JP2002275331A - Polypropylene resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition that can be used to form a molded article having rigidity and transparency that are both well- balanced and improved, particularly an injection-molded thick article having an excellent balance of rigidity and transparency, wherein vacuum bubbles can be prevented. SOLUTION: This polypropylene resin composition comprises 100 pts.wt. of a polypropylene (A) obtained by random copolymerization of propylene and an α-olefin in the presence of a metallocene catalyst, and 0.05-0.5 pt.st. of a nucleant (B), wherein, regarding component (A), the MFR is 8-80 g/10 min, the α-olefin content is 0.05-5.0 wt.%, the ratios of position irregular units based on 2,1-insertion and 1,3-insertion of a propylene monomer in the whole propylene constituent units, the ratios being determined by a<13> C-NMR spectrum, are each <=0.2%, and the Mw/Mn determined by GPC is 0-3.5. The composition can be used to manufacture injection-molded thick articles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition having excellent transparency and impact resistance and its use, and more particularly, to a thick injection molded article formed from the composition.

[0002]

BACKGROUND OF THE INVENTION Polypropylene resins are generally used in a wide range of applications, such as food containers and pharmaceutical containers, because they are excellent in chemical properties, physical properties and moldability, and are inexpensive. . However, the polypropylene resin itself did not always have sufficient transparency and mechanical strength characteristics. In addition, since the polypropylene resin is a crystalline resin, there is a problem that transparency is insufficient and a thick molded product tends to generate vacuum bubbles.

In order to improve transparency and prevent the occurrence of vacuum bubbles, a method of adding a nucleating agent to a polypropylene resin or a method of adding an amorphous ethylene / propylene copolymer to a polypropylene resin is employed. Have been. However, even with these methods, it is difficult to satisfy the transparency and the rigidity at the same time, but it is difficult and unsatisfactory, even if the performance can be imparted to either the transparency or the rigidity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and it is possible to prepare a molded article having improved rigidity and transparency at the same time. An object of the present invention is to provide a polypropylene resin composition. Another object of the present invention is to provide a polypropylene resin composition capable of preparing a molded article which does not easily generate vacuum bubbles even with a thick wall, particularly a thick injection molded article.

Another object of the present invention is to provide a thick-walled injection-molded article comprising the polypropylene resin composition and having excellent performance.

[0006]

SUMMARY OF THE INVENTION A polypropylene resin composition according to the present invention comprises: 100 parts by weight of a polypropylene (A) obtained by random copolymerization of propylene and an α-olefin in the presence of a metallocene catalyst; B) 0.05-0.
5 parts by weight of the polypropylene (A)
Are (i) melt flow rate (ASTM D 1238, 230 ° C,
2.16 kg load) is in the range of 8 to 80 g / 10 min.
i) the content of α-olefin is 0.5 to 5.0% by weight, and (iii) the content is determined from ¹³ C-NMR spectrum.
The proportion of the position irregular units based on 2,1-insertion or 1,3-insertion of the propylene monomer in all the propylene constituent units is 0.2% or less, and (iv) gel permeation chromatography (GPC )) Is characterized in that the molecular weight distribution (Mw / Mn) determined by (1) is from 1 to 3.5.

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]

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(Wherein, 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 may be the same or different from each other and represent 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. 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;
And Y may be a carbon atom or a silicon atom, and may include two or more ring structures including a ring formed with
Represents a metal selected from Group 4 of the periodic table, and j represents 1 to
And Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand and a neutral ligand capable of coordinating with a lone electron pair. When j is 2 or more, Q is the same as each other. It may be different. The α-olefin which is a constituent component of the polypropylene (A) is preferably ethylene.

The nucleating agent (B) is preferably an organic phosphate ester nucleating agent. Further, the organic phosphate ester nucleating agent is preferably an organic phosphate ester nucleating agent represented by the following formula (1) and / or formula (2).

[0011]

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[0012]

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(Wherein R ¹ is a group of ^{1 to} 10 carbon atoms)
R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ may be the same or different, and M is A metal atom having 1 to 3 valences, n is an integer of 1 to 3, and m is 1 or 2
It is. The thick injection molded article according to the present invention is characterized by comprising the above-mentioned polypropylene resin composition according to the present invention.

It is preferable that the maximum thickness of the thick injection molded article is 3 mm or more. Representative examples of the thick injection molded product include a toothbrush handle and a battery container.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polypropylene resin composition according to the present invention and its use will be specifically described. The polypropylene resin composition according to the present invention contains a polypropylene (A) and a nucleating agent (B).

Polypropylene (A) The polypropylene (A) used in the present invention is a random copolymer of propylene and α-olefin. α-
As the olefin, two to two carbon atoms other than propylene
20, preferably 2 to 10 α-olefins can be used, and specific examples include ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Among them, ethylene is preferred.

The polypropylene (A) has the following properties. (I) Melt flow rate (MFR; ASTM D 1238, 230)
° C, 2.16 kg load) is 8 to 80 g / 10 min, preferably 20 to 60 g / 10 min, more preferably 20 to 40 g.
/ 10 minutes. When the melt flow rate is within the above range, the molding having a good balance between the fluidity (moldability) of the obtained polypropylene resin composition and the mechanical strength characteristics of the molded product, and having a good appearance. Goods are obtained. (Ii) polypropylene (A), ie, propylene-α-
The α-olefin content in the olefin random copolymer is 0.5 to 5.0% by weight, preferably 1.0 to 5.0% by weight.
It is in the range of 3.0% by weight. When the content of the α-olefin is within the above range, a polypropylene resin composition capable of preparing a molded article having an excellent balance between mechanical strength characteristics and transparency can be obtained. (Iii) The proportion of the position irregular units based on 2,1-insertion or 1,3-insertion of the propylene monomer in all the propylene constitutional units obtained from the ¹³ C-NMR spectrum is 0.2% or less, preferably 0.1% or less, especially 0.05
% Or less. (Iv) Molecular weight distribution (Mw / M) determined by gel permeation chromatography (GPC)
n) is in the range of 1 to 3.5, preferably 1 to 2.5, more preferably 1 to 2.3.

The polypropylene (A) preferably further has the following characteristics (v) and (vi). (V) n-decane soluble matter (propylene homopolymer is n
-Treated with decane at 150 ° C. for 2 hours, then returned to room temperature,
(% by weight dissolved in n-decane) is 2% by weight or less, preferably 1% by weight or less. (Vi) The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is usually 135.
To 165 ° C, preferably 145 to 160 ° C, more preferably 148 to 153 ° C.

The polypropylene (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).

[0020]

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(Wherein 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 may be the same or different from each other and represent 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. 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;
And Y may be a carbon atom or a silicon atom, and may include two or more ring structures including a ring formed with
Represents a metal selected from Group 4 of the periodic table, and j represents 1 to
And Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand and a neutral ligand capable of coordinating with a lone electron pair. When j is 2 or more, Q is the same as each other. It may be different. In addition, examples of the other metallocene compound catalyst component used in the present invention include a metallocene compound represented by the following general formula (1a) or (2a).

[0022]

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(Wherein, 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 may be the same or different from each other and represent 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 a tri-Merrill silyl group, if R ¹³ and R ¹⁴ is a methyl group or a phenyl group at the same time, R ⁶ and R ¹¹ are not simultaneously hydrogen atoms, R ¹ to represented by R ¹² group May be bonded to 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. ~
A represents a divalent hydrocarbon group of 20, and A may have two or more ring structures including a ring formed with 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, and Q is a halogen atom, a hydrocarbon group, or an anion coordination. Selected from neutral ligands that can coordinate with the
When j is 2 or more, Qs may be the same or different. In addition, examples of the metallocene compound catalyst component other than the above include a metallocene compound represented by the following general formula (1b) or (2b).

[0024]

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(Wherein 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 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, are selected from hydrogen atoms and hydrocarbon groups and silicon-containing hydrocarbon group, R ⁵ to adjacent of R ¹² The groups may be joined together to form a ring;
Represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring;
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, and Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair, and when j is 2 or more, Q is May be the same or different from each other. As a preferred example of the above-mentioned hydrocarbon group, the hydrocarbon group has 1 to 1 carbon atoms.
Examples thereof include an alkyl group having 20 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 be a cyclic hydrocarbon group containing a different atom such as sulfur or oxygen, for example, 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,
And hydrocarbon groups such as naphthyl and tolyl.

Preferred examples of the above-mentioned silicon-containing hydrocarbon group include those having 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. R ³ is preferably a sterically bulky substituent, 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 and are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same groups as described above.

The adjacent substituents of R ¹ to R ^{4 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.

The adjacent substituents of R ⁵ to R ^{12 which} are substituted on the fluorene ring may be bonded to each other to form a ring. Such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl, and the like. Further, the substituents of R ⁵ to R ¹² substituted on the fluorene ring are bilaterally symmetric, that is, R ⁵ and R ¹² , R ⁶ and R ¹¹ , R
Preferably, ⁷ and R ¹⁰ , R ⁸ and R ⁹ are the same group,
More preferably, it is unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Where the 3-, 6-, and 2-positions of the fluorene ring
Positions 7 and 7 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 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 crosslinking 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, and dinaphthylsilylene.

Further, the metallocene compound represented by the above general formula (1) has a ring in which a substituent selected from R ¹ , R ⁴ , R ⁵ or R ¹² and R ¹³ or R ¹⁴ of the cross-linking part 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 illustrated below. In the metallocene compound represented by the following general formula (1c), the crosslinked portion and the cyclopentadienyl group are united to form a tetrahydropentalene skeleton, and in the metallocene compound represented by the following general formula (1d), The pentadienyl group is united to form a tetrahydroindenyl skeleton. Similarly, the crosslinked portion and the fluorenyl group may be bonded to each other to form a ring.

[0033]

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In the metallocene compound represented by the 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 bonds to A to form a cycloalkylidene group, a cyclomethylenesilylene group, or the like.
A may have two or more ring structures including a ring formed with Y.

Preferred specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydro Examples include indanylidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, and cycloheptamethylenesilylene.

In the above general formula (1) or (2),
M is a metal selected from Group 4 of the periodic table, and specific examples include titanium, zirconium, and hafnium. In the above general formula (1) or (2), j is 1 to
4 is an integer. 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 pair of electrons. . When j is 2 or more, Qs 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 as those described above. Specific examples of the anion ligand include an alkoxy group such as methoxy, tert-butoxy and phenoxy; a carboxylate group such as acetate and benzoate; and a sulfonate group such as mesylate and tosylate.

Specific examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, Ethers such as 2-dimethoxyethane; It is preferable that at least one of Q is a halogen or an alkyl group.

Hereinafter, specific examples of the metallocene compound according to the present invention represented by the general formula (1) or (2) will be shown. First, the ligand structure of the metallocene compound excluding MQ _j (metal portion) is divided into three, Cp (cyclopentadienyl ring portion), Bridge (bridge portion), and Flu (fluorenyl ring portion). Specific examples of the partial structure of the above and specific examples of the ligand structure by their combination are shown below.

[0040]

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[0041]

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[0042]

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Specific examples of the metallocene compound having a preferable ligand structure include the following compounds.

[0044]

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[0045] Specific examples of MQ _j, 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 represents a p-toluenesulfonyl group, Ms represents a methanesulfonyl group, and Tf represents a trifluoromethanesulfonyl group.

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

[0047]

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As the metallocene compound according to the present invention represented by the above general formula (1) or (2), the following compounds are preferably exemplified. General formula (1)
Wherein 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, R
⁶ , R ¹¹ is tert-butyl, M is zirconium, Y is carbon,
A metallocene compound wherein Q is chlorine and j is 2.

In the general formula (1), R¹³, R¹⁴Is methyl, R
^ThreeIs 1-methyl-1-cyclohexyl, R ¹, R^Two, 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
2. The metallocene compound which is 2. In the general formula (1), R¹³, R
¹⁴Is methyl, R^ThreeIs tert-butyl, R¹, R^Two, R^Four, R^Five,
R⁸, R⁹, R¹²Is hydrogen, R⁶And R⁷Are bonded to each other to form a ring
Formed-(C (CH _Three)_TwoCH_TwoCH_TwoC (CH_Three)_Two)-, R^TenWhen
R¹¹Are bonded to each other to form a ring-(C (CH_Three)_TwoCH_Two
CH_TwoC (CH_Three)_Two)-, 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 ⁸ ,
R ⁹ and R ¹² are hydrogen, R ⁶ and R ⁷ are bonded to each other to form a ring — (C (CH ₃ ) ₂ CH ₂ CH ₂ C (CH ₃ ) ₂ ) —, and 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 ) —, a metallocene compound in which M is zirconium, Y is carbon, Q is chlorine, and j is 2.

In the general formula (1), R¹³, R¹⁴Is methyl, R
^ThreeIs 1,1-dimethylpropyl, R¹, R ^Two, 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 2.
Certain metallocene compounds. In the general formula (1), R¹³, R¹⁴But
Methyl, R^ThreeIs 1-ethyl-1-methylpropyl, R ¹, R^Two,
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 wherein j is 2.

In the general formula (1), R ¹³ and R ¹⁴ are methyl, 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, 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 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 , 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
^ThreeIs tert-butyl, R¹, R^Two, 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 compounds. In the general formula (1), R^Three, R¹³, R¹⁴But
Phenyl, R¹, R^Two, R^Four, R^Five, R⁸, R ⁹, R¹²But water
Prime, R⁶And R⁷Are bonded to each other to form a ring-(C (C
H_Three)_TwoCH_TwoCH _TwoC (CH_Three)_Two)-, R^TenAnd R¹¹Are connected to each other
-C (CH (CH_Three)_TwoCH_TwoCH_TwoC (C
H_Three)_Two)-, M is zirconium, Y is carbon, Q is chlorine, j
Is a metallocene compound represented by the formula:

In the general formula (1), R ³ is trimethylsilyl, R ¹³ and R ¹⁴ are phenyl, R ¹ , R ² , R ⁴ , R ⁵ ,
R ⁸ , R ⁹ and R ¹² are hydrogen, and R ⁶ and R ⁷ are bonded to each other to form a ring- (C (CH ₃ ) ₂ CH ₂ CH ₂ C (CH ₃ ) ₂ )-, and 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, 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 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, 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 (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 , 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 , R
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), R^ThreeIs tert-butyl,
R¹, R^Two, R^Four, R^Five, R⁶, R⁸, R⁹, R¹¹, R¹²But water
Prime, R⁷, R^TenIs tert-butyl, M is zirconium, and Y is
Carbon, Q is chlorine, j is 2, A is-(CH_Two)_Four-The metallo
Sen compounds. In the general formula (2), R^ThreeIs 1,1-dimethylpro
Pill, R¹, R^Two, R^Four, R^Five, R⁶, R ⁸, R⁹, R¹¹, R
¹²Is hydrogen, R⁷, R^TenIs tert-butyl, M is zirconium
, Y is carbon, Q is chlorine, j is 2, A is-(CH_Two)_Five-
Metallocene compounds.

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
Are 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 carbon, Q is chlorine, j is 2, a is - (CH _{2) 4} - metallocene compound is.

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 , 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 , 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 , 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 , 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 , R ¹² are hydrogen, R ⁷ , R ¹⁰ are tert-butyl,
A metallocene compound in which M is zirconium, Y is carbon, Q is chlorine, and j is 2. Metallocene compounds as described above,
One type may be used alone, or two or more types may be used in combination. The metallocene compound as described above can be used by being supported on a particulate carrier.

As such a particulate carrier, SiO 2 is used.
₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO,
Inorganic carriers such as TiO ₂ , ZnO, SnO ₂ , BaO, and ThO; organic materials such as polyethylene, propylene-based block copolymer, poly-1-butene, poly-4-methyl-1-pentene, and 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 co-catalysts of the metallocene catalyst. As is conventionally known, aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (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.

As the organoaluminum compound used in preparing the aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum Aluminum, trialkylaluminum such as tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum chloride, diethylaluminum Chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide, and dialkylaluminum aryloxy such as diethylaluminum phenoxide And the like.
Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

Further, as the organoaluminum compound used in preparing the aluminoxane, isoprenyl aluminum 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; and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated compounds And hydrocarbon solvents such as bromides.

In addition, ethers such as ethyl ether and tetrahydrofuran can be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred. Note that the organic aluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. Examples of the ionized ionic compound include a Lewis acid, an ionic compound, a borane compound, and a carborane compound.

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

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And 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-dimethylaniliniumtetrakis (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)
And salts of metal borane anions. Examples of the carborane compound include 4-carbanonaborane (14),
Salts of metal carborane anions such as 1,3-dicarbanonaborane (13) and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV) No.

The ionized ionic compound as described above is
One type may be used alone, or two or more types may be used in combination. The organic aluminum oxy compound or the ionized ionic compound can be used by being supported on the above-mentioned particulate carrier. In forming the catalyst, the following organic aluminum compound may be used together with the organic aluminum oxy compound or the ionized ionic compound.

As the organoaluminum compound, a compound having at least one Al-carbon bond in a 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 (wherein R ¹ and R ² may be the same or different from each other and usually have a carbon number of 1 to 15, preferably 1 to 4). X represents a halogen atom, m represents 0 <m ≦ 3, and n represents 0
≦ n <3, p is a number satisfying 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3. The polypropylene (A) used in the present invention is prepared by randomly copolymerizing propylene with a small amount of ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of the above-mentioned metallocene catalyst. Can be.

The polymerization step of the polypropylene (A) is usually carried out at about -50 to 200 ° C, preferably at about 50 to 100 ° C.
It is carried out at a temperature and usually under a pressure of normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . The polymerization of propylene can be performed by any of a batch system, a semi-continuous system, and a continuous system. Nucleator (B) The nucleator (B) used in the present invention includes sorbitol compounds such as dibenzylidene sorbitol, organic phosphate compounds, rosinate compounds, C4 to C12.
Aliphatic dicarboxylic acids and metal salts thereof.

Of these, organic phosphate compounds are preferred. , The organic phosphate compound is
It is a compound represented by the following general formulas (1) and / or (2).

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[0076]

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In the above formulas (1) and (2), R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³
Is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ may be the same or different;
Is a 1 to 3 valent metal atom, n is an integer of 1 to 3, and m is 1 or 2.

Specific examples of the organophosphate compound represented by the general formula (1) include sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene
-Bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene -Bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2 ' -Methylene
-Bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate,
Sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) ) Phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6- Di-t-butylphenyl) phosphate], barium-bis [2,2'-
Methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl-6-
(t-butylphenyl) phosphate, sodium-2,2'-
Methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2 '-Methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-
Ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-
t-butylphenyl) phosphate], magnesium-
Bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) Phosphate]
, Aluminum-tris [2,2'-methylene-bis (4,6-di
-t-butylfell) phosphate], aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and mixtures of two or more thereof. it can.

The hydroxyaluminum phosphate compound represented by the general formula (2) is also an usable organic phosphate compound, and particularly, when both R ² and R ³ are t-
A compound represented by the general formula (3), which is a butyl group, is preferred.

[0080]

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In the formula (3), R ¹ represents 1 carbon atom
And 10 is a divalent hydrocarbon group, and m is 1 or 2. Particularly preferred organic phosphate compound is a compound represented by the general formula (4).

[0082]

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In the formula (4), R ¹ is a methylene group or an ethylidene group. Specifically, hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] or hydroxyaluminum
-Bis [2,2-ethylidene-bis (4,6-di-t-butyl) phosphate]. As the sorbitol compound, specifically, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4- p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2,
4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p
-Ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1, 3,2,4-di (pn-propylbenzylidene)
Sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di ( p-s-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2 , 4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-
p-chlorobenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene- 2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,
Examples thereof include 4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol. . In particular, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol or 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol preferable.

The C4-C12 aliphatic dicarboxylic acids and metal salts thereof usable in the present invention include, specifically,
Succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid and their Li, Na, Mg, Ca, B
a, Al salts and the like. . The aromatic carboxylic acids and metal salts thereof usable as the nucleating agent (B) in the present invention include benzoic acid, allyl-substituted acetic acid, aromatic dicarboxylic acids and their periodic table I, I
Salts of metals belonging to groups I and III, specifically, benzoic acid, p-isopropylbenzoic acid, o-tert-butylbenzoic acid, p-tert-butylbutylbenzoic acid, monophenylacetic acid, diphenylacetic acid , Phenyldimethylacetic acid, phthalic acid, and their Li, Na, Mg, Ca, Ba, and Al salts.

Polypropylene Resin Composition The polypropylene resin composition according to the present invention contains the nucleating agent (B) in an amount of 0.1 part by weight based on 100 parts by weight of the polypropylene (A).
It is contained at a ratio of 0.5 to 0.5 part by weight, preferably 0.1 to 0.3 part by weight. When the nucleating agent (B) is contained in the above ratio, a molded article molded from the polypropylene resin composition can maintain excellent transparency and can improve rigidity.

The melt flow rate (MFR; ASTM D 1238, 230 ° C., load 2.16 kg) of the polypropylene resin composition according to the present invention is preferably in the range of 20 to 60 g / 10 minutes, more preferably 20 to 60 g / 10 minutes. It is desirable to be within the range of 40 g / 10 minutes. The polypropylene resin composition according to the present invention maintains rigidity and transparency at a high level and has a property of not easily forming a vacuum bubble, and thus can be used as various thick molded articles.

The polypropylene resin composition according to the present invention may contain additives such as a weathering stabilizer, a neutralizing agent and a lubricant, if necessary, as long as the object of the present invention is not impaired. After mixing the above-mentioned polypropylene (A), nucleating agent (B), and other additives as necessary using a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, etc., a single-screw extruder,
By melt-kneading using a multi-screw extruder, a kneader, a Banbury mixer, or the like, a high-quality polypropylene resin composition in which the above components and additives are uniformly dispersed and mixed can be obtained.

Thick Injection Molded Article The thick injection molded article according to the present invention is a molded article having excellent rigidity and transparency manufactured from the above-described polypropylene resin composition according to the present invention by means of injection molding. Thus, the generation of vacuum bubbles is prevented even in a thick portion. Specific examples of the thick injection molded product include a toothbrush handle, an automobile handle, chopsticks, and a battery container.

[0089]

The polypropylene resin composition according to the present invention comprises a nucleating agent (B) for a specific polypropylene (A).
, At a specific ratio, it is possible to prepare a molded article having improved rigidity and transparency at the same time. In addition, it is possible to provide a thick-walled injection-molded article in which the generation of vacuum bubbles is prevented and the transparency and rigidity are well balanced.

The thick injection-molded article according to the present invention is composed of the above composition, and thus has the above-mentioned effects.

[0091]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, the physical property in an Example and a comparative example was measured according to the following method. (1) Haze Haze was measured using a 2 mm thick sheet in accordance with ASTM D1003. (2) Flexural modulus The flexural modulus was determined by conducting a bending test in accordance with ASTM D790, and calculating the flexural modulus from the results. (3) Tensile yield stress and elongation at break A tensile test was performed in accordance with ASTM D-638, and the tensile yield stress and elongation at break were measured from the results. (4) Melt flow rate (MFR) The melt flow rate was measured at a load of 2.16 kg at the temperature indicated each time in accordance with ASTM D-1238. For example, when measured at 230 ° C., the MFR was indicated as MFR (230 ° C.).

[0092]

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
38.4 g (289 mmol) of lCl ₃ was added, and CH ₃ N
80 ml of O ₂ was added and dissolved, and this was used as a solution (1). A 500-ml three-necked flask equipped with a dropping funnel and a magnetic stirrer was sufficiently purged with nitrogen, and 25.6 g (152 mmol) of diphenylmethane and 2,6-di-t-butyl- were added thereto.
43.8 g (199 mmol) of 4-methylphenol was added and dissolved by adding 80 ml of CH ₃ NO ₂ . It was cooled in an ice bath with stirring. After the solution of (1) was added dropwise over 35 minutes, 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 is washed with 600 ml of a 5% aqueous sodium hydroxide solution,
Dried at ₄ . After filtering off MgSO ₄ , the oil obtained by evaporating the solvent 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 4,4 ′ was placed in a 200 ml flask equipped with a magnetic stirrer.
-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), concH ₂ SO ₄ 0.4
8 ml was charged. To this was added 17.5 ml of acetic acid and 3.75 of water.
Then, 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
The reaction product was extracted with. The organic layer containing the reaction product was washed with 100 ml of a saturated aqueous solution of NaHSO ₄ , followed by addition of Na ₂ CO ₃ and, after stirring, the Na ₂ CO ₃ was filtered off. Further, the organic layer was washed with 800 ml of water, and dried by adding Mg ₂ SO ₄ . After the Mg ₂ SO ₄ was filtered off, 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'-
3.21 g (6.03 m) of di-t-butyldiphenylmethane
mol) and 2.89 g (47.0 mmol) of copper powder, and the mixture was heated to 230 ° C. and reacted for 5 hours with 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 again applied to the column to collect only the target substance. Recrystallized from methanol to give 3,6-di-t-
Butylfluorene was obtained. The yield was 1.08 g. (4) Synthesis of 1-tert-butyl-3-methylcyclopentadiene Under a nitrogen atmosphere, a 2.0 mol / l tert-butylmagnesium chloride / diethyl ether solution (45
0 ml, 0.90 mol) with dehydrated diethyl ether (3
50 ml) to the solution to which the mixture was added at 0 ° C under ice-cooling.
3-methylcyclopentenone (43.7 g, 0.45 mm
ol) in 150 ml of dehydrated diethyl ether, and the mixture was further stirred at room temperature for 15 hours. To the reaction solution was added ammonium chloride (80.0 g, 1.50 mol) in water (3
50 ml) solution was added dropwise at 0 ° C. under ice cooling. 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 the organic layer while maintaining the temperature at 0 ° C under ice cooling, and the mixture was stirred at room temperature for 6 hours. The organic layer of the reaction solution was separated, washed with water, a saturated aqueous solution of sodium hydrogen carbonate, water and saturated saline, and then dried over anhydrous magnesium sulfate (desiccant). The drying agent was filtered, and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (4
5 to 47 ° C./10 mmHg) to obtain 14.6 g.
A pale yellow liquid (1-tert-butyl-3-methylcyclopentadiene) was obtained. The analytical values are shown below.

¹ H-NMR (270 MHz, CDCl
Among _3, TMS standard) δ6.31 + 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-methylcyclohexane 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) while maintaining the temperature at 0 ° C under ice-cooling, and pyrrolidine (68.0 g, 956.1mmo
After l) was added dropwise, the mixture was stirred at room temperature for 4 days. After diluting the reaction solution with diethyl ether (400 ml),
ml was added. The organic layer containing the reaction product was separated,
5N hydrochloric acid aqueous solution (150 ml × 4), water (200 ml)
× 3), washed with saturated saline (150 ml), and dried over anhydrous magnesium sulfate (desiccant). The drying agent was filtered, and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (70-80 ° C./0.1 mmHg) to obtain 10.5 g of a yellow liquid (3-tert-butyl-5,6,6-trimethylfulvene). The analytical values are 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 (0.9 g, 3.4 mm
ol) in a THF (30 ml) solution under ice cooling with n-butyllithium in hexane (2.1 ml, 3.4 mmol).
l) was added dropwise under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 6 hours. Further, under ice cooling, 3-tert-butyl-5,6,6-trimethylfulvene (0.6 g, 3.5 mm
ol) in THF (15 ml) was added dropwise under a nitrogen atmosphere. After stirring at room temperature for 12 hours, 30 ml of water was added.
The organic layer containing the reaction product extracted and separated with diethyl ether was dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to obtain a solid. The solid was recrystallized from hot methanol to obtain 1.2 g of a pale yellow solid (2-
(3-tert-butyl-5-methylcyclopentadienyl) -2-
(3,6-di-tert-butylfluorenyl) propane) was obtained. The analytical values are 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 (3-tert-butyl-5-methylcyclopentadienyl) -2- (3,6-di-tert-butylfluorenyl) propane (1.3 g, 2.8 mmol) in diethyl ether (40 ml) solution 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 red-orange solid. To this solid was added 150 ml of dichloromethane at −78 ° C. with stirring to dissolve. Then, the solution was cooled to −78 ° C. and zirconium tetrachloride (THF) 2 complex (1.0 g, 2.
(7 mmol) in dichloromethane (10 ml), stirred at -78 ° C for 6 hours, and stirred at room temperature for 24 hours.
The solvent was removed from the reaction solution under reduced pressure to obtain an orange solid. Further, the 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-butyl). Methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl)
(Zirconium dichloride) was obtained. The analytical values are 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 dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride> Organometall
According to the method described in ics, 13,954 (1994), dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was synthesized. [Preparation of Silica-Supported Methylaluminoxane] 20 g of silica (trade name: H-121, manufactured by Asahi Glass Co., Ltd., dried at 150 ° C. for 4 hours under nitrogen) and 200 ml of toluene were placed in a 500-ml reactor sufficiently purged with nitrogen. Was charged, and 60 ml of methylaluminoxane (10% by weight toluene solution, manufactured by Albemarle) was added dropwise with stirring under a nitrogen atmosphere. Next, the mixture was reacted at 110 ° C. for 4 hours, and then the reaction system was allowed to cool to precipitate a solid component, and the supernatant solution was removed by decantation. Subsequently, the solid component was washed three times with toluene and three times with hexane.
It was washed twice to obtain silica-supported methylaluminoxane. [Production of Propylene / Ethylene Random Copolymer (A-1)] In a two-necked flask having a capacity of 1000 ml and sufficiently purged with nitrogen, 20 mmol of methylaluminoxane supported on silica was converted into aluminum and suspended in 500 ml of heptane. Next, dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,
After adding 54 mg (0.088 mmol) of 6-di-tert-butylfluorenyl) zirconium dichloride as a toluene solution, then triisobutylaluminum (80 mmol) was added, and the mixture was stirred for 30 minutes to form a catalyst suspension.

The above-mentioned catalyst suspension was added to an autoclave having an internal volume of 200 liters which had been sufficiently purged with nitrogen.
kg of liquefied propylene, 150 Nl of ethylene,
And 30 Nl of hydrogen were charged, and 3.0 to 3.5.
Polymerization was carried out at 60 ° C. for 60 minutes under a pressure of MPa. After completion of the polymerization, methanol was added to stop the polymerization, and unreacted propylene was purged to obtain a propylene / ethylene random copolymer (A-1). This was dried at 80 ° C. under vacuum for 6 hours. The yield of the propylene / ethylene random copolymer (A-1) after drying was 23 kg.

The propylene / ethylene random copolymer (A-1) obtained as described above has a melting point (Tm) of 149 ° C. and an MFR (ASTM D 1238, 230 ° C., 2.16 kg).
Load) is 30 g / 10 min, and the weight average molecular weight (M
w) is 147,000, the number average molecular weight (Mn) is 71,000, Mw / Mn is 2.1, the ethylene content is 1.3 mol%, and the n-decane soluble component is The amount was 0.3% by weight. The copolymer (A-
Regarding the stereoregularity of 1), the mmmm fraction was 95.0%, the ratio of 2,1-insertion was 0.02%, and the ratio of 1,3-insertion was 0.09%. [Production of polypropylene resin composition] The propylene / ethylene random copolymer (A-
1) Feed 100 parts by weight into a Henschel mixer,
Further, 0.1 part by weight of a phosphorus-based antioxidant [tris (2,4-di-t-butylphenyl) phosphite] and hydroxyaluminum-bis [2,2-methylene-bis (4,6
-Di-t-butylphenyl) phosphate], 3 parts by weight, 0.1 part by weight of calcium stearate and 0.1 part by weight of erucamide were added and mixed with stirring.

Next, the obtained mixture was melt-kneaded at a resin temperature of 200 ° C. using a twin-screw extruder (40 mmφ), and the kneaded product was extruded to obtain pellets of a polypropylene resin composition. The MFR of the resulting composition (230
C) was 30 g / 10 min. Next, a sheet-like test piece having a thickness of 2 mm and a test piece for bending strength test (ASTM D790, a thickness of 3.2 mm, a length of 127) at 200 ° C and a mold temperature of 40 ° C by injection molding using the pellet.
mm, width 12.7 mm) and a test piece (ASTM D256, thickness 3.2 mm, length 63.5 mm, width 12.7 mm) for an Izod impact test, respectively.
Using these test pieces, haze, flexural modulus, and Izod impact strength were measured. In addition, the tensile yield point stress and the elongation at break were measured according to the above methods. The results are shown in Table 1.

[0100]

Comparative Example 1 A commercially available propylene / ethylene random copolymer (A-2) produced using a magnesium chloride-supported titanium catalyst (Ziegler-Natta catalyst) used in Comparative Example 1 [Grand Polymer Co., Ltd.] Made, trade name J
207RT] are as follows.

The propylene / ethylene random copolymer (A-2) has a melting point (Tm) of 154 ° C.
(230 ° C.) was 30 g / 10 min, Mw / Mn was 4.5, and the amount of n-decane soluble matter was 2.0% by weight. Neither the 2,1-insertion nor the 1,3-insertion was detected. Using this propylene / ethylene random copolymer (A-2), a polypropylene resin composition was produced in the same manner as in Example 1, and its physical properties were evaluated. Table 1 shows the results.

[0102]

Comparative Example 2 A propylene / ethylene random copolymer (A-3) 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. )
I got The yield of the obtained propylene / ethylene random copolymer (A-3) was 16.3 kg. This propylene / ethylene random copolymer (A-3) has a melting point (Tm) of 140 ° C and an MFR (230 ° C) of 3
0 g / 10 min, Mw / Mn is 2.4, n-
The decane-soluble content was 0.8% by weight, and the ethylene content was 1.3% by mole. The stereoregularity of the propylene / ethylene random copolymer (A-3) was such that the mmmm fraction was 94.8%, the ratio of 2,1-insertion was 0.91%, The insertion ratio was 0.11%.

Next, a polypropylene resin composition was produced using the propylene / ethylene random copolymer (A-3) in the same manner as in Example 1, and the physical properties were evaluated. Table 1 shows the results.

[0104]

[Table 1]

Continued on the front page (72) Inventor Isao Wada 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Grand Polymer Co., Ltd. BA02B BB00A BB01B BC12B BC13B BC15B BC16B BC24B BC25B CA25A CA27A CA28A EB02 EB04 EB05 EB08 EB10 GA05 GA08 4J128 AA01 AB00 AB01 AC01 AC09 AC10 AC27 AC28 AD00 BA00A BA01B BA02B BB00B13B02 BC12B13BCB BC12B12B12BCB BC

Claims (10)

[Claims] 1) 100 parts by weight of a polypropylene (A) obtained by random copolymerization of propylene and an α-olefin in the presence of a metallocene catalyst, and 0.05 to 0.5 part by weight of a nucleating agent (B). The polypropylene (A) has (i) a melt flow rate (ASTM D 1238, 230 ° C., 2.16 kg load) of 8 to 80 g / 1.
(Ii) the α-olefin content is in the range of 0 minutes.
(Iii) the proportion of regio-irregular units based on 2,1-insertion or 1,3-insertion of propylene monomer in all propylene structural units, as determined from the ¹³ C-NMR spectrum. Are 0.2% or less, and (i
v) Gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 1 to 3.
5. A polypropylene resin composition, which is 5. 2. The polypropylene resin composition according to claim 1, wherein the metallocene compound catalyst component forming the metallocene catalyst is represented by the following general formula (1) or (2): (Wherein, R ³ is selected from a hydrocarbon group and a silicon-containing hydrocarbon group; 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, and among the groups represented by R ¹ to R ¹² may be formed adjacent groups combine with each other to form a ring, when the general formula (1) bond R ^1, R ^4, group and R ¹ selected from R ⁵ and R ^{12 3} or R ¹⁴ with each other 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 anionic 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 or different from each other. ). 3. The polypropylene resin composition according to claim 1, wherein the α-olefin which is a component of the polypropylene (A) is ethylene. 4. The polypropylene resin composition according to claim 1, wherein said nucleating agent (B) is an organic phosphate nucleating agent. 5. The organic phosphate nucleating agent represented by the following formula (1) and / or (2):
A polypropylene resin composition according to the above; Embedded image (In the formula, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ is a hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ may be the same or different, M is a metal atom having 1 to 3 valences, n is an integer of 1 to 3, and m is 1 or 2.) 6. The polypropylene resin composition according to claim 1, which is used in the production of a thick injection molded product. 7. A thick injection molded article comprising the polypropylene resin composition according to any one of claims 1 to 5. 8. The thick injection molded article according to claim 7, wherein the maximum thickness of the thick injection molded article is 3 mm or more. 9. The thick injection molded article according to claim 7, wherein said thick injection molded article is a handle of a toothbrush. 10. The thick injection molded product according to claim 7, wherein the thick injection molded product is a battery container.