JP2002275330A - Polypropylene container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene container excellent in the balance of transparency and rigidity, therefore, suitable as a container for cosmetics and drinking water, etc., excellent in humidity resistance and low temperature impact resistance, and capable of filling a high temperature content for its excellent heat resistance. SOLUTION: This polypropylene container is manufactured by stretch blow molding of a polypropylene composition containing 0.05-0.5 wt.% nucleating agent (B) and 99.5-99.95 wt.% polypropylene (A), which is obtained by random copolymerization of a propylene and an α-olefin in the presence of a metallocene catalyst, and has an MFR of 0.5-50 g/10 min, an α-olefin content of 0.5-5 wt.%, every ratio of position irregular unit based on 2,1- and 1,3-insertion of a propylene monomer in the total propylene composition unit measured by<13> C-NMR spectrometry of not greater than 0.2%, and an Mw/Mn measured by GPC of 2.5-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene container obtained by stretch blow molding.

[0002]

BACKGROUND OF THE INVENTION Polypropylene containers are widely used as containers for foods, toiletries, detergents, medical supplies, etc. because of their light weight, excellent chemical resistance, and excellent transparency. I have. The method for producing a polypropylene container includes a direct blow molding method in which a polypropylene resin is melted, a parison is directly extruded, and a pressurized fluid such as air is pressed into a molten parison in a mold and shaped. After the preform is once molded from polypropylene resin, the preform is reheated and stretched in the longitudinal direction in a softened state, and then a pressurized fluid is pressed into the longitudinally stretched preform to perform biaxial stretching blow. There are mainly two types of so-called injection blow molding methods for manufacturing containers.

[0003] As a blow molding resin, polypropylene cannot be said to have performance suitable for a direct blow molding method because of its low melt tension. Also, in the stretch blow molding, since the polypropylene is easily crystallized, the preform is hardly stretched, so that it cannot be said that the preform has a preferable suitability. For these reasons, polypropylene has hitherto not been used in blow molding applications. Further, since the polypropylene direct blow molded container has a problem of insufficient transparency, a polypropylene blow molded container by an injection blow molding method has recently been developed.

[0004] Polyethylene terephthalate resins are often used as injection blow molding resins. Polypropylene is superior in chemical resistance and heat resistance to polyethylene terephthalate resin, but is slightly inferior in transparency and rigidity. Therefore, improvement in transparency and rigidity is required. Further, further improvement in heat resistance is desired so that the contents can be filled at a higher temperature.

[0005]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a polypropylene container which has an excellent balance between transparency and rigidity and further improved heat resistance. It is intended to be.

[0006]

SUMMARY OF THE INVENTION A polypropylene container according to the present invention is obtained by random copolymerization of propylene and an α-olefin in the presence of a metallocene catalyst, and (i) a melt flow rate (ASTM D 1238, 230 ° C.). , 2.16 kg load) in the range of 0.5 to 50 g / 10 min, (ii) the α-olefin content is 0.5 to 5% by weight, and (iii) ¹³ C
(Iv) gel in which the proportion of regio-irregular units based on 2,1-insertion or 1,3-insertion of propylene monomer in all propylene structural units is 0.2% or less, as determined from the NMR spectrum; Molecular weight distribution (Mw / Mn) determined by permeation chromatography (GPC)
Is from 9 to 9 and the polypropylene (A) is from 9 to 9
It is characterized in that a polypropylene resin composition containing 9.95% by weight and 0.05 to 0.5% by weight of a nucleating agent (B) is stretch blow-molded.

As the metallocene compound catalyst component forming the metallocene catalyst, usually, a metallocene compound represented by the following general formula (1) or (2) is preferably 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 component of the polypropylene (A) is preferably ethylene.

The nucleating agent (B) is preferably an organic phosphate ester nucleating agent.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polypropylene container according to the present invention will be specifically described. The polypropylene resin composition used as a material for the polypropylene container according to the present invention comprises a polypropylene (A) and a nucleating agent (B).
It contains. Polypropylene (A) The polypropylene (A) used in the present invention is a crystalline resin, and is a random copolymer of propylene and an α-olefin.

As the α-olefin, ethylene or an α-olefin having 4 to 20 carbon atoms, specifically, 1-
Butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among them, ethylene and carbon atoms 4
Preferred are α-olefins of from 10 to 10, particularly preferred is ethylene.

Specific examples of the propylene / α-olefin random copolymer include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / 1-pentene random copolymer, propylene Examples thereof include a 1-hexene random copolymer, a propylene / 4-methyl-1-pentene random copolymer, a propylene / 1-octene random copolymer, a propylene / ethylene / 1-butene random copolymer, and the like. Of these, a propylene / ethylene random copolymer is most preferred.

The polypropylene (A) used in the present invention
Is preferably propylene and ethylene and / or C4 to C4 prepared using a metallocene catalyst described below.
20 is a crystalline random copolymer with an α-olefin. The polypropylene (A) used in the present invention has the following properties. (I) Melt flow rate (MFR; ASTM D 1238, 230)
° C, 2.16 kg load) is 0.5 to 50 g / 10 min, preferably 10 to 45 g / 10 min, more preferably 20 to 4 g / 10 min.
It is in the range of 0 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% by weight, preferably 1.0 to 2.0% by weight.
% 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) Gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 2.5 to
4, preferably 2.5 to 3.5, more preferably 2.9
３3.2.

Further, the polypropylene (A) preferably 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 132
To 160 ° C, preferably 137 to 145 ° C, more preferably 139 to 142 ° 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).

[0017]

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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).

[0019]

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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).

[0021]

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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 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 be bonded to 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) is a compound 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 portion 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.

[0030]

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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 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 of the present invention represented by the above 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.

[0037]

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[0038]

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[0039]

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

[0041]

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Specific examples of MQ _j include 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.

[0044]

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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 cocatalysts 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.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include 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 an organoaluminum compound used for preparing an aluminoxane, isoprenyl aluminum represented by the following general formula can also 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 fluorine atom, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group or a fluorine atom). 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 subjecting propylene to a small amount of ethylene and / or α having 4 to 20 carbon atoms in the presence of the above-mentioned metallocene catalyst according to a conventional method.
-It can be prepared by random copolymerization with an olefin.

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. Preferable methods include a method of performing polymerization in two or multiple stages or a method of mixing two or more types of polypropylenes having different molecular weights so that Mw / Mn is within the above-described range.

Nucleating agent (B) The nucleating agent (B) used in the present invention includes sorbitol compounds, organophosphate compounds, C4 to C4
12 aliphatic dicarboxylic acids and metal salts thereof. Of these, organic phosphate compounds are preferred. The organic phosphoric ester compound is a compound represented by the following general formula (1) and / or (2).

[0072]

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[0073]

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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 organic phosphate 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.

A 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.

[0077]

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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).

[0079]

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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 acid and its metal salt 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 used in the present invention contains 0.05 to 0.5% of the nucleating agent (B) based on 100% by weight of the polypropylene (A) and the nucleating agent (B). % By weight, preferably from 0.2 to 0.3% by weight. When the nucleating agent (B) is used in the above ratio, a polypropylene stretch blow molded container having excellent transparency and rigidity can be prepared from the obtained polypropylene resin composition.

The polypropylene resin composition used in the present invention has a melt flow rate (MFR; ASTM D 1238,230).
° C, load 2.16 kg) is preferably in the range of 0.5 to 50 g / 10 min, more preferably 20 to 40 g / min.
It is desirable to be within the range of 10 minutes. The polypropylene resin composition used in the present invention, within a range that does not impair the purpose of the present invention, as necessary, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, Additives such as lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers and the like can be blended.

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, and the like, 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.

Polypropylene Container The polypropylene container according to the present invention is a blow-molded container obtained by stretch-blow-molding the above polypropylene resin composition. In the method for producing a polypropylene container according to the present invention, a container is produced from the polypropylene resin composition by stretch blow molding.

Specifically, a preform is formed by melting a polypropylene resin composition and injection molding the resin composition in a mold. Then, the preform is used as it is or after heating. This preform is forcibly stretched in the longitudinal direction, and then, by introducing a heating gas into the preform in the transverse direction, the preform is stretched in the transverse direction to form the polypropylene container according to the present invention. .

The stretching ratio of the preform depends on the shape of the final container, the molding machine, and the resin composition used, but it is 1.5 to 4.0 times in the longitudinal direction and 1.5 to 4.0 in the transverse direction.
It is desirable to carry out 0-fold stretch molding.

[0088]

According to the present invention, a polypropylene container having an excellent balance between transparency and rigidity can be obtained. Therefore, the polypropylene container according to the present invention is suitable as a container for cosmetics, drinking water, and the like. Further, the polypropylene container according to the present invention is excellent in moisture resistance, low-temperature impact resistance and heat resistance. Therefore, the polypropylene container according to the present invention can be filled with high-temperature contents.

[0089]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The performance evaluation in Examples and Comparative Examples was performed according to the following method. (1) Rigidity Injection blow molding was performed, a test piece for rigidity test was cut out from the obtained container, and the flexural rigidity was measured according to ASTM D790, and the rigidity was evaluated based on the rigidity. (2) Haze (Transparency) Haze was measured according to the method of ASTM D1003. (3) Heat resistance A heat resistance test was performed in accordance with ASTM D648, a dimensional change was measured, and the heat resistance was evaluated based on the dimensional change.

[0090]

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)] 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 a 200-liter autoclave, 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, the polymerization was stopped by adding methanol, and unreacted propylene was purged to obtain a propylene / ethylene random copolymer (A). This was dried at 80 ° C. under vacuum for 6 hours. The yield of the propylene / ethylene random copolymer (A) after drying was 23 kg.

The propylene / ethylene random copolymer (A) obtained as described above has a melting point (Tm) of 14
9 ° C., MFR (ASTM D 1238, 230 ° C., 2.16 kg load) 30 g / 10 min, weight average molecular weight (Mw)
Is 147,000 and the number average molecular weight (Mn) is 7
It was 1,000, Mw / Mn was 2.1, the ethylene content was 1.3 mol%, and the amount of n-decane soluble components was 0.3% by weight. The stereoregularity of the copolymer (A) was such that the mmmm fraction was 95.0%,
The insertion rate is 0.02% and the 1,3-insertion rate is 0.
09%.

In the polymerization of the propylene / ethylene random copolymer (A), the charged amount of hydrogen was adjusted to 15N.
Melting point (Tm)
149 ° C., MFR (ASTM D 1238, 230 ° C., 2.16 kg load) 12 g / 10 min, Mw / Mn 2.1, ethylene content 1.3 mol%, n-decane soluble component amount 0 .3
Producing a propylene / ethylene random copolymer (B) having a weight%, a mmmm fraction of 95.0%, a 2,1-insertion ratio of 0.02%, and a 1,3-insertion ratio of 0.09%. did.

Then, the propylene / ethylene random copolymer (A) and the propylene / ethylene random copolymer (B) are mixed to form a propylene / ethylene random copolymer composition having a Mw / Mn of 2.9. (C) was obtained.
100 parts by weight of the propylene / ethylene random copolymer composition (C) obtained as described above is supplied into a Henschel mixer, and hydroxyaluminum-bis [2,2-methylene-bis ( 4,6-di-t-butylphenyl) phosphate] was added and stirred and mixed.

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 obtained composition (ASTM D 1
238, 230 ° C, 2.16 kg load) was 30 g / 10 min. [Production of Stretch Blow Molding Container] A 500 ml container was molded using the above polypropylene resin composition by an injection stretch blow molding machine [efb2000, manufactured by Frontier Co., Ltd.].

Specifically, first, the polypropylene resin composition was melted at a resin temperature of 200 ° C. by an injection molding machine, and was injection-molded into a first mold whose temperature was controlled at 15 ° C. by a water circulation circuit to form a preform. Molded. Next, the preform is heated to 133 ° C. in a second mold (annealing).
Thereafter, preliminary blowing was performed, and immediately thereafter, the film was stretched 2.4 times in the longitudinal direction with a stretching rod.

Next, 5 kgf /
The preform was expanded to the shape of a bottle container having a capacity of 500 ml by blowing compressed air of cm ² . Then, in this step, after the expanded preform was left for 10 seconds, cooling air at 5 ° C. was injected into the container to cool the container, the mold was opened, and the bottle container was taken out. The bottle container molded by the above method could be molded without any problems at the time of molding, and was extremely excellent in transparency.

The obtained bottle containers were subjected to evaluation tests for rigidity, haze and heat resistance in accordance with the above-mentioned methods. Table 1 shows the results.

[0103]

Comparative Example 1 A commercially available propylene / ethylene random copolymer (D) produced by using a magnesium chloride-supported titanium catalyst (Ziegler-Natta catalyst) used in Comparative Example 1 [manufactured by Grand Polymer Co., Ltd. Product name J20
[7RT] has the following physical properties.

The propylene / ethylene random copolymer (D) has a melting point (Tm) of 154 ° C. and an MFR (2
30 ° C.) is 30 g / 10 min, and Mw / Mn is 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 (D), a polypropylene resin composition was produced in the same manner as in Example 1. [Production of stretch blow molded container] In the same manner as in Example 1 except that the polypropylene resin composition prepared in Comparative Example 1 was used instead of the polypropylene resin composition obtained in Example 1, Done. Table 1 shows the results.

[0105]

Comparative Example 2 The procedure of Example 1 was repeated except that 70 mg of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was used as the metallocene. Thus, a propylene / ethylene random copolymer (E) was obtained.

The yield of the obtained propylene / ethylene random copolymer (E) was 16.3 kg. This propylene / ethylene random copolymer (E) has a melting point (Tm) of 140 ° C and an MFR (230 ° C) of 30.
g / 10 min, Mw / Mn was 2.4, n-decane soluble matter was 0.8% by weight, and ethylene content was 1.3 mol%. The stereoregularity of the propylene / ethylene random copolymer (E) was such that the mmmm fraction was 94.8%, the ratio of 2,1-insertion was 0.91%, and that of 1,3-insertion. The proportion was 0.11%.

Next, using this propylene / ethylene random copolymer (E), a polypropylene resin composition was produced in the same manner as in Example 1. [Production of stretch blow-molded container] In the same manner as in Example 1 except that the polypropylene resin composition prepared in Comparative Example 2 was used instead of the polypropylene resin composition obtained in Example 1, Thus, an attempt was made to produce a bottle container, but the stretching of the bottle was not uniform, and a good product was not obtained.

[0108]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 23:00 B29L 22:00 B29L 22:00 B65D 1/00 A F-term (Reference) 3E033 AA01 BA16 CA03 CA06 CA08 CA18 FA03 GA02 4F208 AA11A AA11C AA11H AB08 AG07 AH55 LA04 LB01 4J002 BB141 BB151 EF066 EF096 EG056 EG076 EL106 EW046 FD206 4J028 AA01A AB01A AC01A AC10A AC28A BA00A BA01B BB00A BB01B BC25B CB65C CB94C EA01 EA02 EA03 EA04 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EC02 EC03 EC04 FA01 FA04 GA06 GA07 GA12 4J128 AA01 AB01 AC01 AC10 AC28 AD00 BA00A BA01B BB00A BB01B BC25B CB65C CB94C EA01 EA02 EA03 EA04 EB02 EB03 EB04 EB05 EB07 EB08 EB09 GA04 EC03 EC04

Claims (3)

[Claims] (1) a copolymer obtained by random copolymerization of propylene and an α-olefin in the presence of a metallocene catalyst, and (i) a melt flow rate (ASTM D 1238 at 230 ° C.,
2.16kg load) is in the range of 0.5-50g / 10min,
(Ii) the α-olefin content is 0.5 to 5% by weight, and (iii) the content is determined from a 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 9) to 99.95% by weight of a polypropylene (A) having a molecular weight distribution (Mw / Mn) determined from 2.5 to 4), and 0.05 to 0.5% by weight of a nucleating agent (B). A polypropylene container obtained by stretch-blowing a polypropylene resin composition containing 2. The polypropylene container 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 container according to claim 1, wherein the nucleating agent (B) is an organic phosphate nucleating agent.