invention, the component (C) contains 45 to 70% by weight of a propylene / ethylene copolymer component (d) having an ethylene content of 10 to 25% by weight. A propylene-based resin composition is provided.

  Further, according to the third invention of the present invention, in the first or second invention, the component (A) is 43 to 87 wt%, the component (B) is 3 to 15 wt%, and the component (C) is 6 to 12 wt%. And a propylene-based resin composition comprising 4 to 30% by weight of component (D).

（一般式［Ｉ］中において、Ａ^１およびＡ^２は、共役五員環配位子〔同一化合物内ではＡ^１およびＡ^２は同一でも異なっていてもよい〕を示し、結合性基Ｑに結合していない共役五員環の炭素は置換基を有してもよく、Ｑは、２つの共役五員環配位子を任意の位置で架橋する結合性基、Ｍは、周期律表４〜６族から選ばれる金属原子を示し、ＸおよびＹは、それぞれ独立してＭと結合した、水素原子、ハロゲン原子、炭化水素基、アミノ基、ハロゲン化炭化水素基、酸素含有炭化水素基、窒素含有炭化水素基、リン含有炭化水素基またはケイ素含有炭化水素基を示す。） According to a fourth invention of the present invention, in any one of the first to third inventions, the metallocene catalyst is (a) a transition metal compound represented by the following general formula [I], and (a) Selected from the group consisting of (a-1) an organoaluminum oxy compound, (b-2) a compound capable of reacting with a transition metal compound to form a cation, and (b-3) an ion-exchange layered compound (including silicate). The propylene-based resin composition is characterized in that it comprises at least one activator as an essential component and (c) an organoaluminum compound as an optional component.

(In the general formula [I], A ¹ and A ² represent a conjugated five-membered ring ligand (in the same compound, A ¹ and A ² may be the same or different). The carbon of the conjugated five-membered ring that is not bonded may have a substituent, Q is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and M is a periodic table 4 A metal atom selected from Group -6, X and Y are each independently bonded to M, a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, Nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group is shown.)

  Furthermore, according to the fifth invention of the present invention, there is provided a molded body characterized by molding the propylene-based resin composition of any one of the first to fourth inventions by injection molding or injection compression molding. The

  By using the propylene-based resin composition of the present invention, it is possible to more economically obtain a molded article having excellent physical property balance and good weld appearance and flow mark appearance in injection molding, injection compression molding and the like.

  This invention contains each component of a component (A) propylene-type block copolymer (I), a component (B) elastomer, a component (C) propylene-type block copolymer (II), and a component (D) inorganic filler. A propylene-based resin composition and a molded body thereof. Hereinafter, each component of a propylene-type resin composition, manufacture of a propylene-type resin composition, and a molded object are demonstrated in detail.

[I] Components of propylene-based resin composition Component (A) Propylene block copolymer (I)
The propylene block copolymer (I) of component (A) used in the propylene resin composition of the present invention is polymerized using a Ziegler catalyst and has the following characteristics 1) to 5). It is a copolymer.
Characteristic 1) It consists of crystalline propylene polymer component (a) 65 to 97% by weight and propylene / ethylene copolymer component (b) 3 to 35% by weight.
Characteristic 2) The MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (a) is 10 to 600 g / 10 minutes.
Characteristic 3) The ethylene content of the propylene / ethylene copolymer component (b) is 30 to 70% by weight.
Characteristic 4) The weight average molecular weight of the propylene / ethylene copolymer component (b) is 50,000 to 2,000,000.
Characteristic 5) MFR (230 ° C., 2.16 kg load) of the whole component is 5 to 300 g / 10 minutes.

(1) Polymerization catalyst A Ziegler polymerization catalyst is used for the production of this propylene-based block copolymer (I).
As the type of the polymerization catalyst, a highly stereoregular catalyst is usually used. For example, a titanium trichloride or titanium trichloride composition obtained by reduction with organoaluminum as a titanium compound is treated with an electron-donating compound and further activated (for example, JP-A-47-34478, JP-A No. 58-23806 and JP-A 63-146906), so-called supported catalysts obtained by loading titanium tetrachloride on a carrier such as magnesium chloride (for example, JP-A 58-157808, JP-A-58-83006, JP-A-58-5310, JP-A-61-2218606, etc.). As these catalysts, known catalysts can be used without any particular limitation.

  Usually, an organoaluminum compound is used as a promoter. Examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, alkylaluminum halide such as diethylaluminum chloride and diisobutylaluminum chloride, alkylaluminum hydride such as diethylaluminum hydride, and diethylaluminum ethoxide. And alkylaluminum alkoxides such as methylalumoxane and tetrabutylalumoxane, and complex organoaluminum compounds such as dibutyl methylboronate and lithium aluminum tetraethyl. Moreover, these may be used individually by 1 type and may be used in combination of 2 or more type.

  In addition, various polymerization additives for the purpose of improving stereoregularity, controlling particle properties, controlling soluble components, controlling molecular weight distribution, and the like can be used for the above-described catalyst. Examples of the polymerization additive include organic silicon compounds such as diphenyldimethoxysilane and tert-butylmethyldimethoxysilane, esters such as ethyl acetate, butyl benzoate, methyl p-toluate, and dibutylphthalate, acetone, and methyl isobutyl ketone. And electron donating compounds such as ketones such as diethyl ether, ethers such as diethyl ether, organic acids such as benzoic acid and propionic acid, and alcohols such as ethanol and butanol.

(2) Production method The production method of this propylene-based block copolymer (I) is not particularly limited, but is a preceding step for producing the crystalline propylene polymer component (a), followed by a copolymer of propylene and ethylene. A polymerization method comprising a subsequent step for producing the component (b) is preferred.
As polymerization methods, slurry polymerization using an inert hydrocarbon such as hexane, heptane, octane, benzene or toluene as a polymerization solvent, bulk polymerization using propylene itself as a polymerization solvent, or polymerization of propylene as a raw material in a gas phase state. Gas phase polymerization is possible.
Moreover, it is also possible to carry out by combining these polymerization formats. For example, a method in which the crystalline propylene polymer component (a) is carried out by bulk polymerization and the propylene / ethylene copolymer component (b) is carried out by gas phase polymerization, or the crystalline propylene polymer component (a) is produced by gas phase polymerization. The propylene / ethylene copolymer component (b) is also conducted by vapor phase polymerization.

(I) Production of crystalline propylene polymer component (a) In the preceding polymerization step for producing crystalline propylene polymer component (a), hydrogen is supplied as propylene and a chain transfer agent, and in the presence of the catalyst. Polymerization is carried out to produce a crystalline propylene polymer component (a).

The polymerization step in the previous stage consists of a propylene homopolymer (propylene homopolymer) or a copolymer of propylene and α-olefin (propylene / α-olefin copolymer) in one stage or multiple stages in total polymerization amount (propylene block copolymer). It is a step of forming so as to correspond to 65 to 97% by weight, preferably 70 to 95% by weight, more preferably 75 to 90% by weight of the whole of the polymer (I). Here, the α-olefin is an α-olefin having 4 to 20 carbon atoms other than propylene including ethylene, such as 1-butene, 1-hexene, 4-methyl-pentene-1, 1-octene, 1-octene, Examples include decene. Of these, ethylene is most preferred. When α-olefin is used, the amount used is 10% by weight or less, preferably 5% by weight or less, based on the total monomers (total of propylene and α-olefin).
When the formation amount of the crystalline propylene polymer component (a) with respect to the total polymerization amount is less than 65% by weight of the total polymerization amount, the rigidity, weld appearance and flow mark appearance of the propylene-based resin composition and the molded product thereof are lowered. If it exceeds 97% by weight, the impact strength is lowered.

  The polymerization temperature in the preceding polymerization step is about 30 to 120 ° C, preferably about 50 to 90 ° C. The polymerization pressure is 0.1 to 6 MPa, preferably 0.1 to 4 MPa. Moreover, it is preferable to use a molecular weight (MFR) adjusting agent so that the fluidity of the polymer is appropriate, and hydrogen is preferable as the adjusting agent.

  The range of MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (a) is 10 to 600 g / 10 minutes, preferably 30 to 400 g / 10 minutes, more preferably 50 to 300 g / 10 minutes. is there. When the MFR is less than 10 g / 10 minutes, the weld appearance and the flow mark appearance of the propylene-based resin composition and the molded product thereof are deteriorated, and when it exceeds 600 g / 10 minutes, the impact strength is reduced.

(Ii) Production of propylene / ethylene copolymer component (b) In the subsequent polymerization step for producing the propylene / ethylene copolymer component (b), propylene, ethylene and hydrogen are continuously supplied, and the catalyst Copolymerization of propylene and ethylene is carried out in the presence of (the catalyst used in the preceding polymerization step) to produce a propylene / ethylene copolymer component (b), and as a final product, component (A) Propylene-based block copolymer (I) is obtained.

In the subsequent step, the propylene / ethylene copolymer component (b) is added in an amount of 3 to 35% by weight, preferably 5 to 30% by weight, more preferably, of the total polymerization amount (total of the propylene-based block copolymer (I)). An amount corresponding to 10-25% by weight is formed. When the formation amount with respect to the total polymerization amount of the propylene / ethylene copolymer component (b) is less than 3% by weight, the impact strength of the propylene-based resin composition and the molded product thereof is lowered, and when it exceeds 35% by weight, Stiffness, weld appearance and flow mark appearance are reduced.
Here, this copolymer component can further contain, for example, an α-olefin having 4 to 20 carbon atoms, a diene monomer, or the like as the third component. In that case, the content of these third components is preferably 10% by weight or less.

  The polymerization temperature in the subsequent polymerization step is about 30 to 120 ° C, preferably about 50 to 80 ° C. The polymerization pressure is 0.1 to 5 MPa, preferably 0.5 to 4 MPa.

  In the subsequent step, a propylene / ethylene copolymer component (b) having an ethylene content in the range of 30 to 70% by weight, preferably 32 to 60% by weight, and more preferably 35 to 55% by weight is produced. When the ethylene content in the propylene / ethylene copolymer component (b) is less than 30% by weight, the impact strength and rigidity of the propylene-based resin composition and the molded product thereof are lowered, and when it exceeds 70% by weight, the impact strength is increased. Deterioration of tensile properties and weld appearance occurs.

  Furthermore, the range of the weight average molecular weight of the propylene / ethylene copolymer component (b) is 50,000 to 2,000,000, preferably 80,000 to 1,000,000, and more preferably 100,000 to 250,000. When the weight average molecular weight of the propylene / ethylene copolymer component (b) is less than 50,000, the impact strength of the propylene-based resin composition and the molded product thereof decreases. The molding appearance due to point generation and the like deteriorates, respectively.

  The range of MFR (230 ° C., 2.16 kg load) of the entire component (A) propylene-based block copolymer (I) is 5 to 300 g / 10 minutes, preferably 10 to 250 g / 10 minutes, and more preferably 15 to 200 g / 10 min. When the MFR is less than 5 g / 10 minutes, the weld appearance and the flow mark appearance of the propylene-based resin composition and the molded product thereof are deteriorated, and when it exceeds 300 g / 10 minutes, the impact strength is reduced.

In addition, the component (A) propylene-based block copolymer (I) is used within the range that does not significantly impair the essence of the present invention, such as α-olefin such as 1-butene, vinyl acetate and the like. It may be a ternary or higher copolymer containing an unsaturated organic acid such as vinyl ester or maleic anhydride or a derivative thereof, or a mixture thereof.
The MFR, propylene / ethylene copolymer component (b) content, ethylene content, and weight average molecular weight were measured with an MFR meter, CFC fractionator, Fourier transform infrared absorption spectrum analysis, and gel permeation chromatography (GPC). The value to be Measurement conditions will be described later in Examples.

(3) Blending ratio The blending ratio of the component (A) propylene-based block copolymer (I) in the propylene-based resin composition of the present invention is 30 to 97% by weight, preferably 30 to 91% by weight, particularly preferably. 43 to 87% by weight. If the blending ratio of component (A) is less than 30% by weight, the rigidity and flow mark appearance of the propylene resin composition and its molded product will decrease, and if it exceeds 97% by weight, the weld appearance and impact strength will decrease. To do.
In addition, as long as a component (A) is in the above-mentioned characteristic range, two or more kinds may be used in combination.

2. Component (B) Elastomer The component (B) elastomer used in the propylene resin composition of the present invention is an ethylene / α-olefin elastomer or a styrene elastomer, and the impact strength of the propylene resin composition and its molded product is increased. It is used for the purpose of improving the balance of physical properties at the center and exhibiting good moldability and dimensional characteristics.
Of the ethylene / α-olefin elastomers and styrene elastomers, it is preferable to use ethylene / α-olefin elastomers in terms of moldability and economy.

Here, the ethylene / α-olefin-based elastomer is a rubber-like random copolymer of ethylene and α-olefin, and is usually also referred to as ethylene-based rubber, and is itself supplied in the form of pellets or crumbs. Examples include Mitsui Chemicals' Toughmer, EBM, and Dow Chemical Japan's Engage.
As this ethylene / α-olefin-based elastomer, it is preferable to use one having an elution component as measured by a CFC analyzer of 98% by weight or more at 40 ° C. or less.
Examples of the α-olefin to be copolymerized include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and the like. Of these, 1-butene, 1-hexene and 1-octene are preferable.
The content of α-olefin in the ethylene / α-olefin elastomer is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the density is preferably 0.80 to 0.90 g / cm ^3. More preferably, it is 0.86-0.88 g / cm < ³ >.

The styrene elastomer is a block or random copolymer of styrene and ethylene, propylene, 1-butene, butadiene, isoprene or the like, or a hydrogenated product thereof. The amount of bound styrene in the styrene elastomer is preferably 5 ˜45 wt%, more preferably 10 to 40 wt%, and the density is preferably 0.88 to 0.95 g / cm ³ , more preferably 0.89 to 0.92 g / cm ³ . is there.

  The ethylene / α-olefin-based elastomer can be produced by polymerization using a known titanium-based catalyst or metallocene-based catalyst. In the case of a styrene-based elastomer, it can be obtained by a usual anionic polymerization method and its polymer hydrogenation technique.

The MFR (230 ° C., 2.16 kg load) of these elastomers needs to be 0.1 g / 10 min or more, preferably 0.1 to 80 g / 10 min, particularly preferably 1 to 30 g / 10 min. is there. If the MFR is less than 0.1 g / 10 min, the weld appearance, flow mark appearance, moldability, and paintability of the propylene-based resin composition and the molded product thereof become inferior.
Two or more of these elastomers may be used in combination.

  The blending ratio of the component (B) elastomer in the propylene-based resin composition of the present invention is 1 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 3 to 15% by weight. When the blending ratio of the elastomer is less than 1% by weight, the impact strength of the propylene-based resin composition and the molded product thereof is insufficient, and when it exceeds 40% by weight, rigidity, heat resistance, weld appearance, flow mark appearance, and economy are achieved. Sex is reduced.

3. Component (C) Propylene-based block copolymer (II)
Component (C) propylene-based block copolymer (II) used in the propylene-based resin composition of the present invention is a propylene-based block copolymer that is polymerized using a metallocene-based catalyst, and has the following characteristic 6): To 11).
Characteristic 6) It consists of 25 to 70% by weight of a crystalline propylene polymer component (c) and 30 to 75% by weight of a propylene / ethylene copolymer component (d).
Characteristic 7) The MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (c) is 40 to 350 g / 10 minutes.
Characteristic 8) The melting point obtained by differential scanning calorimetry (DSC) of the crystalline propylene polymer component (c) is 156 ° C. or higher.
Characteristic 9) The ethylene content of the propylene / ethylene copolymer component (d) is 10 to 30% by weight.
Characteristic 10) The weight average molecular weight of the propylene / ethylene copolymer component (d) is 250,000 to 1,000,000.
Characteristic 11) MFR (230 ° C., 2.16 kg load) of the whole component is 5 to 200 g / 10 minutes.
This propylene-based block copolymer (II) is used in the propylene-based resin composition of the present invention, mainly when the compatibility between the component (A) and the component (B) is controlled and it is insufficient. It is used for the purpose of preventing, suppressing, and further improving the appearance of molded products centering on the appearance of welds that tend to occur and the deterioration of the balance of physical properties centering on impact strength.

(1) Polymerization catalyst Component (C) used in the propylene-based resin composition of the present invention (C) Propylene-based block copolymer (II) requires precise index control, so the molecular weight distribution of the polymer A metallocene catalyst having a narrow and uniform copolymer composition is used.
Furthermore, in order to produce this propylene-based block copolymer (II) industrially easily and inexpensively, (a) a transition metal compound represented by the following general formula [I], and a later-described ( The group consisting of (a) (b-1) an organoaluminum oxy compound, (b-2) a compound capable of reacting with a transition metal compound to form a cation, and (b-3) an ion-exchange layered compound (including silicate). It is preferable to use a metallocene-based catalyst having at least one activator selected from the following as an essential component and (c) an organoaluminum compound as an optional component, and among them, (a) and (b-3) and optional Most preferably, a metallocene catalyst comprising an organoaluminum compound as a component is used.

（一般式［Ｉ］中において、Ａ^１およびＡ^２は、共役五員環配位子〔同一化合物内ではＡ^１およびＡ^２は同一でも異なっていてもよい〕を示し、結合性基Ｑに結合していない共役五員環の炭素は置換基を有してもよく、Ｑは、２つの共役五員環配位子を任意の位置で架橋する結合性基、Ｍは、周期律表４〜６族から選ばれる金属原子を示し、ＸおよびＹは、それぞれ独立してＭと結合した、水素原子、ハロゲン原子、炭化水素基、アミノ基、ハロゲン化炭化水素基、酸素含有炭化水素基、窒素含有炭化水素基、リン含有炭化水素基またはケイ素含有炭化水素基を示す。） (I) (A) Transition metal compound The transition metal compound mainly used in the present invention is a metallocene complex represented by the following formula.

(In the general formula [I], A ¹ and A ² represent a conjugated five-membered ring ligand (in the same compound, A ¹ and A ² may be the same or different). The carbon of the conjugated five-membered ring that is not bonded may have a substituent, Q is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and M is a periodic table 4 A metal atom selected from Group -6, X and Y are each independently bonded to M, a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, Nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group is shown.)

Typical examples of the conjugated five-membered ring ligand include a cyclopentadienyl group. This cyclopentadienyl group may have 4 hydrogen atoms, and as described above, some of the hydrogen atoms may be substituted with substituents. One specific example of the above substituent is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, phenyl group, naphthyl group, butenyl group, butadienyl group, and triphenylcarbyl group. The hydrocarbon group may be bonded to the cyclopentadienyl group as a monovalent group, and two types may be bonded at the end of the substituent to form a condensed ring. Typical examples of the cyclopentadienyl group having a condensed ring include compounds such as indene, fluorene, and azulene, and derivatives thereof. Among these, indene, azulene and derivatives thereof are more preferable, and among them, azulene is most preferable.
Examples of the substituent other than the hydrocarbon group include hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur. Typical examples thereof include methoxy group, ethoxy group, phenoxy group, furyl group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, carbazolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group. , Dimethoxyboron group, thienyl group and the like. Examples of other substituents include a halogen atom or a halogen-containing hydrocarbon group. Typical examples thereof include chlorine, bromine, iodine, fluorine, trichloromethyl group, trifluoromethyl group, fluorophenyl group, pentafluorophenyl group and the like.

By the way, the characteristic of the preferable transition metal compound used in the present invention is that at least one of A ¹ and A ² is bonded to an adjacent substituent on the conjugated five-membered ring ligand and includes two atoms of the five-membered ring. And having a 7-10 membered condensed ring. That is, either ^one of A ¹ and A ² can form a 7 to 10 condensed ring including at least two adjacent carbon atoms of a conjugated five-membered ring.
The carbon of the condensed ring may be saturated or unsaturated except for two atoms of the conjugated five-membered ring. For example, the above-mentioned ligands constituting A ¹ and A ² include hydroazurenyl group, methylhydroazurenyl group, ethylhydroazurenyl group, dimethylhydroazurenyl group, methylethylhydroazurenyl group, methylisopropyl Hydroazurenyl group, methylphenylisopropylhydroazurenyl group, hydrogenated products of various azulenyl groups, bicyclo- [6.3. -Undecanyl group, methyl-bicyclo- [6.3.0] -undecanyl group, ethyl-bicyclo- [6.3.0] -undecanyl group, phenyl-bicyclo- [6.3.0] -undecanyl group, methyl Phenyl-bicyclo- [6.3.0] -undecanyl group, ethylphenyl-bicyclo- [6.3.0] -undecanyl group, methyldiphenyl-bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo -[6.3.0] -undecadienyl group, methylphenyl-bicyclo- [6.3.0] -undecadienyl group, ethylphenyl-bicyclo- [6.3.0] -undecadienyl group, methylisopropyl-bicyclo- [ 6.3.0] -undecadienyl group, bicyclo- [7.3.0] -dodecanyl group and derivatives thereof, bicyclo- [7.3. - dodecadienyl group and derivatives thereof, bicyclo - [8.3.0] - tridecanyl group and derivatives thereof, bicyclo - [8.3.0] - such Toridekajieniru group and a derivative thereof. Examples of the substituent of each group include the hydrocarbon groups described above, hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, sulfur, halogen atoms, or halogen-containing hydrocarbon groups.

Q represents a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position. That is, Q is a divalent linking group and crosslinks A ¹ and A ² .
The type of Q is not particularly limited, and specific examples thereof include (a) a divalent hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, specifically, An unsaturated hydrocarbon group such as an alkylene group, a cycloalkylene group, an arylene, a haloalkylene group, a halocycloalkylene group, (b) a silylene group or an oligosilylene group, and (c) a carbon number of usually 1 to 20, preferably 1 to A silylene group or an oligosilylene group having 12 hydrocarbon groups or a halogenated hydrocarbon group as a substituent, (d) a germylene group, (e) a hydrocarbon group or a halogenated hydrocarbon group usually having 1 to 20 carbon atoms. Examples thereof include a germylene group as a substituent.
Among these, a silylene group or a germylene group having an alkylene group, a cycloalkylene group, an arylene group, or a hydrocarbon group as a substituent is preferable.

  M represents a transition metal atom selected from groups 4 to 6 of the periodic table (short-period type), preferably a group 4 transition metal of titanium, zirconium or hafnium, more preferably zirconium or hafnium. Particularly preferred is hafnium.

X and Y are each independently a hydrogen atom, halogen atom, hydrocarbon group, amino group, halogenated hydrocarbon group, oxygen-containing hydrocarbon group, nitrogen-containing hydrocarbon group or phosphorus-containing hydrocarbon group bonded to M. Or a silicon-containing hydrocarbon group is shown.
Carbon number in each said hydrocarbon group is 1-20 normally, Preferably it is 1-12. Among these, a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamino group, and a diethylamino group are preferable.

As specific examples of the transition metal compound in the present invention, the following compounds are particularly preferable. In addition, although description of a compound is only designated only with the chemical name, the three-dimensional structure means both the compound with asymmetry and the compound with symmetry as used in the present invention.
(1) Chloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4H-azulenyl}] zirconium, (2) Dichloro [1,1′-dimethylsilylenebis {2-methyl -4- (4-t-butylphenyl) -4H-azurenyl}] hafnium, (3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4H -Azurenyl}] hafnium, (4) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4H-5,6,7,8-tetrahydroazurenyl}] Hafnium, (5) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl}] hafnium, (6) dichloro [ 1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-5,6,7,8-tetrahydroazurenyl}] hafnium, (7) dichloro [1,1 '-Dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4H-azulenyl}] hafnium, (8) dichloro [1,1'-dimethylsilylenebis {2-ethyl- 4- (3-chloro-4-trimethylsilylphenyl) -4H-azurenyl}] hafnium, (9) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-3-methyl-phenyl) ) -4H-azulenyl}] hafnium, (10) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-3,5-dichloro) Ro-phenyl) -4H-azurenyl}] hafnium, (11) dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl}] Hafnium, (12) dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dimethylphenyl) -4H-azurenyl}] hafnium, and the like can be exemplified.
One or both of the dichlorides forming the X and Y moieties in the compound as described above are hydrogen atom, fluorine atom, bromine atom, iodine atom, methyl group, ethyl group, isobutyl group, phenyl group, fluorophenyl group, benzyl group, Examples also include compounds substituted for a methoxy group, a dimethylamino group, a diethylamino group, and the like. In addition, compounds in which the central metal of the compound exemplified above is replaced with titanium, tantalum, niobium, vanadium, tungsten, molybdenum or the like instead of zirconium or hafnium can be exemplified.
Among these, a group 4 transition metal compound of zirconium, titanium, and hafnium is preferable, and hafnium is particularly preferable among them.
These components (a) may be used in combination of two or more. Further, the component (a) may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

(Ii) (a) Cocatalyst (activator component)
In the present invention, the component (A) includes (A-1) an organoaluminum oxy compound, (B-2) a compound capable of reacting with a transition metal compound to form a cation, and (A-3) an ion-exchange layered compound. An activator comprising any one or more of (including silicates) is used.

上記各一般式中、Ｒ^１は水素原子または炭化水素基、好ましくは炭素数１〜１０、特に好ましくは炭素数１〜６の炭化水素基を示す。また、複数のＲ^１はそれぞれ同一でも異なっていてもよい。また、ｐは０〜４０、好ましくは２〜３０の整数を示す。
一般式のうち、一番目および二番目の式で表される化合物は、アルミノキサンとも称される化合物であって、これらの中では、メチルアルミノキサンまたはメチルイソブチルアルミノキサンが好ましい。上記のアルミノキサンは、各群内および各群間で複数種併用することも可能である。そして、上記のアルミノキサンは、公知の様々な条件下に調製することができる。
一般式の三番目で表される化合物は、一種類のトリアルキルアルミニウムまたは二種類以上のトリアルキルアルミニウムと、一般式Ｒ^２Ｂ（ＯＨ）_２で表されるアルキルボロン酸との１０：１〜１：１（モル比）の反応により得ることができる。一般式中、Ｒ^１およびＲ^２は、炭素数１〜１０、好ましくは炭素数１〜６の炭化水素基を示す。 In the present invention, the (a-1) organoaluminum oxy compound specifically includes compounds represented by the following general formulas.

In the above general formulas, R ¹ represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. Moreover, several R < ¹ > may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30.
Among the general formulas, the compounds represented by the first and second formulas are compounds also referred to as aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.
The compound represented by the third general formula is 10: 1 to 1 type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ² B (OH) ₂ . It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula, R ¹ and R ² represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

In the present invention, the compound capable of reacting with the transition metal compound (A-2) to form a cation is an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation. A compound or Lewis acid is used. As such an ionic compound, a cation such as a carbonium cation or an ammonium cation and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, or tris (pentafluorophenyl) boron are used. Examples include complexed products.
Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with (A) component and can convert (A) component into a cation.
The reaction product of component (a) and (b-1) or the reaction product of component (a) and (b-2) should be used as a catalyst supported on a particulate carrier such as silica. Is most preferred.

In the present invention, (I-3) an ion-exchange layered compound (including silicate) is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force. Ions can be exchanged. Examples of the ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close-packed packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type.
Specific examples of the ion-exchange layered compound having such a crystal structure include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) 2 .3H. ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, y-Zr (HPO ₄ ) ₂ , y-Ti _{(HPO 4) 2, y-} Ti (NH4PO4) polyvalent metal crystalline acid salts of such 2 · _{H 2} O and the like.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. A synthetic product may be used for these, and the mineral produced naturally may be used. Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Smectites such as stones, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, sea chlorite, etc., attapulgite, sepiolite, pygorskite, bentonite , Kibushi clay, gyrome clay, hysingelite, pyrophyllite, chlorite and the like. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.
Of these specific examples, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, serpentine groups such as chrysotile, lizardite and antigolite, montmorillonite, sauconite and beidellite. , Smectites of nontronite, saponite, hectorite, etc., vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, chlorophyll, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, Preferably, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hector Ito, synthetic saponite, synthetic taeniolite.

These ion-exchangeable layered compounds may be used as they are, but are acid-treated with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , MgSO ₄ , ZnSO ₄ , Ti (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) _{3 and the} like are preferably subjected to salt treatment. In addition, shape control such as pulverization and granulation may be performed, and granulation is preferable in order to obtain a block copolymer having excellent particle properties. The above components are usually used after being dehydrated and dried.

(Iii) (U) Organoaluminum compound An example of an organoaluminum compound used as the (U) component of the present invention is represented by the following formula: AlR _m X _3-m
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, alkoxy group, aryloxy group, m is a number of 0 <m ≦ 3)
Specifically, it is a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or a halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or diethylaluminum ethoxide. .
In addition, aluminoxane such as methylaluminoxane can also be used.
Of these, trialkylaluminum is particularly preferred. These (U) components may be used in combination of two or more. In addition, a component (c) may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

(Iv) Contact treatment of catalyst component The above component (a), component (b), and optional component (c), which are optionally used as necessary, are usually brought into contact when the catalyst is prepared. The contacting method is not particularly limited, and the contacting may be performed at the time of pre-polymerization with olefin, or at the time of polymerization of olefin, in addition to the catalyst preparation. A polymer such as polyethylene or polypropylene and a solid of an inorganic oxide such as silica or alumina may be allowed to coexist or contact when each catalyst component is contacted or after contact.
The contact may be performed in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene. The contact temperature is preferably selected in the range of −20 ° C. to the boiling point of the solvent, particularly in the range of room temperature to the boiling point of the solvent.

(V) Use amount of catalyst component The use amount of each catalyst component is usually in the range of 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, per 1 g of component (a-3). To be elected. The component (c) is selected in the range of 0.001 to 10,000 mmol, preferably 0.01 to 100 mmol.
The atomic ratio of the transition metal in component (a) to aluminum in component (c) is usually in the range of 1: 0.01 to 1,000,000, preferably 0.1 to 100,000. Chosen by
The catalyst thus obtained may be used without washing as it is, or may be used after washing.

(Vi) Prepolymerization Before polymerization, olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and styrene Can be used as a catalyst after preliminary polymerization. This prepolymerization may be performed in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene.

(2) Production method The production method of the component (C) propylene-based block copolymer (II) used in the present invention is not particularly limited, but the preceding step of producing the crystalline propylene polymer component (c), A polymerization method comprising a subsequent step for producing a copolymer component (d) of propylene and ethylene is preferred.
As the polymerization process, a slurry method, a bulk method, a gas phase method, a solution method and the like can be arbitrarily used. Among them, the production of the crystalline propylene polymer component (c) in the previous stage is performed by a bulk method or a gas phase method. It is most preferable to carry out the production of the copolymer component (d) of propylene and ethylene in the latter stage by a gas phase method. As a polymerization method, either a batch polymerization method or a continuous polymerization method can be employed.
The polymerization temperature can be used without any particular problem as long as it is in a commonly used temperature range. Specifically, a range of 0 ° C. to 200 ° C., preferably 40 ° C. to 100 ° C. can be used. Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 and 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, it is possible to coexist an inert gas such as nitrogen.
In addition, the component ratio of the components (c) and (d) can be adjusted by controlling the production amount ratio of each component. Moreover, it is preferable to use a molecular weight (MFR) adjusting agent so that the fluidity of the polymer is appropriate, and hydrogen is preferable as the adjusting agent.

(I) Production of Crystalline Propylene Polymer Component (c) In the preceding polymerization step for producing the crystalline propylene polymer component (c), the production is performed using a metallocene catalyst. That is, a propylene homopolymer (propylene homopolymer) or a copolymer of propylene and an α-olefin (propylene / α-olefin copolymer) is combined in one or more stages with a total polymerization amount (propylene block copolymer (II ) In a total of 25 to 70% by weight, preferably 30 to 65% by weight, more preferably 30 to 55% by weight. Here, the α-olefin is an α-olefin having 4 to 20 carbon atoms other than propylene including ethylene, such as 1-butene, 1-hexene, 4-methyl-pentene-1, 1-octene, 1-octene, Examples include decene. Of these, ethylene is most preferred. When α-olefin is used, the amount used is 10% by weight or less, preferably 5% by weight or less, based on the total monomers (total of propylene and α-olefin).
When the formation amount of the crystalline propylene polymer component (c) with respect to the total polymerization amount (the entire propylene block copolymer (II)) is less than 25% by weight, the rigidity of the propylene resin composition and the molded product thereof The weld appearance and the flow mark appearance deteriorate, and when it exceeds 70% by weight, the impact strength decreases.

  The range of MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (c) is 40 to 350 g / 10 minutes, preferably 50 to 300 g / 10 minutes, more preferably 60 to 250 g / 10 minutes. is there. When the MFR is less than 40 g / 10 minutes, the weld appearance and the flow mark appearance of the propylene-based resin composition and the molded product thereof are deteriorated, and when it exceeds 350 g / 10 minutes, the impact strength is reduced.

  The melting point obtained by differential scanning calorimetry (DSC) of the crystalline propylene polymer component (c) is 156 ° C. or higher, preferably 157 ° C. or higher, more preferably 158 ° C. or higher. When the melting point is less than 156 ° C., the rigidity of the propylene-based resin composition and the molded body thereof is lowered. There is no particular need to define the upper limit of the melting point, but those exceeding 180 ° C. are practically difficult to produce.

(Ii) Production of propylene / ethylene copolymer component (d) In the subsequent polymerization step, the propylene / ethylene copolymer component produced in this step is a rubber component, and it is desirable that it does not elute into the solvent. It is preferable to carry out by gas phase polymerization. A known gas phase polymerization process can be used as the gas phase polymerization process, but a vertical or horizontal gas phase polymerization process that is mechanically stirred is preferable.
In the subsequent step, the propylene / ethylene copolymer component (d) is added in an amount of 30 to 75% by weight, preferably 35 to 70% by weight, more preferably 45% of the total polymerization amount (the entire propylene-based block copolymer (II)). An amount corresponding to ˜70% by weight is formed. When the formation amount with respect to the total polymerization amount of the propylene / ethylene copolymer component (d) is less than 30% by weight, the impact strength of the propylene-based resin composition and the molded product thereof is lowered, and when it exceeds 75% by weight, Stiffness, weld appearance and flow mark appearance are reduced. Here, when the amount of the propylene / ethylene copolymer component (d) formed relative to the total polymerization amount is larger, the amount of the component (B) elastomer, which is generally more expensive than the propylene resin, can be reduced. This is economically preferable.
In addition, this copolymer component can further contain a C4-C20 alpha olefin, a diene monomer, etc. as a 3rd component, for example. In that case, the content of these third components is preferably 20% by weight or less.

  Further, in the subsequent step, a propylene / ethylene copolymer component (d) having an ethylene content in the range of 10 to 30% by weight, preferably 10 to 28% by weight, more preferably 10 to 25% by weight is produced. . When the ethylene content in the propylene / ethylene copolymer component (d) is less than 10% by weight, the rigidity of the propylene-based resin composition and the molded product thereof decreases, and when it exceeds 30% by weight, the weld appearance is remarkably deteriorated. To do.

  The range of the weight average molecular weight of the propylene / ethylene copolymer component (d) is 250,000 to 1,000,000, preferably 250,000 to 800,000, and more preferably 300,000 to 500,000. When the weight average molecular weight of the propylene / ethylene copolymer component (d) is less than 250,000, the impact strength of the propylene-based resin composition and the molded product thereof is lowered. The appearance of molding due to spot generation etc. is reduced.

  Component (C) The range of MFR (230 ° C., 2.16 kg load) of the entire propylene-based block copolymer (II) is 5 to 200 g / 10 minutes, preferably 6 to 100 g / 10 minutes, and more preferably 8 to 50 g / 10 min. When the MFR is less than 5 g / 10 minutes, the weld appearance and the flow mark appearance of the propylene-based resin composition and the molded product thereof are deteriorated, and when it exceeds 200 g / 10 minutes, the impact strength is reduced.

  The MFR, the content of the propylene / ethylene copolymer component (d), the ethylene content, the weight average molecular weight, and the melting point of the crystalline propylene polymer component (c) are MFR meter, CFC fractionator, Fourier transform infrared absorption spectrum. It is a value measured by analysis, gel permeation chromatography (GPC), and differential scanning calorimeter (DSC). Measurement conditions will be described later in Examples.

(3) Blending ratio The blending ratio of the component (C) propylene-based block copolymer (II) in the propylene-based resin composition of the present invention is 1 to 15% by weight, preferably 5 to 13% by weight, particularly preferably. 6 to 12% by weight. When the blending ratio of component (C) is less than 1% by weight, the weld appearance of the propylene-based resin composition and the molded product thereof decreases, and when it exceeds 15% by weight, the rigidity, impact strength, and flow mark appearance decrease. To do. In addition, as long as a component (C) is in the range of the above-mentioned characteristic, you may use 2 or more types together.

4). Component (D) Inorganic filler Component (D) inorganic filler used in the propylene-based resin composition of the present invention is talc, wollastonite, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, barium sulfate, mica, glass Examples include fiber, glass balloon, basic magnesium sulfate whisker, potassium titanate whisker, aluminum borate whisker, carbon fiber, clay, organoclay, aluminum hydroxide, magnesium hydroxide, magnesium oxide, and zinc oxide. It is used for the purpose of improving the physical property balance centering on the rigidity of the propylene-based resin composition and its molded product, and expressing dimensional characteristics. These inorganic fillers may be surface-treated, or may be used in combination of two or more.

Of these, talc is preferable, and talc is effective in improving rigidity, dimensional stability of the molded body, adjustment thereof, and the like. The talc preferably has an average particle size of 1.5 μm to 15 μm, particularly preferably 2 to 8 μm. If the average particle size of talc is less than 1.5 μm, it aggregates and the appearance of the molded product is lowered, and if it exceeds 15 μm, the impact strength is lowered, which is not preferable.
The talc is produced, for example, by pulverizing raw talc with an impact pulverizer or a micron mill type pulverizer, or further pulverizing with a jet mill or the like and then adjusting the classification with a cyclone or micron separator. .

The talc may be chemically or physically surface-treated with various metal soaps or surfactants, and so-called compressed talc having an apparent specific volume of 2.50 ml / g or less may be used. The average particle diameter of the talc is a value measured using a laser diffraction / scattering particle size distribution meter, and examples of the measuring apparatus include Horiba LA-920 type.
The talc has an average aspect ratio of 4 or more, more preferably 5 or more. Measurement of the aspect ratio of the talc is obtained from a value measured with a microscope or the like.

  The blending ratio of the component (D) inorganic filler in the propylene-based resin composition of the present invention is 1 to 45% by weight, preferably 3 to 40% by weight, particularly preferably 4 to 30% by weight. When the blending ratio of the inorganic filler is less than 1% by weight, the rigidity of the propylene-based resin composition and the molded body thereof is insufficient, and when it exceeds 45% by weight, the impact strength, the weld appearance and the flow mark appearance are deteriorated.

5. Other ingredients (E)
In the propylene-based resin composition of the present invention, in addition to the above components (A), (B), (C) and (D), for example, the effects of the present invention can be achieved as long as the effects of the present invention are not significantly impaired. In order to further improve or impart other effects, other components (E) can be blended.
Specifically, antistatic agents such as nonionics, light stabilizers such as hindered amines, UV absorbers such as benzotriazoles, nucleating agents such as sorbitols, foaming agents such as physical foaming agents, organometallic salts Dispersants such as pigments, colorants such as pigments, antioxidants such as phenols, neutralizers such as inorganic compounds, lubricants such as fatty acid amides, metal deactivators such as nitrogen compounds, nonionic interfaces, etc. Activators, antibacterial and antifungal agents such as thiazoles, flame retardants such as halogen compounds, fluorescent brighteners, anti-foaming agents, cross-linking agents, peroxides, process oils (blending oils), anti-blocking agents , Plasticizers, polyolefins other than the above components (A) to (D), thermoplastic resins such as polyamide and polyester, elastomers (rubbers), inorganic (organic) fillers, and the like. These components may be added to the composition, may be added to each component, or two or more of these components may be used in combination.

  As the antistatic agent, for example, a nonionic or cationic antistatic agent is effective for imparting and improving the antistatic properties of the propylene-based resin composition and the molded body thereof. Specific examples include polyoxyethylene alkylamines; polyoxyethylene alkylamides; polyoxyethylene alkylphenyl ethers; stearic acid monoglycerides; alkyldiethanolamines; alkyldiethanolamides; alkyldiethanolamine fatty acid monoesters;

  For example, hindered amine compounds, benzotriazoles, benzophenones, salicylates, and the like as light stabilizers and ultraviolet absorbers are effective for imparting and improving the weather resistance and durability of the propylene resin composition and molded articles thereof. Specific examples of the hindered amine compound include a condensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine; poly [[6- (1, 1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethyl-4-piperidyl) imino]]; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebake Bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and the like, and examples of the benzotriazole type include 2- (2′-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) -5-chlorobenzotriazole; 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole and the like. -Methoxybenzophenone; 2-hydroxy-4-n-octoxybenzophenone and the like. Examples of salicylates include 4-t-butylphenyl salicylate; 2,4-di-t-butylphenyl 3 ', 5'-di -T-butyl-4'-hydroxybenzoate and the like.

  As a nucleating agent, for example, inorganic, sorbitol, carboxylic acid metal salt and organic phosphate are effective for imparting and improving the rigidity, heat resistance, hardness, etc. of the propylene resin composition and its molded product. It is. Specific examples include talc as an inorganic type; silica and the like, and 1,3,2,4-dibenzylidene-sorbitol as a sorbitol type; 1,3,2,4-di- (p-methyl-benzylidene). Sorbitol; 1,3,2,4-di- (p-ethyl-benzylidene) sorbitol; 1,3,2,4-di- (2 ′, 4′-di-methyl-benzylidene) sorbitol; p-chlorobenzylidene-2,4-p-methyl-benzylidene-sorbitol; 1,3,2,4-di- (p-propylbenzylidene) sorbitol and the like. Hydroxy-di-pt-butylbenzoate; sodium benzoate; calcium montanate and the like. 4-t-butylphenyl) phosphate; sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate; lithium-2,2′-methylene-bis (4,6- And di-t-butylphenyl) phosphate.

  As the foaming agent, for example, a physical foaming agent and a chemical foaming agent are effective for reducing the weight of the propylene-based resin composition and its molded product, and for imparting and improving rigidity and dimensional characteristics. Specific examples of the physical blowing agent include carbon dioxide gas; nitrogen gas; air; propane; butane; dichlorodifluoromethane and the like. Examples of the chemical blowing agent include citric acid; baking soda; azodicarbonamide; benzenesulfonylhydrazide; Hydrazide; N, N′-dimethyl-N, N′-dinitrosotephthalamide; P-toluenesulfonyl semicarbazide and the like.

  As a dispersant, for example, an organic metal salt or the like enhances dispersibility of inorganic fillers and coloring pigments, and imparts rigidity, heat resistance, weld appearance, flow mark appearance, texture, etc. of the propylene-based resin composition and its molded body, It is effective for improvement. Specific examples include calcium stearate; magnesium stearate; calcium behenate; magnesium behenate; zinc behenate; zinc montanate; calcium montanate;

  As a colorant, for example, inorganic or organic pigments are effective for imparting or improving the colored appearance, appearance, texture, commercial value, weather resistance, durability, etc. of the propylene resin composition and its molded product. It is. Specific examples of inorganic pigments include titanium oxide; iron oxide (eg, bengara); chromic acid (eg, galvanized lead); molybdic acid; selenide sulfide; ferrocyanide and carbon black. Insoluble azo chelates; insoluble azo chelates; condensable azo chelates; other azo chelates such as azo chelates; phthalocyanine blue; phthalocyanine pigments such as phthalocyanine green; anthraquinones; perinones; perylene; Dye lake; quinacridone type; dioxazine type; isoindolinone type. Moreover, in order to make a metallic tone or a pearl tone, an aluminum flake; a pearl pigment can be contained. Moreover, dye can also be contained.

[II] Production and molding of propylene-based resin composition The propylene-based resin composition of the present invention comprises the above component (A), component (B), component (C), component (D), and other components as necessary. Manufactured by blending (E) in the above blending ratio and kneading and granulating using a conventional kneader such as a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader. To do.
In this case, it is desirable to select a kneading / granulating method capable of improving the dispersion of each component, and usually kneading / granulating using a twin screw extruder. During this kneading and granulation, the above component (A), component (B), component (C), component (D), and, if necessary, other components (E) may be kneaded at the same time. It is also possible to divide each component to improve the performance, for example, first knead a part or all of component (A) and component (C), and then knead and granulate the remaining components.

The propylene-based resin composition is molded by injection molding (including gas injection molding) or injection compression molding (including press injection, hot flow stamping molding, gas injection compression molding) to obtain those molded bodies. be able to.
In this case, a desired molded article can be obtained by a combination of the injection molding related technique and the so-called foam molding technique or expansion molding technique.
If necessary, various molding methods such as hollow molding, extrusion molding, compression (press) molding, foaming (expansion) molding, sheet molding, calendar molding, film molding, thermoforming, stamping molding, powder molding, Each molded body can also be obtained.

  The propylene resin composition of the present invention and the molded product thereof are used as various molded products in the field of industrial parts such as automobile parts and parts of household electrical appliances such as televisions, preferably automobile parts such as bumpers and doors. Examples include protectors, side protectors, side moldings, instrument panels, door trims, and pillars.

Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The analysis methods, physical property measurement methods, evaluation methods and resins used in the examples are as follows.

1. Analysis method, physical property measurement method, evaluation method (1) Content of propylene / ethylene copolymer component, ethylene content, weight average molecular weight: Measured under the following conditions.
(I) Analytical device to be used (i-1) Cross sorter CFC T-100 (abbreviated as CFC) manufactured by Dia Instruments
(I-2) Fourier transform infrared absorption spectrum analysis FT-IR, 1760X manufactured by PerkinElmer
A fixed wavelength infrared spectrophotometer attached as a CFC detector is removed and an FT-IR is connected instead, and this FT-IR is used as a detector. The transfer line from the outlet of the solution eluted from the CFC to the FT-IR is 1 m long, and the temperature is maintained at 140 ° C. throughout the measurement. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ, and the temperature is maintained at 140 ° C. throughout the measurement.
(I-3) Gel permeation chromatography (GPC)
The GPC column in the latter part of the CFC is used by connecting three AD806MS manufactured by Showa Denko KK in series.

(Ii) CFC measurement conditions (ii-1) Solvent: orthodichlorobenzene (ODCB)
(Ii-2) Sample concentration: 4 mg / ml
(Ii-3) Injection amount: 0.4 ml
(Ii-4) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(Ii-5) Fractionation method: Fractionation temperatures are 40, 100, and 140 ° C., and fractionation is performed in a total of three fractions. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
(Ii-6) Solvent flow rate during elution: 1 ml / min

(Iii) Measurement conditions for FT-IR After elution of the sample solution from the GPC at the latter stage of the CFC starts, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above-described fractions 1 to 3. .
(Iii-1) Detector: MCT
(Iii-2) Resolution: 8 cm ⁻¹
(Iii-3) Measurement interval: 0.2 minutes (12 seconds)
(Iii-4) Integration count per measurement: 15 times

(Iv) Method for calculating properties of propylene / ethylene copolymer component Fractionation temperatures are 40, 100, and 140 ° C., and fractionated into three fractions in total. The propylene / ethylene copolymer component is an ethylene component of a 100 ° C. fraction and a 40 ° C. fraction component. That is, the contents of the 40, 100, and 140 ° C. fractions are F40, F100, and F140 (F40 + F100 + F140 = 100 wt%), respectively. The amount of ethylene component in the 100 ° C. fraction is F100E, and the other component amount is F100F (F100E + F100F = F100). The content of the propylene / ethylene copolymer component can be expressed by F40 + F100E.
The ethylene content in the propylene / ethylene copolymer component is a value obtained by dividing the ethylene content in the 40 ° C. and 100 ° C. fractions by the amount of the propylene / ethylene copolymer component. That is, when the amount of ethylene in the 40 ° C. fraction is F40E and the other components are F40F (F40E + F40F = F40), it is represented by the formula of 100 × (F40E + F100E) / (F40 + F100E).
The weight average molecular weight of the propylene / ethylene copolymer component is the weight average molecular weight of the ethylene component of the 100 ° C. fraction and the 40 ° C. fraction component.

(2) MFR: JIS K7210 Method A / Condition M: Measured according to test temperature: 230 ° C., load: 2.16 kg.

(3) Melting point: Using a differential scanning calorimeter, about 5 mg of sample was taken, held at 200 ° C. for 5 minutes, then cooled to 40 ° C. at a cooling rate of 10 ° C./min to crystallize and erase the thermal history. The melting point is the maximum peak temperature of the heat of fusion curve when the temperature is further raised at 10 ° C./min. If multiple melting points are observed, the one observed at the highest temperature is taken as the melting point.

(4) Flexural modulus: Measured in the following manner according to JIS K-7171 (ISO178).
Testing machine: Precision universal testing machine Autograph AG-20KNG (manufactured by Shimadzu Corporation)
Test piece: Creation method = Injection molding, Sampling direction = Flow direction, Shape = Thickness 4 mm, Width 10 mm, Length 80 mm, Condition adjustment = Leave in a constant temperature room at room temperature 23 ° C. and humidity 50% for 24 hours or more Test conditions: Test Temperature = 23 ° C., test humidity = 50%, number of test pieces = 5, distance between fulcrums = 32.0 mm, test speed = 1.0 mm / min

(5) Charpy impact strength: Measured in the following manner in accordance with JIS K-7111 (ISO 179 / 1eA).
Tester: Toyo Seiki Co., Ltd. Fully automatic Charpy impact tester (with constant temperature bath)
Test piece: Creation method = Cutting a notch in an injection-molded test piece (ISO 2818 compliant), Shape = Single notch: Type A notch (notch radius 0.25 mm), thickness 4 mm, width 10 mm, length 80 mm, condition adjustment = Leave in a constant temperature room at room temperature of 23 ° C and humidity of 50% for more than 24 hours Test conditions: When the test temperature = 23 ° C and -30 ° C ... -30 ° C, the temperature chamber was within ± 1 ° C of the test temperature The test is performed after adjusting the condition for 40 minutes or more. Test humidity = 50%, number of test pieces = 5, impact speed = 2.9 m / s, pendulum energy = 4 J

(6) Weld dissipation distance: 350 mm × 100 mm × 3 mmt sheet having an opening of 20 mm × 3 mm × 1 mm at an area of 7 mm from the gate shown in FIG. Using the sheet molding die (100 mm wide gate), injection molding is performed at a molding temperature of 220 ° C. to obtain a sample. About this evaluation molded object, the weld line produced on it is observed visually, and the distance (length) until the weld line disappears from the end of the opening is measured. The shorter this distance, the better the weld appearance.

(7) Flow mark generation distance: The flow mark generated on the evaluation molded body is visually observed, and the distance (length) until the flow mark is generated from the end of the opening is measured. The longer this distance, the better the appearance of the flow mark.

2. Production of raw materials (1) Component (A) Propylene block copolymer (I)
The polymer obtained in the following Production Example 1 was used.

(Production Example 1) Component (A) -1
(I) Production of solid catalyst component (a) 20 liters of dehydrated and deoxygenated n-heptane was introduced into a tank equipped with a stirrer with an internal volume of 50 liters purged with nitrogen, and then 10 moles of magnesium chloride and 20 moles of tetrabutoxytitanium And then reacting at 95 ° C. for 2 hours, lowering the temperature to 40 ° C., introducing 12 liters of methylhydropolysiloxane (viscosity 20 centistokes) and further reacting for 3 hours, then taking out the reaction solution The resulting solid component was washed with n-heptane.
Subsequently, 5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank with a stirrer, and then 3 mol of the solid component synthesized above was introduced in terms of magnesium atom. Next, 5 liters of silicon tetrachloride was mixed with 2.5 liters of n-heptane and introduced at 30 ° C. for 30 minutes. The temperature was raised to 70 ° C. and reacted for 3 hours. Then, the reaction solution was taken out, The resulting solid component was washed with n-heptane.
Subsequently, 2.5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank with a stirrer, and 0.3 mol of phthalic acid chloride was mixed and introduced at 90 ° C. for 30 minutes. And reacted at 95 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 2 liters of titanium tetrachloride was added at room temperature, and the temperature was raised to 100 ° C., followed by reaction for 2 hours. After completion of the reaction, washing with n-heptane was performed. Further, 0.6 liters of silicon tetrachloride and 8 liters of n-heptane were introduced, reacted at 90 ° C. for 1 hour, and sufficiently washed with n-heptane to obtain a solid component. This solid component contained 1.30% by weight of titanium.

Next, 8 liters of n-heptane, 400 g of the solid component obtained above, 0.27 mol of t-butyl-methyl-dimethoxysilane and 0.27 mol of vinyltrimethylsilane were introduced into the tank equipped with a stirrer substituted with nitrogen. And contacted at 30 ° C. for 1 hour. Next, the mixture was cooled to 15 ° C., 1.5 mol of triethylaluminum diluted in n-heptane was introduced over 15 minutes under 15 ° C., and after the introduction, the temperature was raised to 30 ° C. and reacted for 2 hours. By washing with heptane, 390 g of a solid catalyst component was obtained.
The obtained solid catalyst component contained 1.22% by weight of titanium.

  Furthermore, 6 liters of n-heptane and 1 mol of triisobutylaluminum diluted in n-heptane were introduced over 30 minutes at 15 ° C., and then about 0.4 kg / kg of propylene was controlled so as not to exceed 20 ° C. Preliminarily polymerized by introducing for 1 hour. As a result, a polypropylene-containing solid catalyst component (a) in which 0.9 g of propylene was polymerized per 1 g of solid was obtained.

(Ii) Production of propylene-based block copolymer (I) (pre-stage polymerization step: production of crystalline propylene polymer component (a))
Polymerization was carried out using a continuous reaction apparatus in which two fluidized bed reactors having an internal volume of 230 liters were connected. First, in a first reactor, a polymerization temperature of 65 ° C., a propylene partial pressure of 18 kg / cm ² (absolute pressure), and hydrogen as a molecular weight control agent are continuously fed so that the molar ratio of hydrogen / propylene is 0.060. At the same time, triethylaluminum was supplied at 5.25 g / hr as a solid catalyst component (a), and the catalyst described above was supplied so that the polymer polymerization rate was 20 kg / hr, and the crystalline propylene polymer component (a) was added. Manufactured. The powder polymerized in the first reactor (crystalline propylene polymer component (a)) was continuously withdrawn so that the amount of powder retained in the reactor was 40 kg, and was continuously transferred to the second reactor.

(Second-stage polymerization step: Production of propylene / ethylene copolymer component (b))
Subsequently, propylene and ethylene are continuously fed so that the molar ratio of ethylene / (propylene + ethylene) is 0.36 so that the inside of the second reactor has a polymerization temperature of 60 ° C. and a pressure of 2.0 MPa. Furthermore, hydrogen as a molecular weight control agent is continuously supplied so that the molar ratio of hydrogen / (propylene + ethylene) is 0.055, and ethyl alcohol is added as an active hydrogen compound to triethylaluminum. The propylene / ethylene copolymer component (b) was produced by supplying 1.77 times mole. The powder (the propylene-based block copolymer (I) comprising the crystalline propylene polymer component (a) and the propylene / ethylene copolymer component (b)) that has been polymerized in the second reactor is contained in the reactor. The powder was continuously extracted to the vessel so that the amount of powder retained was 60 kg. Nitrogen gas containing water was supplied to stop the reaction to obtain a propylene-based block copolymer (I). The obtained propylene-based block copolymer (I) was used as component (A) -1.
Table 1 shows the physical property values of the components.

(2) Component (B) Elastomer MFR = 3.1 g / 10 min, density = 0.862 g / cm ³ , butene content = 25 wt% ethylene-1-butene rubber-like random copolymer (component (B) -1 ) Was used.

(3) Component (C) Propylene-based block copolymer (II)
The polymers obtained in the following Production Examples 2 to 6 were used.

(Production Example 2) Component (C) -1
(I) Metallocene Complex Dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} hafnium was synthesized according to Japanese Patent Application Laid-Open No. 2000-95791. .

(Ii) Catalyst preparation Into a 5 L separable flask equipped with a stirring blade and a reflux device, 1,698 g of pure water was added, and 501 g of 98% sulfuric acid was added dropwise. Further, 300 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 19.5 μm) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was washed with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. A 900 ml aqueous solution of 324 g of lithium sulfate monohydrate was added to the collected cake and reacted at 90 ° C. for 2 hours. This slurry was washed to pH> 4 with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. The collected cake was dried at 120 ° C. overnight.
As a result, 275 g of a chemically treated product was obtained.
10.0 g of the chemically treated montmorillonite obtained above was weighed into a 1 L flask, 65 ml of heptane and 35.4 ml (25 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the remaining liquid ratio was washed to 1/100 with heptane, and finally the amount of slurry was adjusted to 100 ml.

(Iii) Prepolymerization with Propylene 0.85 ml of a triisobutylaluminum heptane solution was added to the montmorillonite heptane slurry prepared above and treated with triisobutylaluminum, and stirred for 10 minutes at room temperature.
In addition, a toluene (60 ml) solution of dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl]} hafnium synthesized in (i) above was added. And stirred at room temperature for 60 minutes.
Next, 340 ml of heptane was further added to the montmorillonite heptane slurry and introduced into a 1 L stirred autoclave, and propylene was added at 40 ° C. at a constant rate of 238.1 mmol / hr (10 g / hr) for 120 minutes. Supplied. After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave.
The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover a solid catalyst.
The prepolymerization ratio (a value obtained by dividing the prepolymerized polymer amount by the solid catalyst amount) was 1.55.

(Iv) Block polymerization The inside of the stirred autoclave with an internal volume of 3 L was sufficiently replaced with propylene, and then 2.76 ml (2.02 mmol) of triisobutylaluminum / n-heptane solution was added, followed by introduction of 180 ml of hydrogen and 750 g of liquid propylene. The temperature was raised to 65 ° C. and the temperature was maintained. The prepolymerized catalyst prepared in (iii) above was slurried in normal heptane, and 50 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature in the tank was maintained at 65 ° C., and after 1 hour from the catalyst addition, the remaining monomer was purged, and the inside of the tank was replaced with argon five times. Stirring was stopped, and while flowing argon, a Teflon (registered trademark) tube was inserted into the tank, and a small amount of polypropylene was extracted. As a result of measurement after drying at 90 ° C. under a nitrogen stream for 30 minutes, the extraction amount was 10 g.
Thereafter, 0.9 MPa of propylene and then 1.1 MPa of ethylene were introduced, and the internal temperature was raised to 80 ° C. Thereafter, a previously prepared mixed gas of propylene and ethylene was introduced, and the polymerization reaction was controlled for 50 minutes while adjusting the internal pressure of 2.0 MPa so that the monomer composition ratio did not change during the polymerization. As a result, 250 g of a propylene-based block polymer having a good particle property was obtained.
The propylene-based block copolymer (II) (component (C) -1) obtained above was separately collected from the result of CFC-IR, the propylene / ethylene copolymer component (d) content being 52% by weight. The MFR of the crystalline propylene polymer component (c) is 110 (g / 10 min), the melting point of the component (c) is 158 ° C., the ethylene content of the propylene / ethylene copolymer component (d) is 18% by weight, The weight average molecular weight of the component (d) was 380,000, and the MFR of the entire component was 11 (g / 10 minutes).

(Production Example 3) ... Component (C) -2
Polymerization was performed in the same manner as in Production Example 2 except that the ratio of the mixed gas of propylene and ethylene in the second stage polymerization was 40/60, to obtain a propylene-based block polymer. The results are shown in Table 2 together with Production Example 2.

(Production Example 4) ... Component (C) -3
Polymerization was performed in the same manner as in Production Example 2 except that the ratio of the mixed gas of propylene and ethylene in the second stage polymerization was 60/40, to obtain a propylene-based block polymer. The results are shown in Table 2.

(Production Example 5) ... Component (C) -4
Polymerization was carried out in the same manner as in Production Example 2 except that the ratio of the mixed gas of propylene and ethylene in the second stage polymerization was 30/70 to obtain a propylene-based block polymer. The results are shown in Table 2.

(Production Example 6) ... Component (C) -5
Polymerization was carried out in the same manner as in Production Example 2 except that the polymerization time in the second stage polymerization was changed to 15 minutes to obtain a propylene-based block polymer. The results are shown in Table 2.

(Production Example 7) ... Component (C) -6
Polymerization was carried out in the same manner as in (Production Example 6) except that the ratio of the mixed gas of propylene and ethylene in the second stage polymerization was 20/80 to obtain a propylene-based block polymer. The results are shown in Table 2.

(4) Component (D) Inorganic filler Fine powder talc (component (D) -1) having an average particle size of 5.5 μm and an average aspect ratio of 6 was used.

(Examples 1-2)
Each component (A)-(D) was mix | blended in the ratio shown in Table 3, it granulated on the following conditions, and performance evaluation was performed about what was shape | molded. The evaluation results are shown in Table 4.

(1) Additive formulation (i) Antioxidant: Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane 500 ppm, Tris (2,4-di -T-butylphenyl) phosphite 500 ppm
(Ii) Neutralizing agent: calcium stearate 500 ppm

(2) Granulation (i) Extruder: Technobel KZW-15-45MG twin screw extruder (ii) Screw: caliber 15 mm L / D = 45
(Iii) Extruder set temperature: (from below the hopper) 40, 80, 160, 200, 200, 200 (die temperature)
(Iv) Screw rotation speed: 400 rpm
(V) Discharge amount: Adjusted to about 1.5 kg / hr with a screw feeder (vi) Die: 3 mm diameter Strand die Number of holes 2

(3) Molding The obtained raw material pellets were injection molded under the following conditions to obtain flat plate test pieces for physical property evaluation.
(I) Standard number: JIS K-7152 (ISO 294-1)
(Ii) Molding machine: EC20P injection molding machine manufactured by Toshiba Machine Co. (iii) Molding machine set temperature: (from below the hopper) 80, 210, 210, 200, 200 ° C.
(Iv) Mold temperature: 40 ° C
(V) Injection speed: 52 mm / s (screw speed)
(Vi) Holding pressure: 30 MPa
(Vii) Holding pressure time: 8 seconds (viii) Mold shape: Two flat plates (thickness 4 mm, width 10 mm, length 80 mm)

(Comparative Examples 1-6)
Each component (A)-(D) was mix | blended in the ratio shown in Table 3, and it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 4.

From Tables 3 and 4, the propylene-based resin composition having the composition shown in Examples 1 and 2 that satisfies each specified requirement of the present invention and the molded body thereof have good physical property balance (fluidity, rigidity, low temperature). Impact strength), weld appearance, and flow mark appearance, and it can be seen that it has performance suitable for industrial parts such as automobile parts such as bumpers and side moldings.
On the other hand, it can be seen that the propylene-based resin compositions having the compositions shown in Comparative Examples 1 to 6 and molded articles thereof are poor in performance balance.
For example, since the component (C) was not blended at all in Comparative Example 1, the appearance improving effect was not expressed, and a significant difference in weld disappearance distance occurred as compared with Examples 1 and 2.
Further, in Comparative Example 2, although the blending ratio of each component and the type of each component other than the component (C) are the same as in Example 1, the difference in the flow mark generation distance, particularly the bending elastic modulus, is remarkably different. Occurred. This is because in Comparative Example 2, the compatibility improvement between the component (A) and the flexible component (B) is excessively promoted by the component (C) that does not satisfy the characteristics defined in the present invention as compared with the case of Example 1. It is thought that it was because it was done.
On the other hand, in Comparative Example 3, although the blending ratio of each component and the type of each component other than the component (C) are the same as those in Example 1, the flexural modulus, impact strength, especially weld loss distance There were significant differences. This is because in Comparative Example 3, the compatibility improvement between the component (A) and the component (B) can be promoted by another component (C) that does not satisfy the characteristics defined in the present invention as compared with the case of Example 1. Therefore, as a result, it is considered that the expression of the uniform dispersion state of the component (B) is mainly insufficient.
Further, in Comparative Example 4, as compared with Example 1, there were significant differences in bending elastic modulus, impact strength, and flow mark generation distance. This is probably because the component (C) is excessive, and the degree of expression of the properties such as the component (A) and the component (B) is reduced.
Further, in Comparative Example 5, when propylene-based block copolymers having different ethylene contents were used as the component (C), there was a significant difference in weld disappearance distance compared to Examples 1 and 2 (Patent Document). 17). This is presumably because the effect of improving the compatibility between the component (A) and the component (B) is not sufficiently exhibited depending on the component (C).
Furthermore, in Comparative Example 6, since the component (B) and the component (D) were not blended at all, the reinforcing effect was not exhibited, and a significant difference was produced in the flexural modulus and impact strength as compared with Example 1. It was.

  From the results of the above examples and comparative examples, the rationality and significance of the configuration of the present invention and the requirements are demonstrated, and the superiority of the present invention over the prior art is also clarified.

  Polypropylene resin compositions and molded articles thereof have good physical property balance (fluidity, rigidity, low temperature impact strength), weld appearance, and flow mark appearance, and are suitable for industrial parts such as automobile parts such as bumpers and side moldings. It has suitable performance.

The schematic diagram which shows the molded object for evaluation about an external appearance.

Claims (5)

(A) A propylene-based block copolymer (I) 30 composed of a crystalline propylene polymer component and a propylene / ethylene copolymer component, which is polymerized using a Ziegler-based catalyst, and satisfies the following characteristics 1) to 5) Propylene-based block copolymers (II) 1 to 15 satisfying the following characteristics 6) to 11), polymerized using -97 wt%, (B) elastomer 1 to 40 wt%, and (C) a metallocene catalyst. A propylene-based resin composition containing 1% by weight and (D) 1 to 45% by weight of an inorganic filler.
Characteristic 1) It consists of crystalline propylene polymer component (a) 65 to 97% by weight and propylene / ethylene copolymer component (b) 3 to 35% by weight.
Characteristic 2) The MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (a) is 10 to 600 g / 10 minutes.
Characteristic 3) The ethylene content of the propylene / ethylene copolymer component (b) is 30 to 70% by weight.
Characteristic 4) The weight average molecular weight of the propylene / ethylene copolymer component (b) is 50,000 to 2,000,000.
Characteristic 5) MFR (230 ° C., 2.16 kg load) of the whole component is 5 to 300 g / 10 minutes.
Characteristic 6) It consists of 25 to 70% by weight of a crystalline propylene polymer component (c) and 30 to 75% by weight of a propylene / ethylene copolymer component (d).
Characteristic 7) The MFR (230 ° C., 2.16 kg load) of the crystalline propylene polymer component (c) is 40 to 350 g / 10 minutes.
Characteristic 8) The melting point obtained by differential scanning calorimetry (DSC) of the crystalline propylene polymer component (c) is 156 ° C. or higher.
Characteristic 9) The ethylene content of the propylene / ethylene copolymer component (d) is 10 to 30% by weight.
Characteristic 10) The weight average molecular weight of the propylene / ethylene copolymer component (d) is 250,000 to 1,000,000.
Characteristic 11) MFR (230 ° C., 2.16 kg load) of the whole component is 5 to 200 g / 10 minutes.   2. The propylene resin composition according to claim 1, wherein the component (C) contains 45 to 70 wt% of a propylene / ethylene copolymer component (d) having an ethylene content of 10 to 25 wt%. object.   The component (A) is 43 to 87% by weight, the component (B) is 3 to 15% by weight, the component (C) is 6 to 12% by weight, and the component (D) is 4 to 30% by weight. Or the propylene-type resin composition of 2. The metallocene-based catalyst reacts with (a) a transition metal compound represented by the following general formula [I], and (a) (a-1) an organoaluminum oxy compound and (b-2) a transition metal compound to form a cation. At least one activator selected from the group consisting of a compound that can be formed and (I-3) an ion-exchange layered compound (including silicate) is an essential component, and (U) an organoaluminum compound is an optional component. The propylene-based resin composition according to claim 1, wherein the propylene-based resin composition is a product.

(In the general formula [I], A ¹ and A ² represent a conjugated five-membered ring ligand (in the same compound, A ¹ and A ² may be the same or different). The carbon of the conjugated five-membered ring that is not bonded may have a substituent, Q is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and M is a periodic table 4 A metal atom selected from Group -6, X and Y are each independently bonded to M, a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, Nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group is shown.)   A molded article obtained by molding the propylene-based resin composition according to any one of claims 1 to 4 by injection molding or injection compression molding.

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