JP3530143B2 - Polyolefin resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyolefin resin composition, and more particularly to a polyolefin resin composition which can be suitably used as a material for home electric appliances.

[0002]

BACKGROUND OF THE INVENTION Polyolefin resins, such as propylene block copolymers, are used in household goods, kitchen utensils,
It is used in various fields such as packaging films, home electric appliances, mechanical parts, electric parts, and automobile parts, and various additives are blended according to the required performance. Especially for home electric appliances, a composition prepared by blending a propylene block copolymer with an α-olefin copolymer rubber and an inorganic filler such as talc has an excellent balance between rigidity and impact resistance of the molded product. Therefore, it is used in large quantities. However, the resin composition containing the propylene-based block copolymer is apt to cause flow marks during molding, particularly during injection molding.

Further, a composition prepared by blending a propylene block copolymer produced using a metallocene catalyst, an α-olefin copolymer rubber and an inorganic filler is disclosed in JP-A-10-
It is known as the composition described in Japanese Patent No. 1573. However, a propylene-based block copolymer produced with a metallocene catalyst has 1,3-insertion or 2,1-insertion at a rate of about 1% at the time of its production, resulting in low crystallinity, and therefore The melting point is around 150 ° C., which is lower than the melting point of 160 ° C. of a propylene-based block copolymer produced with a titanium-based catalyst. In addition, the propylene-based block copolymer produced with a metallocene catalyst is inferior in tensile strength characteristics, bending strength characteristics, rigidity, etc. as compared with the propylene-based block copolymer produced with a titanium catalyst. As a result, the composition prepared by blending the propylene block copolymer produced with the metallocene catalyst, the α-olefin copolymer rubber, and the inorganic filler is the same as the propylene block copolymer produced with the titanium catalyst and α-. Since the mechanical strength characteristics are inferior to those of the composition in which the olefin copolymer rubber and the inorganic filler are blended, they have not been put to practical use.

The inventors of the present invention have conducted extensive studies to solve the above problems, and found that a propylene-based block copolymer produced with a specific metallocene catalyst has almost no 1,3-insertion or 2,1-insertion of propylene. , Therefore the melting point is high,
It was found that the molded product has high glossiness and excellent rigidity, tensile strength property, and bending strength property, and the resin composition using the propylene block copolymer has excellent performance as a composition for home electric appliances. The present invention has been completed and the present invention has been completed.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. The flow marks are improved, the appearance is excellent, and the balance between rigidity and impact resistance is excellent. It is intended to provide a polyolefin resin composition capable of preparing a molded article having high glossiness, particularly a polyolefin resin composition for home electric appliances.

[0006]

SUMMARY OF THE INVENTION A polyolefin resin composition according to the present invention comprises a propylene homopolymer part and a propylene / α-olefin random copolymer part prepared by using a metallocene catalyst. A)
60-98% by weight and inorganic filler (B) 2-40% by weight
The propylene-based block copolymer (A) has an α-olefin content of 2 to 20% by weight and a melt flow rate (ASTM D1238, 230 ° C, load 2.1).
6 kg) is 8 to 100 g / 10 minutes, and the propylene homopolymer part of the propylene block copolymer (A) is
(I) Melt flow rate (ASTM D 1238, 230 ° C, 2.16
(kg load) is in the range of 0.01 to 1000 g / 10 min, and (ii) the 2,1-insertion or 1,3-insertion of the propylene monomer in all propylene constitutional units determined from the ¹³ C-NMR spectrum. The ratio of positional irregular units based on each is 0.2% or less, and (iii) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 1 to 3 There is.

In the polyolefin resin composition according to the present invention, the elastomer (C) further comprises a total amount of 10 parts of the propylene block copolymer (A) and the inorganic filler (B).
It may be contained in an amount of 20% by weight or less based on 0% by weight. As the metallocene compound catalyst component forming the metallocene catalyst, a metallocene compound represented by the following general formula (1) or (2) is usually used.

[0008]

[Chemical 2]

(In the formula, R ³ is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R ¹ , R ² , R ⁴ , R ⁵ ,
^{R 6, R 7, R 8} , R 9, R 10, R 11, R 12, R 13, and R ^14, which may be the same or different from each other, a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group Among the groups represented by R ¹ to R ¹² , adjacent groups may be bonded to each other to form a ring, and in the case of the general formula (1), R ¹ , R ⁴ , R ⁵ and R group and R ^{1 3} or R ¹⁴ selected from ¹² may be bonded to each other to form a ring, a is,
A divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring is shown, and A is Y
It may contain two or more ring structures including a ring formed together, Y is a carbon atom or a silicon atom, and M is
Indicates a metal selected from Group 4 of the periodic table, and j is 1 to
Is an integer of 4 and Q is selected from a halogen atom, a hydrocarbon group, an anion ligand and a neutral ligand capable of coordinating with a lone electron pair, and when j is 2 or more, Q is the same as each other. It may be different. ) As the inorganic filler (B), talc is particularly preferable.

The polyolefin resin composition according to the present invention is excellent in moldability and is particularly suitably used as a polyolefin resin composition for home electric appliances during the production of home electric appliances.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The polyolefin resin composition according to the present invention will be specifically described below. The polyolefin resin composition according to the present invention contains a propylene block copolymer (A), an inorganic filler (B), and optionally an elastomer (C).

Propylene Block Copolymer (A) The propylene block copolymer (A) used in the present invention is a crystalline block composed of a propylene homopolymer part and an ethylene / propylene random copolymer part. It is a copolymer. The ethylene content in the whole propylene block copolymer (A) is 2 to 20% by weight, preferably 3 to 15% by weight, and the melt flow rate (MFR; ASTM D 123) of the block copolymer (A).
8,230 ° C., load 2.16 kg) is 8 to 100 g / 10 minutes, preferably 30 to 80 g / 10 minutes.

The propylene block copolymer (A) used in the present invention is a propylene homopolymer component which constitutes the n-decane-insoluble component at room temperature, and optionally a polyethylene component and an n-decane-soluble component at room temperature. Random copolymer component of propylene and α- olefin constituting, preferably ethylene, and any other α-olefin (hereinafter,
Propylene / α-olefin random copolymer).

Specific examples of such α-olefins other than ethylene include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-pentene,
An α-olefin having 4 to 20 carbon atoms such as 4-methyl-1-pentene can be mentioned. The propylene homopolymer part of the propylene block copolymer (A) used in the present invention is
It has the following characteristics. (I) The melt flow rate of this propylene homopolymer part (MFR; ASTM D 1238, 230 ° C., 2.16 kg load) is
0.01-1000 g / 10 minutes, preferably 0.05-
500 g / 10 minutes, particularly preferably 0.1-100 g /
It is in the range of 10 minutes, and (ii) the proportion of regio-irregular units based on 2,1-insertion or 1,3-insertion of propylene monomer in all propylene constitutional units determined from ¹³ C-NMR spectrum is 0. 0.2% or less, preferably 0.1%
The following is particularly 0.05% or less, and (iii) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 1 to 3, preferably 1 to
It is in the range of 2.5, more preferably 1 to 2.3.

Further, it is preferable that the propylene homopolymer part further has the following characteristics (iv), (v) and (vi). (Iv) n-decane-soluble content (weight% dissolved in n-decane after treating propylene homopolymer with n-decane at 150 ° C for 2 hours and then returning to room temperature) is 2% by weight or less, preferably 1% by weight % Or less, (v) ¹³ C
-Pentad (pe
ntad) isotacticity is 90% or more, preferably 95% or more.

Isotactic pentad fraction (mmm
m fraction) indicates the abundance of isotactic chains in pentad units in the propylene-based block copolymer (A) molecular chain measured using ¹³ C-NMR,
It is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded.
Specifically, it is a value calculated as the fraction of the mmmm peak in all the absorption peaks in the methyl carbon region observed in the ¹³ C-NMR spectrum. (Vi) The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is usually 153 to 165 ° C, preferably 155 to 163 ° C, more preferably 157 to 161 ° C.
It is desirable to be in the range of.

The propylene block copolymer (A) used in the present invention has an n-decane insoluble matter at room temperature, that is, a propylene homopolymer part of 80 to 99% by weight, preferably 85.
Contained in an amount of up to 97% by weight at room temperature and soluble in n-decane, that is, an ethylene / propylene random copolymer component (F
It is desirable to contain c) in an amount of 1 to 20% by weight, preferably 3 to 15% by weight.

The above propylene block copolymer (A)
Can be used alone or in combination of two or more. The propylene block copolymer (A) used in the present invention is prepared, for example, using a specific metallocene catalyst. The metallocene compound catalyst component forming such a metallocene catalyst is represented by the following general formula (1) or (2).

[0019]

[Chemical 3]

(In the formula, R ³ is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R ¹ , R ² , R ⁴ , R ⁵ ,
^{R 6, R 7, R 8} , R 9, R 10, R 11, R 12, R 13, and R ^14, which may be the same or different from each other, a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group Among the groups represented by R ¹ to R ¹² , adjacent groups may be bonded to each other to form a ring, and in the case of the general formula (1), R ¹ , R ⁴ , R ⁵ and R group and R ^{1 3} or R ¹⁴ selected from ¹² may be bonded to each other to form a ring, a is,
A divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring is shown, and A is Y
It may contain two or more ring structures including a ring formed together, Y is a carbon atom or a silicon atom, and M is
Indicates a metal selected from Group 4 of the periodic table, and j is 1 to
Is an integer of 4 and Q is selected from a halogen atom, a hydrocarbon group, an anion ligand and a neutral ligand capable of coordinating with a lone electron pair, and when j is 2 or more, Q is the same as each other. It may be different. ) Further, examples of the other metallocene compound catalyst component used in the present invention include metallocene compounds represented by the following general formula (1a) or (2a).

[0021]

[Chemical 4]

(In the formula, R ³ is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R ¹ , R ² , R ⁴ , R ⁵ ,
^{R 6, R 7, R 8} , R 9, R 10, R 11, R 12, R 13, and R ^14, which may be the same or different from each other, a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group A compound represented by the general formula (1a), wherein R ³ is t
ert-butyl group or trimerylsilyl group, and when R ¹³ and R ¹⁴ are simultaneously a methyl group or a phenyl group, R ⁶ and R ¹¹ are not hydrogen atoms at the same time, and are a group represented by R ¹ to R ^12. Adjacent groups may combine with each other to form a ring, and in the case of the general formula (1a), R ¹ , R ⁴ ,
A group selected from R ⁵ and R ¹² and R ¹³ or R ¹⁴ may combine with each other to form a ring, and A has 2 carbon atoms which may contain an unsaturated bond and / or an aromatic ring. ~
20 represents a divalent hydrocarbon group, and A may contain two or more ring structures including a ring formed together with Y, Y
Is a carbon atom or a silicon atom, M is a metal selected from Group 4 of the periodic table, j is an integer of 1 to 4, Q is a halogen atom, a hydrocarbon group, anion coordination. Selected from a neutral ligand capable of coordinating with a child and a lone pair of electrons,
When j is 2 or more, Qs may be the same or different. Further, examples of the metallocene compound catalyst component other than the above include metallocene compounds represented by the following general formula (1b) or (2b).

[0023]

[Chemical 5]

(In the formula, R ²¹ and R ²² may be the same or different from each other and are selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and are R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ ,
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ^{14, which} may be the same or different, are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group, and are adjacent to each other among R ⁵ to R ¹² . The groups may combine with each other to form a ring, A
Represents a divalent hydrocarbon group having 2 to 20 carbon atoms, which may have an unsaturated bond and / or an aromatic ring, and A
May include two or more ring structures including a ring formed with Y, M represents a metal selected from Group 4 of the periodic table, Y is a carbon atom or a silicon atom, j
Is an integer of 1 to 4, Q is selected from a halogen atom, a hydrocarbon group, an anion ligand and a neutral ligand capable of coordinating with a lone electron pair, and when j is 2 or more, Q is selected. May be the same or different from each other. ) As a preferable example of the above-mentioned hydrocarbon group, the number of carbon atoms is 1 to
Examples thereof include an alkyl group having 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms.

R ³ may also be a cyclic hydrocarbon group containing a hetero atom such as sulfur or oxygen, such as a thienyl group or a furyl group. Specifically, methyl, ethyl,
n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetra Methylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl
-1-cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl,
Examples thereof include hydrocarbon groups such as naphthyl and tolyl.

Preferred examples of the above silicon-containing hydrocarbon group include 1 to 4 silicon atoms and 3 to 20 carbon atoms.
And an alkylsilyl group or an arylsilyl group. Specific examples include groups such as trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl. In addition, R ³ is preferably a sterically bulky substituent, and more preferably a substituent having 4 or more carbon atoms.

In the above general formula (1) or (2), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different from each other and are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. Specific examples of the preferable hydrocarbon group and silicon-containing hydrocarbon group include the same groups as described above.

Adjacent substituents of R ¹ to R ⁴ substituting on the cyclopentadienyl ring may combine with each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,
4-trimethyltetrahydroindenyl and the like can be mentioned.

Further, the adjacent substituents R ⁵ to R ¹² for substituting the fluorene ring may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like. Further, the substituents of R ⁵ to R ^{12 which} are substituted on the fluorene ring are bilaterally symmetric, that is, R ⁵ and R ¹² , R ⁶ and R ¹¹ , R.
⁷ and R ¹⁰ , and R ⁸ and R ⁹ are preferably the same group,
It is more preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Here, the 3rd, 6th, and 2nd positions of the fluorene ring
The 7th and 7th positions correspond to R ⁷ , R ¹⁰ , R ⁶ and R ¹¹ , respectively.

In the above general formula (1) or (2),
Y is a carbon atom or a silicon atom. In the metallocene compound represented by the above general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridge portion. Preferred specific examples include, for example, methylene, dimethylmethylene, diethylmethylene,
Diisopropylmethylene, methyl tert-butylmethylene, ditert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl tert-butylsilylene, dicyclohexyl Examples thereof include silylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, dinaphthylsilylene and the like.

The metallocene compound represented by the general formula (1) has a ring structure in which the substituent selected from R ¹ , R ⁴ , R ⁵ or R ¹² and the bridging moiety R ¹³ or R ¹⁴ are bonded to each other. May be formed. As an example of such a structure, R
^{The case where 1} and R ¹⁴ are bonded to each other to form a ring is exemplified below. In the metallocene compound represented by the following general formula (1c), the bridging part and the cyclopentadienyl group are integrated to form a tetrahydropentalene skeleton, and in the metallocene compound represented by the following general formula (1d), the bridging part and the cyclopentadiene group are combined. The pentadienyl groups are united to form a tetrahydroindenyl skeleton. Similarly, the bridging portion and the fluorenyl group may be bonded to each other to form a ring.

[0032]

[Chemical 6]

In the metallocene compound represented by the above general formula (2), A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring, Y is bonded to A to form a cycloalkylidene group, a cyclomethylenesilylene group, or the like.
In addition, A may include two or more ring structures including the ring formed together with Y.

Specific preferred examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydro. Examples thereof include indanilidene, cyclodimethylene silylene, cyclotrimethylene silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene, cycloheptamethylene silylene and the like.

In the above general formula (1) or (2),
M is a metal selected from Group 4 of the periodic table, and specific examples thereof include titanium, zirconium, and hafnium. In the above general formula (1) or (2), j is 1 to
It is an integer of 4. In the general formula (1) or (2), Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anion ligand, or a neutral ligand capable of coordinating with a lone electron pair. . When j is 2 or more, Q may be the same or different.

Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include the same ones as described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

Specific examples of the neutral ligand capable of coordinating with a lone pair of electrons include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1, Examples thereof include ethers such as 2-dimethoxyethane. At least one Q is preferably a halogen or an alkyl group.

Specific examples of the metallocene compound represented by the above general formula (1) or (2) according to the present invention are shown below. First, the ligand structure excluding MQ _j (metal part) of the metallocene compound is divided into three parts, Cp (cyclopentadienyl ring part), Bridge (bridging part), and Flu (fluorenyl ring part), respectively, for notation. Specific examples of the partial structure of and the specific example of the ligand structure by the combination thereof are shown below.

[0039]

[Chemical 7]

[0040]

[Chemical 8]

[0041]

[Chemical 9]

The following compounds may be mentioned as specific examples of the metallocene compound having a preferred ligand structure.

[0043]

[Chemical 10]

A specific example of MQ _j is ZrC.
l ₂ , ZrBr ₂ , ZrMe ₂ , Zr (OTs) ₂ , Zr (O
Ms) ₂ , Zr (OTf) ₂ , TiCl ₂ , TiBr ₂ , Ti
Me ₂ , Ti (OTs) ₂ , Ti (OMs) ₂ , Ti (OT
_{f) 2, HfCl 2, HfBr} 2, HfMe 2, Hf (OT
s) ₂ , Hf (OMs) ₂ , Hf (OTf) _{2 and the} like. Here, Ts is a p-toluenesulfonyl group, Ms is a methanesulfonyl group, and Tf is a trifluoromethanesulfonyl group.

Further, examples of the metallocene compound in which the substituent of the Cp ring and the substituent of the cross-linking part are bonded to each other to form a ring include the following compounds.

[0046]

[Chemical 11]

Preferred examples of the metallocene compound represented by the general formula (1) or (2) according to the present invention include the following compounds. General formula (1)
And R ¹ , R ¹³ and R ¹⁴ are methyl, R ³ is tert-butyl,
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are hydrogen and R
⁶ , R ¹¹ is tert-butyl, M is zirconium, Y is carbon,
A metallocene compound in which Q is chlorine and j is 2.

In the general formula (1), R¹³, R¹⁴Is methyl, R
³Is 1-methyl-1-cyclohexyl, R ¹, R², R^Four, R^Five,
R⁶, R⁸, R⁹, R¹¹, R¹²Is hydrogen, R⁷, R^TenIs tert-
Butyl, M is zirconium, Y is carbon, Q is chlorine, j is
A metallocene compound which is 2. In the general formula (1), R¹³, R
¹⁴Is methyl, R³Is tert-butyl, R¹, R², R^Four, R^Five,
R⁸, R⁹, R¹²Is hydrogen, R⁶And R⁷Combine with each other to form a ring
Formed- (C (CH ₃)₂CH₂CH₂C (CH₃)₂)-, R^TenWhen
R¹¹Bonded to each other to form a ring-(C (CH₃)₂CH₂
CH₂C (CH₃)₂)-, M is zirconium, Y is carbon, Q
Is chlorine and j is 2.

In the general formula (1), R ¹³ and R ¹⁴ are methyl and R
³ is trimethylsilyl, R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ ,
R ^9, R ¹² are hydrogen, R ⁶ and R ⁷ are bonded to the each other to form a ring _{- (C (CH 3) 2} CH 2 CH 2 C (CH 3) 2) -, R 10 and R ¹¹
Bonded to each other to form a ring- (C (CH ₃ ) ₂ CH ₂ CH ₂
A metallocene compound in which C (CH ₃ ) ₂ )-, M is zirconium, Y is carbon, Q is chlorine, and j is 2.

In the general formula (1), R¹³, R¹⁴Is methyl, R
³Is 1,1-dimethylpropyl, R¹, R ², R^Four, R^Five, R⁶,
R⁸, R⁹, R¹¹, R¹²Is hydrogen, R⁷, R^TenIs tert-butyl
Le, M is zirconium, Y is carbon, Q is chlorine, j is 2.
A metallocene compound. In the general formula (1), R¹³, R¹⁴But
Methyl, R³Is 1-ethyl-1-methylpropyl, R ¹, R²,
R^Four, R^Five, R⁶, R⁸, R⁹, R¹¹, R¹²Is hydrogen, R⁷, R
^TenIs tert-butyl, M is zirconium, Y is carbon, and Q is
Chlorine, a metallocene compound in which j is 2.

In the general formula (1), R ¹³ and R ¹⁴ are methyl and R
³ is 1,1,3-trimethylbutyl, R ¹ , R ² , R ⁴ , R ⁵ ,
R ⁶ , R ⁸ , R ⁹ , R ¹¹ , and R ¹² are hydrogen, and R ⁷ and R ¹⁰ are tert-
A metallocene compound in which butyl, M is zirconium, Y is carbon, Q is chlorine, and j is 2. In the general formula (1), R ¹³ , R
¹⁴ is methyl, R ³ is 1,1-dimethylbutyl, R ¹ , R ² ,
R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R ¹² are hydrogen, R ⁷ and R
^A metallocene compound in which ¹⁰ is tert-butyl, M is zirconium, Y is carbon, Q is chlorine, and j is 2.

In the general formula (1), R¹³, R¹⁴Is methyl, R
³Is tert-butyl, R¹, R², R^Four, R^Five, R⁷, R⁸,
R⁹, R^Ten, R¹²Is hydrogen, R⁶, R¹¹Is tert-butyl, M
Is zirconium, Y is carbon, Q is chlorine, and j is 2.
Talocene compound. In the general formula (1), R³, R¹³, R¹⁴But
Phenyl, R¹, R², R^Four, R^Five, R⁸, R ⁹, R¹²But water
Elementary, R⁶And R⁷Bound to each other to form a ring-(C (C
H₃)₂CH₂CH ₂C (CH₃)₂)-, R^TenAnd R¹¹Tied to each other
Combined to form a ring-(C (CH₃)₂CH₂CH₂C (C
H₃)₂)-, M is zirconium, Y is carbon, Q is chlorine, j
Wherein the metallocene compound is 2.

In the general formula (1), R ³ is trimethylsilyl, R ¹³ and R ¹⁴ are phenyl, R ¹ , R ² , R ⁴ and R ⁵ ,
R ^8, R ^9, R ¹² are hydrogen, R ⁶ and R ⁷ are bonded to the each other to form a ring _{- (C (CH 3) 2} CH 2 CH 2 C (CH 3) 2) -, R 10 and R ¹¹ bonded to each other to form a ring- (C (CH ₃ ) ₂ CH _{2
CH 2 C (CH 3) 2} ) -, M is zirconium, Y is carbon, Q
Is chlorine and j is 2.

In the general formula (1), R ¹³ is methyl, R ¹⁴ is phenyl, R ³ is tert-butyl, R ¹ , R ² , R ⁴ , R ⁵ ,
R ⁶ , R ⁸ , R ⁹ , R ¹¹ , and R ¹² are hydrogen, and R ⁷ and R ¹⁰ are tert-
A metallocene compound in which butyl, M is zirconium, Y is carbon, Q is chlorine, and j is 2. In the general formula (1), R ¹³ , R
¹⁴ is ethyl, R ³ is tert-butyl, R ¹ , R ² , R ⁴ , R ⁵ ,
R ⁶ , R ⁸ , R ⁹ , R ¹¹ , and R ¹² are hydrogen, and R ⁷ and R ¹⁰ are tert-
A metallocene compound in which butyl, M is zirconium, Y is carbon, Q is chlorine, and j is 2.

In the general formula (2), R ¹ is methyl and R ³ is tert.
- ^{butyl, R 2, R 4, R} 5, R 6, R 7, R 8, R 9, R 10,
A metallocene compound in which R ¹¹ and R ¹² are hydrogen, M is zirconium, Y is carbon, Q is chlorine, j is 2, and A is — (CH ₂ ) ₅ —. In the general formula (2), R ¹ is methyl, R ³ is tert-butyl, R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R ¹² are hydrogen, R ⁷ and R ^10. Is tert-butyl, M is zirconium, Y is carbon, Q is chlorine, j is 2, and A is-(CH ₂ ) _5- .

In the general formula (2), R ³ is trimethylsilyl, R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹²
Is hydrogen, R ⁶ and R ¹¹ are tert-butyl, M is zirconium,
A metallocene compound in which Y is carbon, Q is chlorine, j is 2, and A is — (CH ₂ ) ₅ —. In the general formula (2), R ³ is trimethylsilyl, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R 3.
A metallocene compound in which ¹² is hydrogen, R ⁷ and R ¹⁰ are tert-butyl, M is zirconium, Y is carbon, Q is chlorine, j is 2 and A is — (CH ₂ ) ₅ —.

In the general formula (2), R³Is tert-butyl,
R¹, R², R^Four, R^Five, R⁶, R⁸, R⁹, R¹¹, R¹²But water
Elementary, R⁷, R^TenIs tert-butyl, M is zirconium, Y is
Carbon, Q is chlorine, j is 2, A is-(CH₂)_Four-Is a metallo
Sen compound. In the general formula (2), R³Is 1,1-dimethylpro
Pill, R¹, R², R^Four, R^Five, R⁶, R ⁸, R⁹, R¹¹, R
¹²Is hydrogen, R⁷, R^TenIs tert-butyl and M is zirconium
Mu, Y is carbon, Q is chlorine, j is 2, A is-(CH₂)_Five-And
Metallocene compound.

In the general formula (2), R ³ is tert-butyl,
R ¹ , R ² , R ⁴ , R ⁵ , R ⁸ , R ⁹ , and R ¹² are hydrogen, R ⁶ and R ⁷
Bonded to each other to form a ring- (C (CH ₃ ) ₂ CH ₂ CH ₂
C (CH ₃ ) ₂ )-, R ¹⁰ and R ¹¹ are bonded to each other to form a ring,-(C (CH ₃ ) ₂ CH ₂ CH ₂ C (CH ₃ ) ₂ )-, M is zirconium, and Y is A metallocene compound in which carbon, Q is chlorine, j is 2, and A is — (CH ₂ ) ₄ —.

In the general formula (1), R ¹ , R ¹³ and R ¹⁴ are methyl, R ³ is tert-butyl, R ² , R ⁴ , R ⁵ , R ⁶ and R ⁸ ,
R ⁹ , R ¹¹ and R ¹² are hydrogen, R ⁷ and R ¹⁰ are tert-butyl, M
Is zirconium, Y is carbon, Q is chlorine, and j is 2. In the general formula (1), R ¹³ and R ¹⁴ are methyl, R ³ is tert-butyl, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ ,
A metallocene compound in which R ⁸ , R ⁹ , R ¹¹ , and R ¹² are hydrogen, R ⁷ and R ¹⁰ are tert-butyl, M is zirconium, Y is carbon, Q is chlorine, and j is 2.

In the general formula (1), R ¹ , R ¹³ and R ¹⁴ are methyl, R ³ is tert-butyl, R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ ,
A metallocene compound in which R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are hydrogen, M is zirconium, Y is carbon, Q is chlorine, and j is 2. In the general formula (1), R ¹³ and R ¹⁴ are methyl, R ³ is trimethylsilyl, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ ,
A metallocene compound in which R ¹¹ and R ¹² are hydrogen, R ⁷ and R ¹⁰ are tert-butyl, M is zirconium, Y is carbon, Q is chlorine, and j is 2.

In the general formula (1), R ¹³ and R ¹⁴ are phenyl,
R ³ is trimethylsilyl, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R
⁸ , R ⁹ , R ¹¹ and R ¹² are hydrogen, R ⁷ and R ¹⁰ are tert-butyl,
A metallocene compound in which M is zirconium, Y is carbon, Q is chlorine, and j is 2. The metallocene compound as described above,
They may be used alone or in combination of two or more. The metallocene compound as described above can also be used by supporting it on a particulate carrier.

As such a particulate carrier, SiO
₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO,
Inorganic carrier such as TiO ₂ , ZnO, SnO ₂ , BaO, ThO, organic such as polyethylene, propylene block copolymer, poly-1-butene, poly-4-methyl-1-pentene, styrene-divinylbenzene copolymer A carrier can be used. These particulate carriers can be used alone or in combination of two or more.

In the present invention, aluminoxane can be used as one of the promoters for the metallocene catalyst. As conventionally known, aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butyl. Trialkyl aluminum such as aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricycloalkyl aluminum such as tricyclohexyl aluminum, tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum Chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum aryloxy such as diethyl aluminum phenoxide. Do and the like.
Among these, trialkyl aluminum and tricycloalkyl aluminum are preferable, and trimethyl aluminum is particularly preferable.

Further, as the organoaluminum compound used in preparing the aluminoxane, isoprenylaluminum represented by the following general formula can be used. Solvents used for the solution or suspension of aluminoxane include benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane, cyclopentane,
Alicyclic hydrocarbons such as cyclohexane, cyclooctane, and methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, especially chlorinated products , Hydrocarbon solvents such as bromide.

In addition, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable. The organoaluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. Examples of ionized ionic compounds include Lewis acids, ionic compounds, borane compounds and carborane compounds.

As the Lewis acid, a compound represented by BR ₃ (wherein R is a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group or a fluorine atom). And trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl).
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, Tris (p-
Trily) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts. Specifically, as the trialkyl-substituted ammonium salt, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl)
Examples thereof include ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

As the borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III)
Examples thereof include salts of metal borane anions. Carborane compounds include 4-carbanonaborane (14),
Salts of metal carborane anions such as 1,3-dicarbanonaborane (13) and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) Can be mentioned.

The above-mentioned ionized ionic compound is
They may be used alone or in combination of two or more. The organoaluminum oxy compound or the ionized ionic compound can also be used by supporting it on the above-mentioned particulate carrier. In forming the catalyst, the following organoaluminum compounds may be used together with the organoaluminum oxy compound or the ionized ionic compound.

As the organoaluminum compound, a compound having at least one Al-carbon bond in the molecule can be used. Examples of such a compound include an organoaluminum compound represented by the following general formula. (R ¹ ) m Al (O (R ² )) nHpXq (In the formula, R ¹ and R ² may be the same or different from each other, and the carbon number is usually 1 to 15, preferably 1 to 4) Represents a hydrogen group, X represents a halogen atom, m is 0 <m ≦ 3, and n is 0.
≦ n <3, p is 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3. ) The propylene block copolymer (A) used in the present invention comprises a step of polymerizing propylene in the presence of the above-mentioned metallocene catalyst to form a propylene homopolymer component, and propylene and an α-olefin, preferably ethylene. And the step of forming a propylene / α-olefin copolymer component by copolymerizing the above in any order.

The polymerization process of the propylene block copolymer (A) is usually about -50 to 200 ° C, preferably about 5
At a temperature of 0 to 100 ° C., and usually at atmospheric pressure to 100 kg / c
It is carried out under a pressure of m ² , preferably about ² to 50 kg / cm ² . Polymerization of propylene can be carried out by any of batch, semi-continuous and continuous methods. Inorganic filler (B) Specific examples of the inorganic filler (B) used in the present invention include talc, clay, calcium carbonate, mica, silicates, carbonates, glass fibers, barium sulfate and the like. . Among these, talc and barium sulfate are preferable, and talc is particularly preferable. The average particle size of talc is
It is desirable to be in the range of 1 to 5 μm, preferably 1 to 3 μm. The inorganic filler (B) may be used alone or in combination of two or more.

Elastomer (C) The elastomer (C) optionally used in the present invention includes a propylene / α-olefin random copolymer (C-1) and an ethylene / α-olefin random copolymer (C-). 2) and mixtures thereof.
The propylene / α-olefin random copolymer (C
-1) is propylene and ethylene or having 4 to 4 carbon atoms.
It is a random copolymer rubber with 20 α-olefins.

As the α-olefin having 4 to 20 carbon atoms, specifically, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like can be mentioned. These α-olefins and ethylene can be used alone or in combination of two or more kinds. Of these, ethylene is particularly preferably used.

The propylene / α-olefin random copolymer (C-1) has a molar ratio of propylene and α-olefin (propylene / α-olefin) of from 90/10 to 7
It is desirable that it is in the range of 0/30, preferably 80/20 to 65/35. The melt flow rate (MFR; ASTM D 1238, 230 ° C, load 2.16 kg) of the propylene / α-olefin random copolymer (C-1) was 0.
It is desirable to be in the range of 1 g / 10 minutes or more, preferably 0.5 to 5 g / 10 minutes.

The ethylene / α-olefin random copolymer (C-2) is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-eikosen and the like. These α-olefins can be used alone or in combination of two or more kinds. Among these, especially propylene, 1-butene,
1-hexene and 1-octene are preferably used.

The ethylene / α-olefin random copolymer (C-2) has a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of 95/5 to 70/3.
Desirably, it is within the range of 0, preferably 90/10 to 75/25. In addition, the ethylene / α-olefin random copolymer (C-2) has a melt flow rate (MF
R; ASTM D 1238, 230 ° C, load 2.16 kg) is 0.1 g /
It is desirable that the time is 10 minutes or more, preferably 0.5 to 5 g / 10 minutes.

The elastomer (C) as described above may be used alone or in combination of two or more. Polyolefin Resin Composition The polyolefin resin composition according to the present invention contains 60% of the propylene block copolymer (A) based on 100% by weight of the total of the propylene block copolymer (A) and the inorganic filler (B). To 98% by weight, preferably 70 to 95% by weight, particularly preferably 80 to 90% by weight, and 2 to 40% by weight, preferably 5% by weight of the inorganic filler (B).
To 30% by weight, particularly preferably 10 to 20% by weight, and if necessary, the elastomer (C) is 20% by weight or less, usually 1 to 20% by weight, preferably 0 to 10% by weight. %, Particularly preferably 0 to 5% by weight.

The polyolefin resin composition according to the present invention obtained by blending the above-mentioned component (A), component (B) and optionally component (C) in the above proportion is excellent in fluidity during molding. In addition, it is possible to provide a molded article having an excellent balance of physical properties such as flexural modulus, impact resistance, hardness, gloss and embrittlement temperature. Therefore, the resin composition of the present invention,
It can be suitably used as a resin raw material for injection molding, and an injection molded product in which the generation of flow marks is prevented can be obtained.

In the polyolefin resin composition according to the present invention, in addition to the above-mentioned propylene block copolymer (A), inorganic filler (B) and elastomer (C), heat resistance may be added, if necessary. Other additives such as stabilizers, antistatic agents, weather resistance stabilizers, light resistance stabilizers, antioxidants, antioxidants, fatty acid metal salts, softeners, dispersants, fillers, colorants, lubricants, pigments, etc. It can be blended within a range that does not impair the object of the present invention.

As the above-mentioned antioxidant, any conventionally known antioxidant of phenol type, sulfur type or phosphorus type can be blended. The antioxidants can be used alone or in combination of two or more. The amount of the antioxidant to be added is 0.01 to 1 part by weight, preferably 0.05 to 0.3 part by weight, based on 100 parts by weight of the propylene block copolymer (A).

Examples of the light resistance stabilizer include hindered amine light stabilizers (HALS) and ultraviolet absorbers. Specific examples of the hindered amine light stabilizer include tetrakis (1,2,2,6,6-pentamethyl
-4-piperidine) -1,2,3,4-butanetetracarboxylate (molecular weight = 847), ADEKA STAB LA-52 [molecular weight = 847, tetrakis (1,2,2,6,6-pentamethyl-4
-Piperidine) -1,2,3,4-butanetetracarboxylate], ADEKA STAB LA-62 (molecular weight = about 900),
ADEKA STAB LA-67 (molecular weight = approximately 900), ADEKA STAB LA-63 (molecular weight = approximately 2000), ADEKA STAB LA-68LD (molecular weight = approximately 1900) (all manufactured by Asahi Denka Co., Ltd.), Chimassorb (CHIMASSOR)
B) 944 (molecular weight = 72500, manufactured by Ciba Specialty Chemicals Co., Ltd., trademark).

As the ultraviolet absorber, specifically, Tinuvin 326 (molecular weight = 316), Tinuvin 32 are used.
7 (molecular weight = 357), Tinuvin 120 (molecular weight = 43
8) (all are trademarks of Ciba Specialty Chemicals Co., Ltd.). These light resistance stabilizers may be used alone or in combination of two or more.

The content of the hindered amine light stabilizer or the ultraviolet absorber is preferably 100 parts by weight of the propylene block copolymer (A), the inorganic filler (B) and the optional elastomer (C). Is 0.0
1 to 1 part by weight, particularly preferably 0.1 to 0.5 part by weight. The fatty acid metal salt is a neutralizing agent for the catalyst contained in the polyolefin resin composition containing the propylene block copolymer (A), and a filler (inorganic filler (B Of the resin composition containing a fatty acid metal salt, a molded product having excellent physical properties such as strength required for automobile interior parts can be obtained.

Specific examples of the fatty acid metal salt include calcium stearate (melting point = 158 ° C.) and lithium stearate (melting point = 220 ° C.). The amount of the fatty acid metal salt compounded is preferably 0.1 part by weight per 100 parts by weight based on 100 parts by weight of the total of the propylene block copolymer (A), the inorganic filler (B) and the optional elastomer (C). It is from 1 to 1 part by weight, particularly preferably from 0.05 to 0.5 part by weight. When the amount of the fatty acid metal salt is within the above range, the functions of the neutralizing agent and the dispersant can be sufficiently exerted, and the amount of sublimation from the molded product can be reduced.

As the above pigment, known pigments can be used,
Inorganic pigments such as metal oxides, sulfides, and sulfates;
Examples thereof include phthalocyanine-based, quinacridone-based, benzidine-based organic pigments, and the like. The amount of the pigment blended is preferably 0.01 to 10 parts by weight, particularly preferably 100 parts by weight with respect to the total 100 parts by weight of the propylene block copolymer (A), the inorganic filler (B) and the optional elastomer (C). Is preferably 0.05 to 2 parts by weight.

The polyolefin resin composition according to the present invention contains the above-mentioned propylene block copolymer (A), inorganic filler (B), and optionally elastomer (C), and other additives in a Banbury mixer, It can be obtained by mixing or melt-kneading with a mixing device such as a single-screw extruder, a twin-screw extruder, or a high-speed twin-screw extruder.

[0088]

Since the polyolefin resin composition according to the present invention contains the specific propylene block copolymer (A) and the inorganic filler (B) in a specific ratio, it has a good balance between rigidity and impact resistance. It is possible to provide a molded product (including an injection molded product) which is excellent in appearance, is less likely to generate a flow mark, is inconspicuous even if it occurs, and has an excellent appearance and a high gloss. In particular, when the composition is blended with the elastomer (C), a molded article having more excellent impact resistance can be obtained.

The polyolefin resin composition according to the present invention can be suitably used for producing home electric appliances such as hot plates, rice cookers, pot bodies, washing machines, and air purifiers by taking advantage of the above characteristics. You can

[0090]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0091]

Example 1 [Synthesis of metallocene compound] <Dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl)
Synthesis of zirconium dichloride> (1) Synthesis of 4,4'-di-t-butyldiphenylmethane A two-necked flask with a capacity of 300 ml was sufficiently replaced with nitrogen, and A
lCl ₃ (38.4 g, 289 mmol) was added, and CH ₃ N was added.
80 ml of O ₂ was added and dissolved to obtain a solution (1). A 500 ml three-necked flask equipped with a dropping funnel and a magnetic stirrer was sufficiently replaced with nitrogen, and 25.6 g (152 mmol) of diphenylmethane and 2,6-di-t-butyl-
43.8 g (199 mmol) of 4-methylphenol was added, and 80 ml of CH ₃ NO ₂ was added and dissolved. Cooled with ice bath with stirring. The solution of (1) was added dropwise over 35 minutes, and then the reaction solution was stirred at 12 ° C. for 1 hour. The reaction solution was poured into 500 ml of ice water, and the reaction product was extracted with 800 ml of hexane. The organic layer containing the reaction product was washed with 600 ml of 5% aqueous sodium hydroxide, followed by MgSO 4.
Dried at ₄ . After the MgSO ₄ was filtered off, the solvent was evaporated and the resulting oil was cooled to −78 ° C. to precipitate a solid, which was collected by filtration and washed with 300 ml of ethanol. Drying under reduced pressure gave 4,4'-di-t-butyldiphenylmethane. The yield was 18.9 g. (2) Synthesis of 2,2'-diiodo-4,4'-di-t-butyldiphenylmethane In a 200 ml flask equipped with a magnetic stirring bar, 4,4 '
-Di-t-butyldiphenylmethane 1.95 (6.96 mm
ol) and 0.78 g (3.48 mmol) of HIO ₄ , I ₂
1.55 g (6.12 mmol), conc H ₂ SO ₄ 0.4
8 ml was added. Acetic acid 17.5 ml, water 3.75
ml was added, and the mixture was heated to 90 ° C. with stirring and reacted for 5 hours. The reaction solution was poured into 50 ml of ice water and (C ₂ H ₅ ) ₂ O was added.
The reaction product was extracted with. The organic layer containing the reaction product was washed with 100 ml of a saturated aqueous NaHSO ₄ solution, subsequently Na ₂ CO ₃ was added, and after stirring, Na ₂ CO ₃ was filtered off. Further, the organic layer was washed with 800 ml of water, Mg ₂ SO ₄ was added and dried. After filtering off Mg ₂ SO ₄ , the solvent was distilled off to obtain a yellow oil. This yellow oil was purified by column chromatography to obtain 2,2'-diiodo-4,4'-di-t-butyldiphenylmethane. The yield was 3.21 g. (3) Synthesis of 3,6-di-t-butylfluorene 2,2'-diiodo-4,4'-in a two-necked flask having a capacity of 50 ml.
3.21 g (6.03 m) of di-t-butyldiphenylmethane
mol) and 2.89 g (47.0 mmol) of copper powder were added, and the mixture was heated to 230 ° C. and reacted for 5 hours while stirring. The reaction product was extracted with acetone and the solvent was distilled off to obtain a reddish brown oil. A pale yellow oil was obtained from this reddish brown oil by column chromatography. The fraction containing the unreacted raw material was applied again to the column to collect only the target substance. Recrystallization from methanol gave a white solid 3,6-di-t-
Butyl fluorene was obtained. The yield was 1.08 g. (4) Synthesis of 1-tert-butyl-3-methylcyclopentadiene Under a nitrogen atmosphere, a tert-butylmagnesium chloride / diethyl ether solution having a concentration of 2.0 mol / l (45
0 ml, 0.90 mol) was added to dehydrated diethyl ether (3
50 ml) was added to the solution while keeping it at 0 ° C under ice cooling.
3-Methylcyclopentenone (43.7g, 0.45mm
ol) in anhydrous diethyl ether (150 ml) was added dropwise, and the mixture was further stirred at room temperature for 15 hours. Ammonium chloride (80.0 g, 1.50 mol) in water (3
(50 ml) solution was added dropwise under ice cooling while maintaining 0 ° C. After adding water (2500 ml) to this solution and stirring,
The organic layer containing the reaction product was separated and washed with water. A 10% aqueous hydrochloric acid solution (82 ml) was added to this organic layer while keeping it at 0 ° C. under ice cooling, and then the mixture was stirred at room temperature for 6 hours. The organic layer of this reaction solution was separated, washed with water, saturated aqueous sodium hydrogen carbonate solution, water, and saturated saline, and then dried over anhydrous magnesium sulfate (drying agent). The desiccant was filtered and the solvent was distilled off from the filtrate to obtain a liquid. This liquid is distilled under reduced pressure (4
5 to 47 ° C / 10 mmHg)
To obtain a pale yellow liquid (1-tert-butyl-3-methylcyclopentadiene). The analysis value is shown below.

¹ H-NMR (270 MHz, CDCl
₍₃ , TMS standard) δ 6.31 + 6.13 + 5.94 + 5.87 (s + s + t +
d, 2H), 3.04 + 2.95 (s + s, 2H), 2.
17 + 2.09 (s + s, 3H), 1.27 (d, 9H) (5) Synthesis of 3-tert-butyl-5,6,6-trimethylfulvene 1-tert-butyl-3-methylcyclone under nitrogen atmosphere Dehydrated acetone (55.2 g, 950.4 mmol) was added dropwise to a solution of pentadiene (13.0 g, 95.6 mmol) in dehydrated methanol (130 ml) under ice-cooling, and pyrrolidine (68.0 g, 956.1 mmo
l) was added dropwise, and the mixture was stirred at room temperature for 4 days. After diluting the reaction solution with diethyl ether (400 ml), water 400
ml was added. The organic layer containing the reaction product is separated,
5N hydrochloric acid aqueous solution (150 ml x 4), water (200 ml)
× 3), washed with saturated saline (150 ml), and then dried over anhydrous magnesium sulfate (drying agent). The desiccant was filtered and the solvent was distilled off from the filtrate to obtain a liquid. By distilling this liquid under reduced pressure (70 to 80 ° C./0.1 mmHg), 10.5 g of a yellow liquid (3-tert-butyl-5,6,6-trimethylfulvene) was obtained. The analysis value is shown below.

¹ H-NMR (270 MHz, CDCl
₍₃ , TMS standard) δ 6.23 (s, 1H), 6.05 (d, 1H), 2.2
3 (s, 3H), 2.17 (d, 6H), 1.17 (s,
9H) (6) Synthesis of 2- (3-tert-butyl-5-methylcyclopentadienyl) -2- (3,6-di-tert-butylfluorenyl) propane 3,6-di-tert- Butylfluorene (0.9g, 3.4mm
ol) in THF (30 ml) under ice-cooling, n-butyllithium hexane solution (2.1 ml, 3.4 mmo).
1) was added dropwise under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 6 hours. Furthermore, under ice cooling, 3-tert-butyl-5,6,6-trimethylfulvene (0.6 g, 3.5 mm) was added to this red solution.
sol) in THF (15 ml) was added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for 12 hours, and then 30 ml of water was added.
The organic layer containing the reaction product separated and extracted with diethyl ether was dried over magnesium sulfate and then filtered, and the solvent was removed from the filtrate under reduced pressure to obtain a solid. The solid was recrystallized from hot methanol to give 1.2 g of a pale yellow solid (2-
(3-tert-butyl-5-methylcyclopentadienyl) -2-
(3,6-di-tert-butylfluorenyl) propane) was obtained. The analysis value is shown below.

¹ H-NMR (270 MHz, CDCl
₃ , TMS standard) δ7.72 (d, 2H), 7.18-7.05 (m, 4
H), 6.18-5.99 (s + s, 1H), 4.32-
4.18 (s + s, 1H), 3.00-2.90 (s +
s, 2H), 2.13-1.98 (t + s, 3H), 1.
38 (s, 18H), 1.19 (s, 9H), 1.10
(D, 6H) (7) Synthesis of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride 2- To a solution of (3-tert-butyl-5-methylcyclopentadienyl) -2- (3,6-di-tert-butylfluorenyl) propane (1.3 g, 2.8 mmol) in diethyl ether (40 ml). A hexane solution of n-butyllithium (3.6 ml, 5.8 mmol) was added dropwise under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 16 hours. The solvent was removed from the reaction mixture under reduced pressure to give a reddish orange solid. To this solid, 150 ml of dichloromethane was added at −78 ° C. to dissolve with stirring, and then this solution was cooled to −78 ° C. and zirconium tetrachloride (THF) 2 complex (1.0 g, 2.
7 mmol) in dichloromethane (10 ml), and the mixture was stirred at -78 ° C for 6 hours and at room temperature for 24 hours.
The solvent was removed from this reaction solution under reduced pressure to obtain an orange solid. Furthermore, this solid was extracted with toluene, filtered through Celite, the solvent was removed from the filtrate under reduced pressure, and then recrystallized from diethyl ether to obtain 0.18 g of an orange solid (dimethylmethylene (3-tert-butyl-5- Methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl)
Zirconium dichloride) was obtained. The analysis value is shown below.

¹ H-NMR (270 MHz, CDCl
₍₃ , TMS standard) δ 7.98 (dd, 2H), 7.90 (d, 1H), 7.
69 (d, 1H), 7.32-7.25 (m, 2H),
6.01 (d, 1H), 5.66 (d, 1H), 2.54
(S, 3H), 2.36 (s, 3H), 2.28 (s, 1
H), 1.43 (d, 18H), 1.08 (s, 9H) <Synthesis of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride> Organometall
Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was synthesized according to the method described in ics, 13,954 (1994). [Preparation of silica-supported methylaluminoxane] In a 500 ml-capacity reactor that was sufficiently replaced with nitrogen, 20 g of silica (H-121, trade name H-121, manufactured by Asahi Glass Co., Ltd., dried under nitrogen at 150 ° C. for 4 hours), and 200 ml of toluene. Was charged, and 60 ml of methylaluminoxane (manufactured by Albemarle, 10 wt% toluene solution) was added dropwise under nitrogen atmosphere while stirring. Then, this mixture was reacted at 110 ° C. for 4 hours, the reaction system was allowed to cool to precipitate solid components, and the supernatant solution was removed by decantation. Subsequently, the solid component was washed 3 times with toluene and 3 times with hexane.
It was washed twice to obtain silica-supported methylaluminoxane. [Production of Propylene-based Block Copolymer (A-1)] 20 mmol of silica-supported methylaluminoxane in terms of aluminum was put into an autoclave having a capacity of 20 liters that had been sufficiently replaced with nitrogen, and suspended in 500 ml of heptane. Then, dimethylmethylene (3-tert
-Butyl-5-methylcyclopentadienyl) (3,6-di-ter
t-Butylfluorenyl) zirconium dichloride 54
After adding mg (0.088 mmol) as a toluene solution, then triisobutylaluminum (80 mm
ol) was added and stirred for 30 minutes to obtain a catalyst suspension.

An autoclave having an internal volume of 20 liters, which had been sufficiently replaced with nitrogen, was charged with 5 kg of propylene and 3 liters of hydrogen, and the above catalyst suspension was added to the autoclave to give 3.0 to 3.5.
Bulk homopolymerization was performed at 70 ° C. for 40 minutes under a pressure of MPa. After completion of the homopolymerization, the vent valve was opened, and unreacted propylene was depressurized until the pressure inside the polymerization vessel became normal pressure. After completion of depressurization, ethylene and propylene were subsequently copolymerized. That is, ethylene / propylene mixed gas (25 mol% ethylene, 75 mol% propylene)
Is continuously supplied while adjusting the vent opening of the polymerization vessel so that the pressure in the polymerization vessel becomes 1 MPa, and the pressure is increased to 60 at 70 ° C.
Polymerization was carried out for a minute. The polymerization reaction was stopped by adding a small amount of methanol, and the unreacted gas in the polymerization vessel was purged.

The yield of the propylene block copolymer (A-1) obtained as described above was 2.9 kg. This copolymer (A-1) has MFR (ASTM D 123
8,230 ℃, 2.16kg load) is 42g / 10 minutes, n-
The amount of the decane-soluble component was 11% by weight, the intrinsic viscosity [η] of the n-decane-soluble component measured in 135 ° C. decalin was 2.2 dl / g, and the ethylene content was 41 mol%. . The propylene homopolymer part of the copolymer (A-1) has a melting point (Tm) of 158 ° C., a weight average molecular weight (Mw) of 140,000 and a number average molecular weight (Mn) of 70. 1,000 and Mw / Mn of 2.0
Met. Further, the stereoregularity of the propylene homopolymer part was such that the mmmm fraction was 95.8%, and the 2,1-insertion and 1,
3-Neither insertion was detected.

The amount, composition, molecular weight, stereoregularity, etc. of the polymer obtained in each stage were fixed as follows. First, a propylene block copolymer (A-
1) was heat-treated with n-decane at 150 ° C for 2 hours, cooled to room temperature, and then the precipitated solid component was filtered. The solid component obtained at this time was used as the propylene homopolymer obtained in the first stage. The component obtained by concentrating and drying the filtrate under reduced pressure was defined as an n-decane-soluble component. Each component was subjected to various analyzes according to the conventional method. [Production of Polyolefin Resin Composition] The propylene block copolymer (A-1) obtained as described above,
Talc (B-1) [Inorganic filler, manufactured by Hayashi Kasei Co., Ltd., K-
1 (trademark), average particle diameter 2 μm], Irganox 1010 (trademark) [antioxidant (manufactured by Ciba Geigy)], and Irgafos 16
8 (trademark) [antioxidant (manufactured by Ciba Geigy)], ADEKA STAB LA-52 (trademark) [hindered amine light stabilizer, molecular weight = 847, manufactured by Asahi Denka Co., Ltd.] and calcium stearate are shown in Table 1. After being mixed with a tumbler type mixer, the mixture was melt-kneaded and pelletized with a twin-screw extruder.

From the polyolefin resin composition thus obtained, an injection molding machine [manufactured by Niigata Iron Works, AN10
0] using a flat plate (100 mm × 300 mm × 3 mm
(Thickness) was injection-molded and the flow mark was observed. Also, using an injection molding machine [IS100 manufactured by Toshiba Machine Co., Ltd.]
TM test pieces were injection-molded and various physical properties were measured. The results are shown in Table 1.

The physical property measuring methods are as follows. [Tensile Properties] Tensile properties were measured by performing a tensile test according to ASTM D638-84 and measuring tensile elongation under the following conditions. <Test Conditions> Test piece: ASTM D638-84 No. 1 Distance between dumbbell chucks: 114 mm Temperature: 23 ° C. Tensile speed: 10 mm / min [Bending characteristics] Bending characteristics are determined by performing a bending test under the following conditions according to ASTM D-790 to obtain a bending elastic modulus. It was

<Test conditions> Test piece: 6.4 mm (thickness) x 12.7 mm (width) x 12
7 mm (length) Span: 100 mm Bending speed: 2 mm / min Measurement temperature: 23 ° C [Izod impact strength] Izod impact strength is ASTM
According to D-256, an impact test was conducted under the following conditions to obtain the value.

<Test conditions> Test piece: 12.7 mm (width) x 6.4 mm (thickness) x 64
mm (length) Notch: Machining Measurement temperature: 23 ° C [Glossiness] Glossiness is based on ASTM D523.
The measurement was performed under the conditions of an incident angle of 60 degrees and a detection angle of 60 degrees.

The injection molding conditions for the test pieces used for the flow mark observation and the ASTM test are as follows. <Injection molding conditions> Resin temperature: 230 ° C Mold temperature: 40 ° C Injection time: 5 seconds Pressure holding time: 5 seconds Cooling time: 25 seconds

[0104]

[Comparative Example 1] [Propylene-based block copolymer (A-
Production of 2)] A propylene-based block copolymer was prepared in the same manner as in Example 1 except that 70 mg of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was used as the metallocene compound. A combined product (A-2) was obtained.

The propylene block copolymer (A-2) obtained as described above was MFR (ASTM D 1238, 2
30 ° C., 2.16 kg load) is 40 g / 10 minutes, the amount of n-decane-soluble component is 11.0% by weight, and the intrinsic viscosity [η] of n-decane-soluble component measured in decalin at 135 ° C. Was 2.2 dl / g and the ethylene content was 41 mol%. The propylene homopolymer part of the copolymer (A-1) has a melting point (Tm) of 150 ° C., a weight average molecular weight (Mw) of 141,000 and a number average molecular weight (Mn) of 60. , And Mw / Mn is 2.3.
Met. Further, the stereoregularity of the propylene homopolymer part was such that the mmmm fraction was 95.9%, the 2,1-insertion ratio was 0.80%, and the 1,3-insertion ratio was 0.05. %Met. [Production of Polyolefin Resin Composition] Using this propylene block copolymer (A-2), a polyolefin resin composition was produced in the same manner as in Example 1 and its physical properties were evaluated. The results are shown in Table 1.

[0106]

[Comparative Example 2] A commercially available propylene / ethylene block copolymer (A-3) manufactured using a magnesium chloride-supported titanium catalyst (Ziegler-Natta catalyst) [trade name J
708, manufactured by Grand Polymer Co., Ltd.] are as follows. Propylene / ethylene block copolymer (A
-3) propylene homopolymer part has a melting point (Tm) of 16
0 ° C, MFR (ASTM D 1238, 230 ° C, load 2.16k
g) is 40 g / 10 min, Mw / Mn is 4.4, the amount of decane-soluble matter is 11.5% by weight, and the n-decane-soluble matter has an intrinsic viscosity [135] measured in decalin. η] was 2.8 dl / g. In addition, the stereoregularity of the polymer in the decane-insoluble portion has a mmmm fraction of 96.5%.
And neither the 2,1-insertion nor the 1,3-insertion was detected.

This propylene block copolymer (A-
Using 3), a polyolefin resin composition was produced in the same manner as in Example 1, and its physical properties were evaluated. The results are shown in Table 1.

[0108]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-9-316147 (JP, A) JP-A-10-1573 (JP, A) JP-A-11-349779 (JP, A) JP-A-2000-239462 (JP, A) International publication 99/011680 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 53/00 C08F 4/64 C08F 297/08

Claims (5)

(57) [Claims] 1. A propylene-based block copolymer (A) comprising 60 to 98% by weight of a propylene homopolymer part and a propylene / α-olefin random copolymer part prepared by using a metallocene catalyst, and an inorganic material. The filler (B) is contained in an amount of 2 to 40% by weight, the propylene block copolymer (A) has an α-olefin content of 2 to 20% by weight, and a melt flow rate (ASTM D1238, 230 ℃, load 2.16kg) is 8
˜100 g / 10 min, and the propylene homopolymer part of the propylene block copolymer (A) is (i) a melt flow rate (ASTM D 123
8,230 ℃, 2.16kg load) 0.01-1000g / 10
And (ii) the proportion of regio-irregular units based on 2,1-insertion or 1,3-insertion of propylene monomer in all propylene constitutional units, which is (ii) determined from ¹³ C-NMR spectrum, is 0. 2% or less, and (iii) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 1 to 3, which is a polyolefin resin composition. 2. The elastomer (C) is contained in an amount of 20% by weight or less based on 100% by weight of the total amount of the propylene block copolymer (A) and the inorganic filler (B). The polyolefin resin composition according to claim 1, wherein 3. The polyolefin resin composition according to claim 1 or 2, wherein the metallocene compound catalyst component forming the metallocene catalyst is represented by the following general formula (1) or (2): 1] (In the formula, R ³ is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ and R ^{14, which} may be the same or different from each other, are selected from the group consisting of a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group, and among the groups represented by R ¹ to R ^12. , Adjacent groups may be bonded to each other to form a ring, and in the case of the general formula (1), a group selected from R ¹ , R ⁴ , R ⁵ and R ¹² and R ^{1 3} or R ¹⁴ are bonded to each other. To form a ring, and A represents a divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain an unsaturated bond and / or an aromatic ring,
A may include two or more ring structures including a ring formed with Y, Y is a carbon atom or a silicon atom, M is a metal selected from Group 4 of the periodic table, j is an integer of 1 to 4, Q is selected from a halogen atom, a hydrocarbon group, an anion ligand and a neutral ligand capable of coordinating with a lone electron pair, and when j is 2 or more, Q may be the same as or different from each other. ). 4. The polyolefin resin composition according to claim 1, wherein the inorganic filler (B) is talc. 5. The polyolefin resin composition according to any one of claims 1 to 4, which is used in the production of home electric appliances.