JP2006143769A - Polypropylene-based resin composition and foam molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based resin composition which can provide foam moldings excellent in balance of foamability and productivity and also excellent in drawdown properties during thermoforming. <P>SOLUTION: The polypropylene-based resin composition comprises (A), (B) and (C). (A): 10-50 wt% of a polyolefin component having branched structure and 5-30 g of melt tension at 230°C; (B): 20-70 wt% of a polypropylene-based resin satisfying (B-1) to (B-4): (B-1) melt tension at 190°C being 0.5-5 g, (B-2) a melt flow rate being 1-10 g/min, (B-3) the ratio of weight average molecular weight to number average molecular weight being 2-4.5, and (B-4) relaxation time (τ) at angular frequency ω=0.1 rad/s being 0.5-2.0 s in the melt viscoelasticity behavior; and (C) 20-70 wt% of a random copolymer polypropylene satisfying (C-1) and (C-2): (C-1) a melt flow rate being 1-8 g/10 min, and (C-2) ethylene unit content being 1-5 wt%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polypropylene resin composition and a foamed molded product thereof. More specifically, the present invention relates to a polypropylene resin composition for foam molding, and more particularly, to a polypropylene resin composition for extrusion foam molding and a foam molded body comprising the same.

  Recently, with the spread of microwave ovens and the increase in convenience stores, the demand for containers for microwave ovens has increased. The container is required to have properties such as heat insulation, heat resistance, and oil resistance. In the case of producing the container, a polypropylene-based resin can be cited as one of preferable materials. However, since this resin is a crystalline resin, the melt viscosity becomes extremely low above this melting point, and the foaming temperature becomes higher than this melting point. There was a problem that it was easy to break the bubbles without being able to hold the bubbles. For such problems, a high melt tension polypropylene having a free-end long-chain branched structure is used, and a foam excellent in foaming characteristics (high foaming ratio, cell miniaturization, low open cell ratio) is obtained. Yes. However, these resins have the disadvantage of being expensive.

Therefore, a polypropylene resin mixture is proposed in which a specific polypropylene resin is mixed at a specific ratio with a polypropylene resin having a free-end long-chain branched structure (see, for example, Patent Document 1). However, this mixture has a problem that the balance between the foaming characteristics and the productivity is lowered when the proportion of the polypropylene resin having a free-end long-chain branched structure is decreased.
Therefore, a resin that solves these problems is desired from the viewpoint of productivity and cost reduction.
JP 2001-226510 A

In view of the above problems, the present inventors blended a high melt tension polypropylene with a specific MFR obtained by a specific manufacturing method and a polypropylene having a molecular weight distribution, thereby improving foaming characteristics (improvement of foaming ratio, refinement of cells). The invention has invented a polypropylene resin composition capable of obtaining excellent performance in both the reduction of open cell ratio and productivity (stretchability) (Japanese Patent Application No. 2004-160665).
However, in the thermoforming process, which is a process necessary for obtaining the container, there is a problem that the container made of a non-uniform thickness occurs because the drawdown property of the sheet made of the polypropylene resin composition is large.

  The present invention has been made in view of the above circumstances, and a polypropylene-based resin composition that provides a foamed molded article that has an excellent balance between foaming characteristics and productivity, and that is also excellent in drawdown properties during thermoforming, and the molded article thereof The purpose is to provide.

According to the present invention, the following polypropylene resin compositions and the like are provided.
1. A polypropylene resin composition comprising the following (A), (B) and (C).
(A) Polyolefin component having a branched structure with a melt tension at 230 ° C. of 5 to 30 g: 10 to 50% by weight
(B) Polypropylene resin satisfying the following (B-1) to (B-4): 20 to 70% by weight
(B-1) The melt tension at 190 ° C. is 0.5 to 5 g.
(B-2) Melt flow rate is 1 to 10 g / min (B-3) Ratio of weight molecular weight to number average molecular weight is 2 to 4.5
(B-4) In melt viscoelastic behavior measured using a rotary rheometer, the relaxation time (τ) at an angular frequency ω = 0.1 rad / sec is 0.5 to 2.0 seconds (C) (C) -1) and random copolymer polypropylene satisfying (C-2): 20 to 70% by weight
(C-1) Melt flow rate is 1 to 8 g / 10 min. (C-2) Ethylene unit content is 1 to 5% by weight.

2. 2. The polypropylene resin composition according to 1, wherein the component (A) is a polypropylene into which long-chain branches have been introduced by irradiating ionizing radiation.
3. 2. The polypropylene resin composition according to 1, wherein the component (A) is a propylene polymer composition obtained by bringing polypropylene, an organosilicon compound, and a high molecular weight acid-modified α-olefin polymer into contact with each other.
4). The component (A) is a polymer or copolymer of one or more monomers selected from ethylene, propylene, α-olefins having 4 to 20 carbon atoms, styrenes and cyclic olefins by a two-stage polymerization method in the presence of polyene. 2. The polypropylene resin composition according to 1, which is a polyolefin resin obtained by polymerization.

5. The polypropylene resin composition according to any one of 1 to 4, wherein the polypropylene resin (B) is a polypropylene resin obtained by melt-kneading a polypropylene resin in the presence of an organic peroxide.
6). In the presence of a catalyst in which the polypropylene resin (B) is a combination of a catalyst component and a promoter component selected from the group 4 transition metal compounds of the periodic table having a cyclopentadienyl skeleton, propylene The polypropylene resin composition according to any one of 1 to 4, which is a polypropylene resin obtained by polymerization.
7). Furthermore, the polypropylene resin composition in any one of 1-6 which contains 1-100 weight part of inorganic fillers as (D) component with respect to 100 weight part of said polypropylene resin compositions.
8). A foam molded article satisfying the following (1) to (4) obtained by foam molding of the polypropylene resin composition according to any one of the above 1 to 7.
(1) Average cell diameter is 500 μm or less (2) Open cell ratio is 1 to 30%
(3) Stretchability is 5 m / min or more (4) Foaming ratio is 1 to 5 times

  ADVANTAGE OF THE INVENTION According to this invention, the polypropylene resin composition from which the foaming molding which is excellent in the balance of a foaming characteristic and productivity, and is excellent also in the drawdown property of thermoformability is obtained, and its molding can be provided. The composition of the present invention can improve productivity and reduce costs compared to conventional compositions.

Hereinafter, the components contained in the polypropylene resin composition of the present invention will be described.
(A) Polyolefin Component The polyolefin component (A) (hereinafter referred to as component (A)) has a melt tension (MT ₂₃₀ ) at 230 ° C. of 5 to 30 g, preferably 8 to 30 g, more preferably 20 to 30 g. When MT ₂₃₀ is less than 5 g, the foaming characteristics are lowered (decrease in foaming ratio and open cell ratio is increased), and thermoformability is lowered, which is not preferable. On the other hand, when MT ₂₃₀ exceeds 30 g, productivity is lowered, which is not preferable. The component (A) has a branched structure.

As such component (A), it is preferable to use a polypropylene resin obtained by irradiating a polypropylene resin (for example, homopolypropylene, block polypropylene, random polypropylene, random block polypropylene, etc.) with ionizing radiation. it can. Examples of the ionizing radiation include α rays, β rays, γ rays, X rays, electron beams, and the like. Of these, the electron beam is most preferable for practical use. The resin obtained by this method (ionizing radiation) has a free-end long-chain branched structure. As specific production conditions in the most preferred electron beam crosslinking method, for example, the conditions described in JP-A-62-1121704 and JP-A-2-69533 can be used.
Examples of such commercially available resins include Profax PF-814, Pro-fax SD-632 (manufactured by Montel SDK Sunrise Co., Ltd., trade name), and the like.
In the present specification, unless otherwise specified, the “polypropylene resin” includes all of the above structural examples.

  As the component (A), a propylene polymer composition obtained by bringing a polypropylene resin, an organosilicon compound, and a high molecular weight acid-modified α-olefin polymer into contact with each other can be suitably used. In this method, a melt tension developing component having a branched structure is formed in the polymerization composition.

  Preferably, it is a propylene polymer composition obtained by bringing a polypropylene resin, an organosilicon compound, and a high molecular weight modified α-olefin polymer modified with an unsaturated carboxylic acid and / or an anhydride thereof into contact with each other.

More preferably, 100 parts by mass of a polypropylene resin having an intrinsic viscosity [η] measured in tetralin of 135 ° C. of 0.7 to 5 dl / g, and an organosilicon compound represented by the general formula (1) 0.001 to 1 The intrinsic viscosity [η] measured in 135 ° C. and tetralin is 0.7 dl / g or more, containing 0.001 to 1% by mass of an acid derived from part by mass and an erodible carboxylic acid and / or an anhydride thereof. Is a propylene polymer composition obtained by contacting 0.1 to 30 parts by mass of an acid-modified α-olefin polymer having 2 to 20 carbon atoms.
X _n SiY _m (OR) _{4− (n + m)} (1)
[Wherein, X represents a substituent containing a group capable of reacting with a carboxylic acid or its anhydride, Y represents a hydrocarbon group, a hydrogen atom or a halogen atom, R represents a hydrocarbon group, n represents 1 to 3, m Represents an integer of 0 to 2, and n + m = 1 to 3. ]

Examples of the organosilicon compound represented by the general formula (1) include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, and p-aminophenyltrimethoxysilane. Can be mentioned.
The high molecular weight acid-modified α-olefin polymer was modified with maleic anhydride, acrylic acid, methacrylic acid or the like having an intrinsic viscosity [η] measured in tetralin of 135 ° C. of 0.7 dl / g or more. A propylene polymer, 1-butene polymer, etc. are mentioned.
As other specific manufacturing conditions in this manufacturing method, for example, the conditions described in JP-A-2004-75946 can be used.

  In addition, as the component (A), ethylene, propylene, carbon number 4 to 20 in the presence of polyene (for example, 1,7-octadiene, 1,9-decadiene, 1,5-hexadiene, etc.) is obtained by a two-stage polymerization method. Α-olefins (eg, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc.), styrenes (eg, styrene, p-methylstyrene, etc.) and cyclic olefins (eg, norbornene) Etc.), a polyolefin resin obtained by polymerizing or copolymerizing one or two or more monomers selected from the above can be suitably used. In this method, a melt tension developing component having a branched structure is formed in the resin.

  Specifically, in the presence of a catalyst in which a catalyst component including a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton and a promoter component is combined, ethylene, propylene, and a carbon number of 4 to 20 a first polymerization step of polymerizing or copolymerizing one or more monomers selected from α-olefin, styrenes and cyclic olefins, and a homopolymer or a copolymer obtained in the first polymerization step, One or two selected from ethylene, propylene, α-olefins having 4 to 20 carbon atoms, styrenes and cyclic olefins in the presence of a polyene having at least two carbon-carbon double bonds polymerizable in one molecule It can manufacture from the manufacturing method including the 2nd polymerization process of copolymerizing the above monomer.

Examples of the catalyst component used in this method include a transition metal compound represented by the formula (I).
(Cp-A-Cp) M ¹ R ¹ _d R ² _e (I)
[Wherein, M ¹ represents a transition metal of Group 4 of the periodic table, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, or a substituted tetrahydroindenyl group. , A group selected from a fluorenyl group and a substituted fluorenyl group, R ¹ and R ² each independently represent a ligand, and A represents a covalent bond. d and e each represent an integer of 0 to 2. Two or more of R ¹ and R ² may be bonded to each other to form a ring. The two Cp may be the same or different from each other. ]

In the formula (I), examples of the Group 4 transition metal of the periodic table represented by M ¹ include titanium, zirconium, and hafnium.
Examples of the substituent on Cp include each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and the substituents adjacent to each other are bonded. To form a ring. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, and n-decyl group. And alkyl groups such as phenyl group, aryl groups such as 1-naphthyl group and 2-naphthyl group, and aralkyl groups such as benzyl group. Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include groups in which one or more of the hydrogen atoms of the hydrocarbon group are substituted with an appropriate halogen atom.

For example, in the case of a substituted cyclopentadienyl group, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, tetramethylcyclopenta Dienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilyl A cyclopentadienyl group etc. are mentioned.
Moreover, as an example in which an adjacent group forms a ring, in the case of an indenyl group, for example, a 4,5-benzoindenyl group, an α-acetoindenyl group, and an alkyl substituent having 1 to 10 carbon atoms thereof can be mentioned. .

R ¹ and R ² in the above formula (I) each independently represent a ligand such as a sigma-binding ligand, a chelating ligand, or a Lewis base. Specific examples of the σ bond ligand include a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , An alkylaryl group or an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, and the like. Examples of chelating ligands include acetylacetonate groups and substituted acetylacetonate groups. Two or more of R ¹ and R ² may be bonded to each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms.

Specific examples of R ¹ and R ² include, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group as an alkyl group having 1 to 20 carbon atoms. , N-butyl group, octyl group, 2-ethylhexyl group, alkoxy group having 1 to 20 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group Alternatively, phenyl group, tolyl group, xylyl group, benzyl group as arylalkyl group, heptadecylcarbonyloxy group as C1-C20 acyloxy group, trimethylsilyl group as substituent containing silicon atom, (trimethylsilyl) methyl group, Lewis base As dimethyl ether, diethyl ether, tetrahydro Ethers such as orchids, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2'- Amines such as bipyridine and phenanthroline, phosphines such as triethylphosphine and triphenylphosphine, chain unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof, benzene, toluene And cyclic unsaturated hydrocarbons such as xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof.

  Examples of the crosslink by covalent bond of A in the above formula (I) include, for example, methylene bridge, dimethylmethylene bridge, ethylene bridge, 1,1′-cyclohexylene bridge, dimethylsilylene bridge, dimethylgermylene bridge, dimethylstannylene. Examples include cross-linking.

  Examples of the compound represented by the above formula (I) include methylenebis (indenyl) dichlorozirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (indenyl) monochloromonohydridozirconium, ethylenebis (indenyl) chloromethylzirconium, ethylene Bis (indenyl) chloromethoxyzirconium, ethylenebis (indenyl) diethoxyzirconium, ethylenebis (indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydroindenyl) dichlorozirconium, ethylenebis (2-methylindene) Nyl) dichlorozirconium, ethylenebis (2-ethylindenyl) dichlorozirconium, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethyl) Rucyclopentadienyl) dichlorozirconium, ethylene (2-methyl-4-tert-butylcyclopentadienyl) (3′-tert-butyl-5′-methylcyclopentadienyl) dichlorozirconium, ethylene (2,3 , 5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) dichlorozirconium, isopropylidenebis (indenyl) dichlorozirconium, isopropylidenebis (2,4-dimethylcyclopentadienyl) ) (3 ′, 5′-dimethylcyclopentadienyl) dichlorozirconium, isopropylidenebis (2-methyl-4-tert-butylcyclopentadienyl) (3′-tert-butyl-5′-methylcyclopentadiene) Enyl) dichlorozirconium, iso Ropyridene (cyclopentadienyl) (fluorenyl) dichlorozirconium, 1,7-cyclohexylidene (2,5-dimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (indenyl) dichlorozirconium, dimethylsilylenebis (4,5 , 6,7-tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (2-methylindenyl) dichlorozirconium, dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) dichlorozirconium, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) dichlorozirconium, phenylmethylsilylenebis (indenyl) dichlorozirconium, phenylmethylsilyle Bis (4,5,6,7-tetrahydroindenyl) dichlorozirconium, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) dichlorozirconium, phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) dichlorozirconium, diphenylenesilylenebis (indenyl) dichlorozirconium, tetramethyldisiylenebis (indenyl) Dichlorozirconium, tetramethyldisilenebis (3-methylcyclopentadienyl) dichlorozirconium, dicyclohexylsilylenebis (indenyl) dichlorozirconium, dicyclohexylsilylenebis (2-methylindenyl) dichloro Zirconium, dicyclohexylsilylene bis (2,4,7-trimethylindenyl) dichlorozirconium, dimethylgermanium bis (indenyl) dichlorozirconium, dimethylgermanium (cyclopentadienyl) (fluorenyl) dichlorozirconium, methylaluminum bis (indenyl) dichlorozirconium , Phenylaluminum bis (indenyl) dichlorozirconium, phenylphosphinobis (indenyl) dichlorozirconium, ethyleneboranobis (indenyl) dichlorozirconium, phenylaminobis (indenyl) dichlorozirconium, phenylamino (cyclopentadienyl) (fluorenyl) dichloro Zirconium etc. are mentioned.

  Examples of the compound represented by the above formula (I) include compounds described in JP-A-6-184179, JP-A-6-345809, and the like. Specific examples include rac-dimethylsilanediyl-bis-1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-phenylmethylsilanediyl-bis-1- (2-methyl-4, 5-benzoindenyl) -zirconium dichloride, rac-ethanediyl-bis-1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-butanediyl-bis-1- (2-methyl-4, 5-benzoindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- (4,5-benzoindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- (2-methyl-α- Methyl-α-acenaphthoindenyl) -zirconium dichloride, rac-phenylmethylsila Benzoindenyl-type or acenaphtho-indenyl-type compounds such as N-diyl-bis-1- (2-methyl-α-acenaphthoindenyl) -zirconium dichloride, and those obtained by replacing zirconium in these compounds with titanium or hafnium, etc. Is mentioned.

Further, examples of the compound represented by the above formula (I) include JP-A-4-268308, JP-A-5-306304, JP-A-6-1005209, JP-A-6-157661, and JP-A-7-149815. And compounds described in JP-A-7-188318, JP-A-7-258321, and the like. Among them, M ¹ is hafnium or 2-position substituted indenyl complex, 4-position substituted indenyl complex, 2,4-position substituted indenyl complex, or M ¹ is hafnium and 2-position substituted indenyl complex, 4-position substituted indenyl. A complex or a 2,4-substituted indenyl complex is preferred.

  Specific examples include dimethylsilanediyl-bis-1- (2-methyl-4-phenylindenyl) -zirconium dichloride, dimethylsilanediyl-bis-1- [2-methyl-4- (1-naphthyl) indenyl]. Zirconium dichloride, dimethylsilanediyl-bis-1- (2-ethyl-4-phenylindenyl) -zirconium dichloride, dimethylsilanediyl-bis-1- [2-ethyl-4- (1-naphthyl) indenyl] zirconium Dichloride, phenylmethylsilanediyl-bis-1- (2-methyl-4-phenylindenyl) -zirconium dichloride, phenylmethylsilanediyl-bis-1- [2-methyl-4- (1-naphthyl) indenyl]- Zirconium dichloride, phenylmethylsilanediyl-bis-1- ( Aryl substituted products such as -ethyl-4-phenylindenyl) -zirconium dichloride, phenylmethylsilanediyl-bis-1- [2-ethyl-4- (1-naphthyl) indenyl] -zirconium dichloride, rac-dimethylsilylene- Bis-1- (2-methyl-4-ethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (2-methyl-4-isopropylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis- 1- (2-methyl-4-tertiarybutylindenyl) -zirconium dichloride, rac-phenylmethylsilylene-bis-1- (2-methyl-4-isopropylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis -1- (2-ethyl-4-methyl) Denyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (2,4-dimethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (2-methyl-4-ethylindenyl) -zirconium 2,4-position substitution products such as dimethyl, rac-dimethylsilylene-bis-1- (4,7-dimethylindenyl) -zirconium dichloride, rac-1,2-ethanediyl-bis-1- (2-methyl-4 , 7-dimethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (3,4,7-trimethylindenyl) -zirconium dichloride, rac-1,2-ethanediyl-bis-1- (4 7-dimethylindenyl) -zirconium dichloride, rac-1,2-butanediyl- 4,7-position, 2,4,7-position or 3,4,7-position substitution product such as bis-1- (4,7-dimethylindenyl) -zirconium dichloride, dimethylsilanediyl-bis-1- ( 2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, phenylmethylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis- 1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-1,2-ethanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac- Diphenylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconi Mudichloride, rac-phenylmethylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- (2,4,6-trimethylindenyl) ) -2,4,6-position substitution such as zirconium dichloride, 2,5,6-position substitution such as rac-dimethylsilanediyl-bis-1- (2,5,6-trimethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis- (2-methyl-4,5,6,7-tetrahydro-1-indenyl) -zirconium dichloride, rac-ethylene-bis- (2-methyl-4,5,6,7-tetrahydro- 1-indenyl) -zirconium dichloride, rac-dimethylsilylene-bis- (2-methyl-4, , 6,7-tetrahydro-1-indenyl) -zirconium dimethyl, rac-ethylene-bis (2-methyl-4,5,6,7-tetrahydro-1-indenyl) -zirconium dimethyl, rac-ethylene-bis- ( 4,5,6,7-tetrahydroindenyl compound such as 4,7-dimethyl-4,5,6,7-tetrahydro-1-indenyl) -zirconium dichloride and the like, and zirconium in these compounds is converted to titanium or hafnium. Substituted ones are listed.

［式中、Ｍ^１はチタン、ジルコニウム又はハフニウムを示す。Ｒ^３〜Ｒ^１３、Ｘ^１及びＸ^２は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基又はリン含有基を示し、Ｒ^５とＲ^６及びＲ^１０とＲ^１１は、互いに結合して環を形成してもよい。Ｘ^１及びＸ^２は、それぞれ独立に、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基又はリン含有基を示す。Ａは二つの配位子を結合する二価の架橋基であって、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、ケイ素含有基、ゲルマニウム含有基、スズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＮＲ^１４−、−ＰＲ^１４−、−Ｐ（Ｏ）Ｒ^１４−、−ＢＲ^１４−又は−ＡｌＲ^１４−を示し、Ｒ^１４は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基又は炭素数１〜２０のハロゲン含有炭化水素基を示す。］ Moreover, as a compound represented by Formula (I), the compound represented by Formula (Ia) is preferable. This transition metal compound is a single bridge type complex.

[Wherein M ¹ represents titanium, zirconium or hafnium. R ^{3 to} R ¹³ , X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, oxygen A containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and R ⁵ and R ⁶ and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. X ¹ and X ² are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, or a nitrogen-containing group. Represents a group or a phosphorus-containing group. A is a divalent bridging group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, tin containing _{group, -O -, - CO -,} - S -, - SO 2 -, - NR 14 -, - PR 14 -, - P (O) R 14 -, - BR 14 - or -AlR ¹⁴ - are shown , R ¹⁴ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. ]

In the formula (Ia), among R ^{3 to} R ¹³ , X ¹ and X ² , examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, and n-decyl group. And alkyl groups such as phenyl group, aryl groups such as 1-naphthyl group and 2-naphthyl group, and aralkyl groups such as benzyl group. Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include groups in which one or more hydrogen atoms of the hydrocarbon group such as trifluoromethyl are substituted with an appropriate halogen atom. Examples of the silicon-containing group include a trimethylsilyl group and a dimethyl (t-butyl) silyl group. Examples of oxygen-containing groups include methoxy groups and ethoxy groups, and examples of sulfur-containing groups include thiol groups and sulfonic acid groups. Examples of the nitrogen-containing group include a dimethylamino group. Examples of the phosphorus-containing group include a phenylphosphine group. R ⁵ and R ⁶ and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring such as fluorene. Preferable examples of R ⁶ , R ⁷ , R ⁹ , R ¹¹ and R ¹² include a hydrogen atom. R ³ , R ⁴ , R ⁵ , R ⁸ , R ¹⁰ and R ¹³ are preferably an alkyl group having 6 or less carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group or a cyclohexyl group, and particularly preferably an isopropyl group. . X ¹ and X ² are preferably a halogen atom, a methyl group, an ethyl group, or a propyl group.

Specific examples of A include methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene, dimethylsilylene, tetramethyldisylylene, dimethylgermylene, methylboridene (CH ₃ -B =), Methylaluminidene (CH ₃ -Al =), phenylphosphilidene (Ph-P =), phenylphospholidene (PhPO =), 1,2-phenylene, vinylene (-CH = CH-), vinylidene (CH ₂ = C =), methylimide, oxygen (—O—), sulfur (—S—) and the like, among which methylene, ethylene, ethylidene and isopropylidene are preferable.
M ¹ represents titanium, zirconium or hafnium, with hafnium being particularly preferred.

  Specific examples of the transition metal compound represented by the formula (Ia) include 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl) hafnium. Dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7-diisopropylindenyl) hafnium dichloride, isopropylidene (1- (4,7-diisopropylindenyl)) (2- (4,7- Diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (1- (4,7-dimethylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7-dimethylindenyl)) hafnium dichloride, isopropylidene (1- (4,7-di) Chiruindeniru)) (2- (4,7-diisopropyl-indenyl) hafnium dichloride and the like, but are not limited to, those obtained by replacing hafnium in the zirconium or titanium in these compounds, but is not limited thereto.

［式中、Ｍ^２はチタン、ジルコニウム又はハフニウムを示し、Ｅ^１及びＥ^２はそれぞれシクロペンタジエニル基、置換シクロペンタジエニル基、インデニル基、置換インデニル基、ヘテロシクロペンタジエニル基、置換ヘテロシクロペンタジエニル基、アミド基、ホスフィド基、炭化水素基及びケイ素含有基の中から選ばれた配位子であって、Ａ^１及びＡ^２を介して架橋構造を形成しており、また、それらは互いに同一でも異なっていてもよく、Ｆ^１はσ結合性の配位子を示し、Ｆ^１が複数ある場合、複数のＦ^１は同じでも異なっていてもよく、他のＦ^１、Ｅ^１、Ｅ^２又はＧ^１と架橋していてもよい。Ｇ^１はルイス塩基を示し、Ｇ^１が複数ある場合、複数のＧ^１は同じでも異なっていてもよく、他のＧ^１、Ｅ^１、Ｅ^２又はＦ^１と架橋していてもよく、Ａ^１及びＡ^２は二つの配位子を結合する二価の架橋基であって、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、ケイ素含有基、ゲルマニウム含有基、スズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−Ｓｅ−、−ＮＲ^１５−、−ＰＲ^１５−、−Ｐ（Ｏ）Ｒ^１５−、−ＢＲ^１５−又は−ＡｌＲ^１５−を示し、Ｒ^１５は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基を示し、それらは互いに同一でも異なっていてもよい。ｑは１〜５の整数で〔（Ｍ^２の原子価）−２〕を示し、ｒは０〜３の整数を示す。］ Moreover, as a catalyst component used by this method, the transition metal compound represented by Formula (II) is mentioned, for example.

[Wherein, M ² represents titanium, zirconium or hafnium, and E ¹ and E ² represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted group, respectively. A ligand selected from a heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which forms a cross-linked structure via A ¹ and A ² ; , they may be the same or different from each other, F ¹ represents a σ-bonding ligand, and when F ¹ is plural, F ¹ may be the same or different, the other F ^1, It may be crosslinked with E ¹ , E ² or G ¹ . G ¹ represents a Lewis base, and ^{when G 1} is located more, more in ^{G 1} may be the same or different, the other in ^{G 1,} E 1, it may be crosslinked with ^{E 2} or ^{F 1,} A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, and a germanium-containing group. group, a tin-containing _{group, -O -, - CO -,} - S -, - SO 2 -, - Se -, - NR 15 -, - PR 15 -, - P (O) R 15 -, - BR 15 - or -AlR ¹⁵ - ^{indicates, R 15} is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, even they be the same or different from each other Good. q is an integer of 1 to 5 and represents [(M ² valence) -2], and r represents an integer of 0 to 3. ]

In the above formula (II), M ² represents titanium, zirconium or hafnium, but zirconium and hafnium are preferred, and hafnium is more preferred. E ¹ and E ² are each a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (—N <) as described above. , Phosphide group (-P <), hydrocarbon group [>CR'-,> C <] and silicon-containing group [>SiR'-,> Si <] (where R 'is hydrogen or having 1 to 20 carbon atoms. A ligand selected from hydrocarbon groups or heteroatom-containing groups), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same as or different from each other. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.

Specific examples of the σ bond ligand represented by F ¹ include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. , An amide group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, and the like. . If the ^{F 1} there are a plurality, the plurality of ^{F 1} may be the same or different, the other ^{F 1,} E 1, may be crosslinked with ^{E 2} or ^{G 1.}

On the other hand, specific examples of the Lewis base represented by G ¹ include amines, ethers, phosphines, thioethers, and the like. If the ^{G 1} is located more, more in ^{G 1} may be the same or different, may be crosslinked with other in ^{G 1, E} 1, ^{E 2} or ^{F 1.}

［Ｒ^１６及びＲ^１７は、それぞれ水素原子又は炭素数１〜２０の炭化水素基で、それらは互いに同一でも異なっていてもよく、また、互いに結合して環構造を形成していてもよい。ｐは１〜４の整数を示す。］ Next, it is preferable that at least one of the crosslinking groups represented by A ¹ and A ² is a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms. Examples of such a cross-linking group include the following groups.

[R ¹⁶ and R ¹⁷ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same as or different from each other, and may be bonded to each other to form a ring structure. p shows the integer of 1-4. ]

Specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, a 1,2-cyclohexylene group, and a vinylidene group (CH ₂ ═C═). Among these, a methylene group, an ethylene group, and an isopropylidene group are preferable. A ¹ and A ² may be the same as or different from each other.

In the transition metal compound represented by the formula (II), when E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, the bond between the bridging groups of A ¹ and A ² is (1 , 1 ′) (2, 2 ′) double cross-linked type, or (1, 2 ′) (2, 1 ′) double cross-linked type.

Among the transition metal compounds represented by the formula (II), a transition metal compound having a double bridged biscyclopentadienyl derivative represented by the formula (II-a) as a ligand is preferable.

In the formula (II-a), M ² , F ¹ , G ¹ , A ¹ , A ² , q and r are the same as described above. F ¹ represents a σ-bonding ligand, and when F ¹ is plural, F ¹ may be the same or different, may be crosslinked with other F ¹ or G ^1. The specific examples of F ¹ may be the same as those exemplified in the description of F ¹ of the formula (II). G ¹ represents a Lewis base, and when G ¹ is located more, more in G ¹ may be the same or different, may be crosslinked with other in G ¹ or F ^1. Specific examples of G ¹ include the same examples as those exemplified in the description of G ^{1 in} formula (II). R ^{18 to} R ²³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{18 to} R ²³ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.

  The transition metal compound having this double-bridged biscyclopentadienyl derivative as a ligand has a ligand of (1,1 ′) (2,2 ′) double-bridge type and (1,2 ′) ( 2,1 ′) Double-crosslinking type may be used.

Specific examples of the transition metal compound represented by the formula (II-a) include (1,1′-ethylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene). ) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) ( 2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (3-methylindene ) Zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene)- Bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,1'-ethylene ) (2,2′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, ( 1,1′-ethylene) (2,2′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene -Bis (5,6-dimethylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'- Ethylene) (2,1′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4-phenylindenyl) zirconium Dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (3 -Methyl-4-isopropylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (3-methyl-4-isopropylin Nyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene ) -Bis (5,6-benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) (2 , 1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2 , 1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-ethylene) -bis (indenyl) zirconium Dichloride, (1,1′-ethylene) (2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride , (1,2'-methylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1'-isopropylidene) (2,2'-methylene) -bis (indenyl) zirconium dichloride , (1,1′-methylene) (2,2′-methylene) (3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′- Isopropylidene) (3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1′-propylidene) 2,2'-propylidene) (3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1'-ethylene) (2,2'-methylene) -bis (3-methylcyclopentadi Enyl) zirconium dichloride, (1,1′-methylene) (2,2′-ethylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′- Ethylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1, 1'-methylene) (2,2'-methylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1'-methyle) ) (2,2′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (3-methylcyclopenta) Dienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2 '-Isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1'-methylene) (2,2'-methylene) -bis (3,4-dimethylcyclopentadienyl) Zirconium dichloride, (1,1′-methylene) (2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium Chloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′- Methylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1, 2'-methylene) (2,1'-methylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) -bis (3-methyl Cyclopentadienyl) zirconium dichloride, (1,2'-isopropylidene) (2,1'-isopropylidene) -bis (3-methylcyclopentadi) Nyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1 ' -Isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium Dichloride, (1,2'-methylene) (2,1'-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-isopropylidene) (2,1'- Isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride and the like, and zirconium in these compounds to titanium Include those substituted on hafnium.
The transition metal compounds described above may be used alone or in combination of two or more.

  The co-catalyst components used in this method include (i) aluminoxane, (ii) ionic compounds that can be converted to cations by reacting with the transition metal compounds, and (iii) clays, clay minerals, and ion-exchange layered compounds. At least one selected from among them can be used.

［式中、Ｒ^２４は、炭素数１〜２０、好ましくは１〜１２のアルキル基、アルケニル基、アリールアルキル基等の炭化水素基或いはハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。尚、各Ｒ^２４は同じでも異なっていてもよい］ (I) Examples of the aluminoxane include a chain aluminoxane represented by the formula (III) and a cyclic aluminoxane represented by the formula (IV).

[Wherein, R ²⁴ represents a hydrocarbon group such as an alkyl group, an alkenyl group, or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen atom, and w represents an average degree of polymerization. -50, preferably an integer of 2-40. Each R ²⁴ may be the same or different.]

  Examples of the method for producing these aluminoxanes include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, a crystal water contained in a metal salt or the like There are a method of reacting water adsorbed on an inorganic or organic material with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and a reaction with water.

The aluminoxane may be insoluble in a hydrocarbon solvent or may be soluble in a hydrocarbon solvent. Preferably, it is soluble in a hydrocarbon solvent and the residual organoaluminum compound (compound other than aluminoxane) measured by ¹ H-NMR is 10% by weight or less. More preferably, the residual organoaluminum compound is 3 to 5% by weight, particularly preferably 2 to 4% by weight. When such an aluminoxane is used, in a catalyst using a carrier, the proportion of the aluminoxane supported on the carrier (also referred to as the loading rate) is preferable. Furthermore, since it is soluble in a hydrocarbon solvent, there is also an advantage that the unsupported aluminoxane can be recycled and reused. Furthermore, since the properties of the aluminoxane are stable, there is an advantage that no special treatment is required for use. Use of such an aluminoxane is preferable because it improves the average particle size and particle size distribution (also collectively referred to as morphology) of the polyolefin obtained by polymerization. If the residual organoaluminum compound exceeds 10% by mass, the supporting rate may decrease, and the polymerization activity may decrease.

  Examples of a method for obtaining such an aluminoxane include a method in which a solvent of an aluminoxane is distilled off by heating under reduced pressure (also referred to as a dry-up method). In the dry-up method, the evaporation of the solvent by heating under reduced pressure is preferably 80 ° C. or lower, more preferably 60 ° C. or lower.

Examples of the method for removing components unnecessary for the hydrocarbon solvent from the aluminoxane include a method in which a component insoluble in the hydrocarbon solvent is naturally precipitated and then separated by decantation. Or the method of isolate | separating by operation, such as centrifugation, may be used. Thereafter, it is preferable to filter the recovered soluble components using a G5 glass filter or the like under a nitrogen stream because insoluble components are sufficiently removed. The aluminoxane thus obtained may increase the gel component over time, but is preferably used within 48 hours after preparation, and particularly preferably immediately after preparation. The ratio of the aluminoxane and the hydrocarbon solvent is not particularly limited, but it is preferably used at a concentration such that the aluminum atom in the aluminoxane is 0.5 to 10 mol relative to 1 L of the hydrocarbon solvent.
The hydrocarbon solvent includes aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, cyclopentane, and cyclohexane. And alicyclic hydrocarbons such as cyclooctane and methylcyclopentane, and petroleum fractions such as naphtha, kerosene, and light gas oil.

(Ii) As the ionic compound, those represented by the formulas (V) and (VI) can be preferably used from the viewpoint that a polymerization active site can be formed particularly efficiently.
([L ¹ −R ²⁵ ] ^{h +} ) _a ([Z] ⁻ ) _b (V)
([L ² ] ^{h +} ) _a ([Z] ⁻ ) _b (VI)
(However, ^{L 2} is ^{M 3, R 26 R 27 M} 4, R 28 3 C or ^R 29 ^{M 4.)}
[Wherein L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ or [Z ² ] ⁻ , wherein [Z ¹ ] ⁻ is an anion in which a plurality of groups are bonded to an element. That is, [M ⁵ H ¹ H ² ... H ^f ] (wherein M ⁵ represents a group 5 to 15 element of the periodic table, preferably a group 13 to 15 element of the periodic table. H ¹ to H ^f is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. -20 aryloxy group, C7-40 alkylaryl group, C7-40 arylalkyl group, C1-20 halogen-substituted hydrocarbon group, C1-20 acyloxy group, organic metalloid Group or carbon atoms containing 2-20 carbon atoms Two or more may form a ring .f of showing the original ^.H 1 to H ^f represents an integer of [(valence of central metal ^{M 5)} +1].), ^{[Z 2] −} Represents a Bronsted acid alone having a logarithm (pKa) of reciprocal acid dissociation constant of −10 or less, or a conjugate base in which Bronsted acid and Lewis acid are combined, or a conjugate base generally defined as a super strong acid. In addition, a Lewis base may be coordinated. R ²⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ²⁶ and R ²⁷ are each a cyclopentadienyl group, A substituted cyclopentadienyl group, indenyl group or fluorenyl group, R ²⁸ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ²⁹ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. h is an integer of 1 to 3 in terms of ionic valences of [L ¹ -R ²⁵ ] and [L ² ], a is an integer of 1 or more, and b = (h × a). M ³ contains elements of Group 1 to ³ , 11 to 13 and 17 of the periodic table, and M ⁴ represents elements of Group 7 to 12 of the periodic table. ]

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ²⁵ include hydrogen, methyl group, ethyl group, benzyl group, trityl group and the like. Specific examples of R ²⁶ and R ²⁷ include cyclopentadienyl group, methylcyclopentadienyl. Group, ethylcyclopentadienyl group, pentamethylcyclopentadienyl group and the like. Specific examples of R ²⁸ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ²⁹ include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. Specific examples of M ³ include Li, Na, K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ⁴ include Mn, Fe, Co, Ni, Zn. Etc.

In [Z ¹ ] ⁻ , that is, [M ⁶ H ¹ H ² ... H ^f ], specific examples of M ⁶ include B, Al, Si, P, As, Sb, etc., preferably B or Al Is mentioned. Specific examples of H ¹ and H ^{2 to} H ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group and the like as an alkoxy group or an aryloxy group, Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Romechiru) phenyl group, bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, diphenyl boron, and the like.

Specific examples of non-coordinating anions, that is, Bronsted acids having a pKa of −10 or less, or conjugate bases [Z ² ] ⁻ in which Bronsted acids and Lewis acids are combined, include trifluoromethanesulfonate anions ( CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ⁻ , fluorosulfonate anion (FSO ₃ ) ⁻ , chlorosulfonate anion (ClSO ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF) ₅ ) ^- , Fluorosulfonic acid anion / 5-arsenic fluoride (FSO ₃ / AsF ₅ ) ⁻ , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{− and the} like.

Specific examples of such ionic compounds include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl tetraphenylborate (tri-n-butyl). ) Ammonium, benzyl tetraphenylborate (tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzyltetraphenylborate Pyridinium, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylanborate Ni-, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetrakis (pentafluorophenyl) tetraethylammonium borate Benzyl tetrakis (pentafluorophenyl) ammonium borate (tri-n-butyl), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Methylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) ) Trimethylanilinium borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate ( 2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [3,5-di (trifluoromethyl) phenyl] dimethylanilinium borate , Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetra Kiss (pentafluorophenyl) borate ferrocenium, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, Tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, hexa Examples thereof include silver fluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.
These ionic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

(Iii) As clays, clay minerals and ion-exchangeable layered compounds, the following are preferably used.
Clay is an aggregate of fine hydrated silicate minerals that is plastic when it is kneaded with a suitable amount of water, shows rigidity when dried, and sinters when baked at high temperatures. The clay mineral is a hydrous silicate that is a main component of clay. These are not limited to natural products but may be artificially synthesized.

  The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are weakly bonded to each other and have a parallel stacked structure, and the contained ions can be exchanged. Some clay minerals are ion-exchangeable layered compounds.

For example, phyllosilicates are mentioned as clay minerals. Examples of phyllosilicates include phyllosilicate and phyllosilicate. Examples of phyllosilicates include natural products such as montmorillonite, saponite, hectorite, illite, sericite, and smectite and mica group or mixed layer mineral of mica group and vermiculite group that belong to mica group. . In addition, examples of the synthetic product include fluorine tetrasilicon mica, laponite, and smecton. In addition, it has a layered crystal structure which is not a clay mineral such as α-Zr (HPO ₄ ) ₂ , γ-Zr (HPO ₄ ) ₂ , α-Ti (HPO ₄ ) ₂ and γ-Ti (HPO ₄ ) _2. Examples include ionic crystalline compounds.
In addition, clays and clay minerals that do not belong to the ion-exchange layered compound include clay called bentonite because of its low montmorillonite content, xylem clay, gallome clay, which contains many other components in montmorillonite, and sepiolite that exhibits a fibrous form. , Palygorskite, amorphous or low crystalline allophane, imogolite and the like.
The promoter component described above may be used alone or in combination of two or more.
Regarding other specific production conditions in this production method, the conditions described in WO 02/072649 can be used.

  In addition, the component (A) is composed of titanium trichloride-based compound or a catalyst component in which titanium, magnesium and a halogen element are essential components, and an organic aluminum compound in the presence of a catalyst, ethylene, propylene and a carbon number of 4 to Polymerization or copolymerization of one or two or more monomers selected from 20 α-olefins and the homopolymer or copolymer obtained in the first polymerization step can be polymerized in one molecule A second polymerization step of copolymerizing one or more monomers selected from ethylene, propylene and an α-olefin having 4 to 20 carbon atoms in the presence of a polyene having at least two carbon-carbon double bonds. It can be manufactured from a manufacturing method.

Examples of the α-olefin and polyene having 4 to 20 carbon atoms are the same as those described above. Examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, and the like.
Regarding other specific production conditions in this production method, the conditions described in WO 02/072649 can be used.

  The proportion of the component (A) in the resin composition of the present invention is 10 to 50% by weight, preferably 15 to 40% by weight. If it is less than 10% by weight, the foaming characteristics are lowered (decrease in foaming ratio and open cell ratio is increased), and thermoformability is lowered, which is not preferable. On the other hand, if it exceeds 50% by weight, it is not economical and is not preferable.

(B) Polypropylene resin The polypropylene resin (B) (hereinafter referred to as component (B)) contained in the composition of the present invention satisfies the following (B-1) to (B-4).
(B-1) The melt tension (MT ₁₉₀ ) at 190 ° C. is 0.5 to 5 g.
(B-2) Melt flow rate (MFR) is 1 to 10 g / 10 min. (B-3) Ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) is 2 to 4.5.
(B-4) In the melt viscoelastic behavior measured using a rotary rheometer, the relaxation time (τ) at an angular frequency ω = 0.1 rad / sec is 0.5 to 2.0 seconds.

In the above (B-1), when MT ₁₉₀ is less than 0.5 g, an increase in the open cell ratio, an increase in the foam cell diameter, a deterioration in mold reproducibility during thermoforming, and the like are not preferable. On the other hand, if it exceeds 5 g, the high molecular weight component is increased, and the stretchability is lowered. (B) MT ₁₉₀ of a component becomes like this. Preferably it is 0.6-4g, More preferably, it is 0.8-3g.

  In the above (B-2), if the MFR is less than 1 g / 10 minutes, it is not preferable because the stretch breakage occurs at the time of foam molding and the productivity is lowered. On the other hand, if it exceeds 10 g / 10 minutes, the foaming characteristics are lowered (such as an increase in the open cell ratio), which is not preferable. The MFR of the component (B) is preferably 2 to 9 g / 10 minutes, more preferably 3 to 8 g / 10 minutes.

  In the above (B-3), if Mw / Mn is less than 2, it is not preferable because it becomes difficult to produce the resin. On the other hand, if it exceeds 4.5, it is not preferable because drawing breakage occurs during foam molding. Mw / Mn of (B) component becomes like this. Preferably it is 2-4, More preferably, it is 2-3.5.

  In the above (B-4), if the relaxation time (τ) is less than 0.5 seconds, the tension is so weak that foam molding cannot be performed. On the other hand, if it exceeds 2.0 seconds, it is not preferable because a stretching break occurs. The relaxation time (τ) of the component (B) is preferably 0.6 to 1.8 seconds, more preferably 0.8 to 1.6 seconds.

Here, the relaxation time (τ) of the component (B) will be described in detail.
When an external force is applied to a material system that is in an equilibrium state, and the external force is removed after reaching a new equilibrium state or steady state, the phenomenon that the system recovers to the initial equilibrium state by the internal motion of the system is called a relaxation phenomenon. A characteristic time constant that is a measure of the time required for relaxation is called relaxation time. In the case of a polymer molding process (for example, extrusion molding), a molten polymer is flowed. At this time, molecular chains are stretched and aligned in the flow direction (this is referred to as “orientation”). When the flow is finished and the cooling is started, the stress applied to the molecules disappears, each molecular chain starts to move and eventually turns in a selfish direction (this is called “relaxation of molecular chains”).

The relaxation time (τ) of the component (B) is expressed by τ = G ′ / ωG ″ = G ′ / G ″ (angular frequency ω = 10 ⁰ = 1 sec ⁻¹ ). Here, G 'is a storage elastic modulus and shows the elastic property of (B) component. G ″ is a loss elastic modulus and indicates the viscous property of the component (B). As is clear from this equation, when the relaxation time (τ) becomes longer (becomes larger), it means that G ′ is larger, and the component (B) has more elastic components. Further, when the relaxation time (τ) is shortened (decreased), it means that G ″ is large, and the component (B) having a viscous property increases.

As described above, the relaxation time (τ) is related to the ease of return of the component (B) oriented during extrusion (in the extrusion direction). When the relaxation time (τ) is short, When it is easy to return and the relaxation time (τ) is long, it indicates that it is difficult to return.
Thus, the relaxation time (τ) is a time for the molecular chain to relax (return to the original state) when the component (B) is deformed, and the relaxation time (τ) is short (B ) Means that the molecular weight distribution of the component is narrow or the molecular weight is small.

  Since this relaxation time (τ) reflects a high molecular weight component in the component (B) that exhibits elastic behavior, the relaxation time (τ) can be controlled by controlling the molecular weight. For example, when the supply amount of hydrogen is increased during the production of component (B), the MFR increases (molecular weight decreases) and the relaxation time (τ) decreases. On the other hand, when the supply amount of hydrogen is reduced, the MFR decreases (molecular weight increases) and the relaxation time (τ) increases.

  Also, when the molecular weight distribution is wide, the ratio of the high molecular weight component is relatively large, so the relaxation time (τ) is large. When the molecular weight distribution is narrow, the ratio of the high molecular weight component is small, so the relaxation time is small. (Τ) becomes smaller. Therefore, the relaxation time (τ) can be controlled by controlling the molecular weight distribution.

Examples of the method for controlling the molecular weight distribution include the following methods.
(1) A polypropylene resin is produced using a metallocene catalyst. The metallocene catalyst can narrow the molecular weight distribution of the resin as compared with other catalysts, and as a result, the relaxation time (τ) can be reduced.
(2) The catalyst system co-catalyst is changed from, for example, triisobutylaluminum to triethylaluminum or trimethylaluminum.
(3) The organosilane compound used as the donor component in the catalyst system is changed from, for example, dicyclopentyldimethoxysilane to cyclohexylmethyldimethoxysilane.
(4) The polymerized polypropylene resin is washed with a hydrocarbon solvent to remove low molecular weight components.
(5) Melt kneading by mixing a peroxide with a polypropylene resin. This reduces both the molecular weight and the molecular weight distribution.
As described above, the relaxation time (τ) of the component (B) can be controlled by controlling the molecular weight or controlling the molecular weight distribution.

As the component (B), a polypropylene resin obtained by melt-kneading a polypropylene resin in the presence of an organic peroxide can be suitably used.
In this method, the polypropylene resin and the organic peroxide are mixed when performing melt kneading, but the mixing method is not particularly limited, and for example, mechanical mixing is performed using a blender such as a blender or a mixer. Method, organic peroxide is dissolved in an appropriate solvent (for example, isoparaffin hydrocarbon oil (IP Solvent (trade name), manufactured by Idemitsu Kosan Co., Ltd.)), adhering to a polypropylene resin, and mixed by drying the solvent And the like.

  The melt kneading temperature is preferably higher than the melting temperature of the polypropylene resin and higher than the decomposition temperature of the organic peroxide. However, if the heating temperature is excessively high, the polymer may be thermally deteriorated. Therefore, in general, the melting temperature is preferably set in the range of 170 to 300 ° C, particularly 180 to 250 ° C.

  As the organic peroxide, known compounds can be generally used. Specifically, peroxides such as methyl ethyl peroxide and methyl isobutyl peroxide, diacyl peroxides such as isobutyryl peroxide and acetyl peroxide, and diisopropylbenzene. Hydroperoxide such as hydroperoxide, dialkyl peroxide such as 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 1,3-bis- (t-butylperoxyisopropyl) benzene Peroxyketals such as 1,1-di-t-butylperoxy-cyclohexane, alkyl peresters such as t-butyl peroxyacetate and t-butyl peroxybenzoate, and parkabons such as t-butyl peroxyisopropyl carbonate Doors and the like.

  The amount of the organic peroxide used can be adjusted as appropriate within the range satisfying the above (B-1) to (B-4), but is preferably 0.1% relative to 100 parts by weight of the polypropylene resin used as a raw material. The amount is generally 001 to 1.0 parts by weight, more preferably 0.005 to 0.5 parts by weight.

  The polypropylene resin used for melt kneading is not particularly limited, and those obtained by a known slurry polymerization method, gas phase polymerization method or the like can be used. These polymerization methods may be performed in one stage or may be performed in multiple stages.

The component (B) is a polypropylene obtained by polymerizing propylene in the presence of a catalyst component in which a catalyst component containing a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton and a promoter component is combined. Series resins can be used preferably.
As the transition metal compound and the cocatalyst, those similar to the above can be used. Moreover, about the other specific manufacturing conditions in this manufacturing method, the conditions as described in an international publication 02/072649 pamphlet can be used.

  The proportion of the component (B) in the resin composition of the present invention is 20 to 70% by weight, preferably 30 to 60% by weight. If it exceeds 70% by weight, the foaming characteristics are lowered, which is not preferable. On the other hand, less than 20% by weight is not preferable because the cost cannot be reduced.

(C) Random copolymer polypropylene (C) Random copolymer polypropylene (hereinafter referred to as (C) component) has an MFR of 1 to 8 g / 10 min and an ethylene unit content in the copolymer of 1 to 5 weights. %.
When the MFR of the component (C) is less than 1, stretch breakage occurs at the time of foam molding and productivity is lowered. On the other hand, when it exceeds 8, foaming characteristics such as drawdown property and sheet appearance deteriorate, which is not preferable. Preferably, the MFR is 1.5-5 g / 10 min.

  If the ethylene unit content in the copolymer is less than 1% by weight, the effect of improving the drawdown property is small, and if it exceeds 5% by weight, the sheet appearance tends to deteriorate. Preferably, the ethylene unit content is 2 to 4.5% by weight.

The manufacturing method of the random copolymer polypropylene which is (C) component is not specifically limited, Any may be sufficient if it is a manufacturing method with which said copolymer polypropylene is obtained. Hereinafter, an example of a manufacturing method is shown.
The catalyst that can be used for the production is a catalyst formed from a solid catalyst component (a) containing magnesium, titanium, and halogen as essential components, an organoaluminum compound (b), and a specific organosilicon compound (c), As typical ones, the following catalyst components can be used.

(A) Solid catalyst component The preferred carrier for the solid catalyst component is obtained from magnesium metal, an alcohol and a halogen and / or a halogen-containing compound. In this case, magnesium, such as granular form, ribbon form, and powder form, can be used as the metallic magnesium. Further, the metal magnesium is preferably one in which a coating such as magnesium oxide is not generated on the surface. As the alcohol, it is preferable to use a lower alcohol having 1 to 6 carbon atoms, and in particular, when ethanol is used, the above-mentioned carrier that remarkably improves the expression of the catalyst performance can be obtained. As the halogen, chlorine, bromine, or iodine is preferable, and iodine can be particularly preferably used. As the halogen-containing compound, MgCl ₂ and MgI ₂ can be preferably used. The amount of alcohol is preferably 2 to 100 mol, particularly preferably 5 to 50 mol, per 1 mol of metal magnesium.

  The amount of halogen or halogen-containing compound used is such that the halogen atom or halogen atom in the halogen-containing compound is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 1 gram atom of metal magnesium. , 0.001 gram atom or more. Each of the halogen and the halogen-containing compound may be used alone or in combination of two or more. As for the reaction method of metallic magnesium, alcohol, halogen and / or halogen-containing compound, for example, generation of hydrogen gas is recognized under reflux (about 79 ° C.) between metallic magnesium, alcohol and halogen and / or halogen-containing compound. This is a method of obtaining a carrier by reacting until it disappears (usually 20 to 30 hours). This is preferably performed in an inert gas (eg, nitrogen gas, argon gas) atmosphere. When the obtained support is used for the synthesis of the next solid catalyst component, a dried product may be used, or a product washed with an inert solvent such as heptane after filtration may be used.

  Further, this carrier is nearly granular and has a sharp particle size distribution. Furthermore, even if each particle is taken, the variation in the particle shape is very small. In order to produce a solid catalyst component, at least a titanium compound is brought into contact with the above support.

As this titanium compound, general formula (VII)
TiX ³ _y (OR ³⁰ ) _4-y (VII)
(In the formula, X ³ is preferably a halogen atom, particularly a chlorine atom, R ³⁰ is a hydrocarbon group having 1 to 10 carbon atoms, particularly a linear or branched alkyl group, and when a plurality of R ¹ are present. They may be the same as or different from each other, and y is an integer of 0 to 4). Specifically, Ti (OiC ₃ H ₇ ) ₄ , Ti (O—C ₄ H ₉ ) ₄ , TiCl (O—C ₂ H ₅ ) ₃ , TiCl (OiC ₃ H _7). ) ₃ , TiCl (O—C ₄ H ₉ ) ₃ , TiCl ₂ (O—C ₄ H ₉ ) ₂ , TiCl ₂ (OiC ₃ H ₇ ) ₂ , TiCl _{4 and the} like. TiCl ₄ is particularly preferable.

  The solid catalyst component can be obtained by further contacting an electron donating compound with the above support. As this electron-donating compound, aromatic dicarboxylic acid diester is preferable, and di-n-butyl phthalate is particularly preferable. Further, when the titanium compound and the electron donating compound are brought into contact with the above-mentioned carrier, a halogen-containing silicon compound such as silicon tetrachloride is preferably brought into contact.

  Said solid catalyst component can be prepared by a well-known method. For example, the above-mentioned carrier, electron donating compound and halogen-containing silicon compound are added to an inert hydrocarbon such as pentane, hexane, peptane or octene as a solvent, and a titanium compound is added while stirring. Usually, the electron-donating compound is added in an amount of 0.01 to 10 mol, preferably 0.05 to 5 mol in terms of magnesium atom, and titanium in an amount of magnesium atom in terms of magnesium atom. The compound is added in an amount of 1 to 50 mol, preferably 2 to 20 mol, and contact reaction is performed at 0 to 200 ° C. for 5 minutes to 10 hours, preferably at 30 to 150 ° C. for 30 minutes to 5 hours. Can be done. In addition, after completion | finish of reaction, it is preferable to wash | clean the produced | generated solid catalyst component with an inert hydrocarbon (for example, n-hexane, n-heptane).

(B) Organoaluminum compound As this organoaluminum compound, the general formula (VIII)
AlR ³¹ _z X ⁴ _3-z (VIII)
(In the formula, R ³¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, X ⁴ is a halogen atom, and is preferably a chlorine atom or a bromine atom. Z is an integer of 1 to 3. .) Is widely used.
Specific examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum monoethoxide, ethylaluminum sesquichloride and the like. These may be used alone or in combination of two or more. Of these, triethylaluminum and triisobutylaluminum are preferable.

(C) Organosilicon compound As the organosilicon compound, dicyclopentyldimethoxysilane can be preferably used. The solid catalyst component is pretreated and then used for polymerization. For example, the above solid catalyst component, organoaluminum compound, and organosilicon compound are added to an inert hydrocarbon such as pentane, hexane, peptane, or octene as a solvent, and propylene is supplied and reacted while stirring. Usually, the organoaluminum compound is added in an amount of 0.01 to 10 mol, preferably 0.05 to 5 mol, with respect to 1 mol of titanium atom in the solid catalyst component, and the organosilicon compound is added to titanium in the solid catalyst component. 0.01 to 20 mol, preferably 0.1 to 5 mol, may be added to 1 mol of an atom. Propylene is preferably supplied under a partial pressure of propylene higher than atmospheric pressure and pretreated at 0 to 100 ° C. for 0.1 to 24 hours. In addition, after completion | finish of reaction, it is preferable to wash | clean what was pre-processed by inert hydrocarbon (for example, n-hexane, n-heptane).

The polymerization conditions are not particularly limited, and the same conditions as known methods can be used. For example, it can be produced at a temperature of −80 to 150 ° C. under a partial pressure of propylene higher than atmospheric pressure. Preferably, at a temperature of 20 to 150 ° C., the partial pressure of propylene is in the range of atmospheric pressure to 40 kg / cm ² G. In general, the organoaluminum compound is added in an amount of 0.1 to 400 mol, preferably 1 to 200 mol, per mol of titanium atom in the solid catalyst component. 0.1 to 100 mol, preferably 1 to 50 mol, may be added to mol. The ethylene content and molecular weight are affected by both ethylene and hydrogen in the polymerization apparatus, but the ethylene content is mainly adjusted by the ethylene supply amount, and the copolymer molecular weight and MFR are mainly the hydrogen supply amount. And to select the desired ethylene content, molecular weight and MFR.

  The proportion of component (C) in the resin composition of the present invention is 20 to 70% by weight, preferably 30 to 60% by weight. If it exceeds 70% by weight, the sheet is likely to be cut at the time of molding, and productivity is lowered, which is not preferable. If it is less than 20% by weight, the drawdown property at the time of thermoforming is lowered, which is not preferable.

The composition of the present invention may further contain (D) an inorganic filler (hereinafter referred to as component (D)). The proportion of the component (D) is not particularly limited as long as it does not affect the appearance of the foamed sheet, but is preferably 1 to 100 weights with respect to 100 parts by weight of the composition comprising the components (A) to (C). Parts, more preferably 5 to 80 parts by weight. If it is less than 1 part by weight, mechanical properties such as rigidity are not improved. On the other hand, when the amount exceeds 100 parts by weight, the appearance of the foam sheet may be greatly deteriorated with respect to the improvement of mechanical properties.
Examples of the component (D) include talc, silica, calcium carbonate, clay, zeolite, alumina, barium sulfate, magnesium hydroxide and the like. Of these, talc is preferred because it provides a good balance between sheet appearance and mechanical properties.

  If necessary, additives such as an ultraviolet absorber, an antioxidant, an antistatic agent, and a colorant can be added to the composition of the present invention.

  The composition of the present invention can be molded into various molded articles such as foamed sheets and pipes by foam molding after mixing the components. As a molding method, a general molding method such as annular die molding or T-die molding can be used.

A molded product formed by foam molding of the composition of the present invention satisfies the following (1) to (4).
(1): Average cell diameter is 500 μm or less, preferably 400 μm or less (2): Open cell ratio is 1-30%, preferably 2-15%
(3): Stretchability is 5 m / min or more, preferably 6 m / min or more. (4): Foaming ratio is 1 to 5 times. The foamed molded product satisfying the above (1) to (4) has heat insulation and container appearance. It is preferable because it is excellent. A foam-molded composition of the present invention easily satisfies these conditions.

  The molded body of the present invention, for example, a foam sheet, is obtained by melting and kneading each of the above-mentioned components in the form of pellets and a foaming agent in an extruder, and then forming an annular die having an annular lip with the melt kneaded product attached to the tip of the extruder. The cylindrical foam can be obtained by extruding and foaming from the lip of this die, and then the cylindrical foam can be cut to form a sheet.

In obtaining the foamed sheet or other molded article of the present invention, an inorganic foaming agent, a volatile foaming agent, a decomposable foaming agent, or the like can be used as the foaming agent.
Examples of the inorganic foaming agent include carbon dioxide, air, and nitrogen. Examples of volatile blowing agents include propane, n-butane, i-butane, a mixture of n-butane and i-butane, chain aliphatic hydrocarbons such as pentane and hexane, and cyclic aliphatic carbonization such as cyclobutane and cyclopentane. Hydrogen etc. are mentioned. Examples of the decomposable foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, sodium bicarbonate and the like. These foaming agents can be mixed and used as appropriate.

  The foamed molded product of the present invention can be further thermoformed. As a thermoforming method, a general vacuum forming method, a pressure forming method, a vacuum pressure forming method, or the like is used. Thermoformed bodies obtained by these molding methods can be used in food containers, electronic material trays, and the like.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, parameter measurement and evaluation of the resin and molded body obtained in each example were performed as follows.
(1) Melt tension (MT)
The measurement was performed at a measuring temperature of 230 ° C. or 190 ° C. and a take-up speed of 3.1 m / min using Toyo Seiki Co., Ltd. Capillograph 1C. In the measurement, an orifice having a length of 8 mm and a diameter of 2.095 mm was used. In Table 1, MT at a measurement temperature of 230 ° C. is denoted as MT _230, and MT at 190 ° C. is denoted as MT ₁₉₀ .

(2) Ratio of weight average molecular weight to number average molecular weight (molecular weight distribution, Mw / Mn)
It calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin measured by the gel permeation chromatograph (GPC) method with the following apparatus and conditions. In addition, Mw and Mn were calculated | required from the molecular weight distribution curve measured by GPC.
[measuring device]
Column: TOSOGMMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS150C
[Measurement condition]
Solvent: 1,2,4-trichlorobenzene Temperature: 145 ° C

(3) Melt flow rate (MFR)
Based on JIS-K7210, the measurement was performed at a measurement temperature of 230 ° C. and a load of 2.16 kg.

(4) Relaxation time (τ)
The relaxation time (τ) is an angular frequency ω when a frequency dispersion measurement is performed at a temperature of 175 ° C. with a cone plate of 25 mmφ, a cone angle of 0.10 rad in a rotational rheometer manufactured by Rheometrics. The relaxation time at 0.1 rad / sec was determined. Specifically, the complex elastic modulus G ^* (iω) measured for the resin pellets was defined as σ ^* / γ ^* by the stress σ ^* and the strain γ ^* , and obtained by the following formula.
G ^* (iω) = σ ^* / γ ^* = G ′ (ω) + iG ″ (ω)
τ (ω) = G ′ (ω) / ωG ″ (ω)
(In the formula, G ′ represents a storage elastic modulus and G ″ represents a loss elastic modulus)

(5) Stretchability When foam molding is performed using a foam molding machine (TEM-41SS, manufactured by Toshiba Machine Co., Ltd.), the screw rotation speed is 60 rpm, the cylinder temperature is 210 ° C., the die temperature is 170 ° C., and the carbon dioxide injection amount is 200 g / hr. Under these conditions, when the take-up speed was gradually increased, the speed at which the foamed sheet (about 1.0 mm thick) started to be stretched was evaluated. When forming a foamed sheet having a foaming ratio of 3 times, the case where the take-off speed at which the sheet is cut is 5 m / min or more was evaluated as x, and the case where it was less than 5 m / min was evaluated as x.

(6) Foaming ratio The specific gravity was determined by dividing the weight of the obtained foamed sheet by the volume determined by the underwater substitution method, and the foaming ratio was calculated.

(7) Open cell ratio It measured using the air comparison type hydrometer 1000 type | mold (made by Tokyo Science).

(8) Cell diameter (average particle diameter)
Using a scanning electron microscope JSM-6100 (manufactured by JEOL Ltd.), the cross section of the sheet was observed at a magnification of 70 times, and the diameter of 100 cells in the screen was measured to obtain an average value.

(9) Thermoformability (mold reproducibility)
The shape of the tray obtained by vacuum forming the foamed sheet was visually observed with a tray mold using a vacuum pressure thermoforming machine FK-0431-10 (manufactured by Asano Laboratories). Evaluation based on the criteria. The indirect heating temperature was 500 ° C. (set).
○: Excellent mold reproducibility ×: Inferior mold reproducibility

(10) Thermoformability (draw down property)
Evaluation of drawdown property was performed on the same heating conditions as said (9) using the foam sheet of shape 30cmx30cmx1mm thickness. The drawdown behavior was screened, and the most restored state after shrinkback was determined as the minimum drawdown amount based on the initial state where the drawdown starts. The case where this amount was less than 20 mm was evaluated as ◯, and the case where it was 20 mm or more was evaluated as ×.
Moreover, the time of drawing down to 30 mm on the basis of the initial state after shrinkback was determined as the maximum holding time. The case where this time was longer than 15 seconds was evaluated as ◯, and the case where it was 15 seconds or less was evaluated as ×.

(11) the ethylene content of the content of copolymer of ethylene unit, create a 300μm thick sheet under the following conditions, by the following equation from the absorbance 718,733Cm ^-1 using a Nippon Bunko FT / IR5300 Calculated.
(A) Sheet molding conditions Press temperature: 220 ° C. Clamping pressure during heating and cold pressure: 50 kg / cm ² G
Residual heat: 5 min Pressurization: 5 min Cold pressure: 3 min
(B) IR measurement conditions Integration count: 20 times Resolution: 4 cm ⁻¹
Calculation formula of ethylene content χ (wt%) χ ₁ = 0.599 × (A ₇₃₃ /d·l)−0.161×(A ₇₁₈ / d · l)
χ ₂ = 0.599 × (A ₇₁₈ /d·l)−0.161×(A ₇₃₃ / d · l)
χ = 0.809 × (χ ₁ + χ ₂ )
“However, A ₇₁₈ : Absorbance at ₇₁₈ cm ⁻¹ , A ₇₃₃ : Absorbance at ₇₃₃ cm ⁻¹ , d: 0.9, l: Sample thickness.”

Production Example 1
[Polyolefin component (component (A))]
(1) Preparation of solid catalyst component After substituting a 3-L flask with an internal volume of 0.5 L with a stirrer with nitrogen gas, 60 ml of dehydrated octane and 16 g of diethoxymagnesium were added. After heating to 40 ° C. and adding 2.4 ml of silicon tetrachloride and stirring for 20 minutes, 1.6 ml of dibutyl phthalate was added. This solution was heated to 80 ° C., 77 ml of titanium tetrachloride was subsequently added dropwise, and stirred for 2 hours at an internal temperature of 125 ° C. for the first contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated seven times. Furthermore, 122 ml of titanium tetrachloride was added and stirred for 2 hours at an internal temperature of 125 ° C., and a second contact operation was performed. Thereafter, the washing with 125 ° C. dehydrated octane was repeated 6 times to obtain a solid catalyst component.

(2) Preparation of pre-polymerization catalyst component After replacing the three-flask with a stirrer having an internal volume of 0.5 L with nitrogen gas, 400 ml of dehydrated heptane, 25 mmol of triisobutylaluminum, 2.5 mmol of dicyclopentyldimethoxysilane, 4 g of the solid catalyst component prepared in (1) above was added. Propylene was introduced with stirring at room temperature. After 1 hour, stirring was stopped, and as a result, a prepolymerized catalyst component in which 4 g of propylene was polymerized per 1 g of the solid catalyst component was obtained.

(3) Polymerization of propylene A stainless steel autoclave with a stirrer with an internal volume of 10 L was sufficiently dried, and after nitrogen substitution, 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.3 mmol of dicyclopentyldimethoxysilane were added. Here, after nitrogen in the system was replaced with propylene, 0.098 MPa of hydrogen was introduced, and then propylene was introduced with stirring. After the system was stabilized at an internal temperature of 80 ° C. and a total pressure of 0.785 MPa, 50 ml of heptane slurry containing 0.025 mmol of the prepolymerized catalyst component prepared in (2) above in terms of titanium atoms was added, and propylene was continuously added. While feeding, polymerization was carried out at 80 ° C. for 3 hours. After completion of the polymerization, 50 ml of methanol was added, and the temperature was lowered and the pressure was released. The entire contents were transferred to a filtration tank equipped with a filter, heated to 85 ° C., and solid-liquid separated. Further, the solid part was washed twice with 6 L of heptane at 85 ° C. and vacuum-baked to obtain 2.5 kg of polypropylene resin. The catalyst activity per gram of the solid catalyst component was 33.1 kg / g-Cat.・ It was 3 hours.
The intrinsic viscosity [η] measured in tetralin at 135 ° C. of this resin was 1.70 dl / g, and the mesopentad fraction [mmmm] by ¹³ C-NMR was 98.0 mol%.

(4) Polymerization of propylene In the above (3), a polypropylene resin was synthesized in the same manner as in the above (3) except that hydrogen was not added. The intrinsic viscosity [η] measured in tetralin at 135 ° C. of the obtained resin was 7.65 dl / g.

(5) Synthesis of maleic anhydride-modified propylene polymer 2 kg of the propylene polymer obtained in (4) above, 6 g of maleic anhydride and perhexine 25B / 40 (trade name, manufactured by NOF Corporation, 2, 5 2 g of dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 40% inert solid diluted product) was dry blended and melt-kneaded with a 20 mm twin screw extruder. 0.5 kg of acetone and 0.7 kg of heptane were added to 1 kg of the obtained pellet-like sample, and the mixture was heated and stirred at 85 ° C. for 2 hours. This reaction was carried out in a pressure vessel. After the operation was completed, the pellets were collected with a wire mesh and then immersed in 1.5 kg of acetone for 15 hours. Thereafter, the pellets were collected with a wire mesh, air dried, and then vacuum dried at 80 ° C. for 6 hours and 130 ° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer.

(6) Preparation of propylene polymer composition To 380 g of the polypropylene resin powder obtained in (3) above, 0.95 g of 3-aminopropyltriethoxysilane (APTE, organosilicon compound) and Irganox 1010 (phenolic oxidation) Inhibitor, 0.24 g of Ciba Specialty Chemicals, trade name), 0.56 g of Irgafos 168 (Phosphorus Antioxidant, Ciba Specialty Chemicals, trade name), and 0.6 mg of calcium stearate. 2g was added and blended thoroughly. Next, 20 g of the maleic anhydride-modified propylene polymer obtained in (4) above was added, mixed, and then melt-kneaded at 230 ° C. using a twin screw extruder to prepare a propylene polymer composition. The obtained composition had an MFR of 4.8 g / 10 min and an MT ₂₃₀ of 8 g.

Production Example 2
[Polyolefin component (component (A))]
(1) Preparation of aluminum oxy compound A solvent of 1,000 ml of a toluene solution of methylaluminoxane (1.47 mol / L, Albemarle Inc., containing 14.5% by weight of trimethylaluminum) was removed at 60 ° C. under reduced pressure (about 20 mmHg). Distilled off. After maintaining in this state for 4 hours, the volume was returned to the volume before distilling off the solvent, and trimethylaluminum in methylaluminoxane was determined by ¹ H-NMR. As a result, it was 3.6% by weight. Moreover, it was 1.32 mol / L as a result of measuring the total amount of aluminum by the fluorescent X ray (ICP) method. Thereafter, this solution was allowed to stand for 48 hours to precipitate insoluble components. Subsequently, the solution part was filtered with a G5 glass filter to obtain toluene-soluble methylaluminoxane. The concentration by the IPC method was 1.06 mol / L.

(2) Preparation of carrier and preparation of supported methylaluminoxane 70 g of SiO ₂ (manufactured by Fuji Silysia Co., Ltd., P-10) was dried at 140 ° C. for 15 hours under a slight nitrogen stream. 22.0 g of dry SiO ₂ was weighed and put into 200 ml of dehydrated toluene. After maintaining the temperature constant at 0 ° C. with stirring in a nitrogen atmosphere, 200 ml of a toluene solution of methylaluminoxane prepared in (1) above was added dropwise over 60 minutes. After completion of the dropping, the temperature was raised to room temperature, the reaction was carried out for 30 minutes in this state, and the reaction was further carried out at 70 ° C. for 3 hours. After completion of the reaction, the temperature was maintained at 60 ° C., and the solid component was washed twice with 200 ml of dehydrated toluene and twice with 200 ml of dehydrated heptane and dried under reduced pressure at 50 ° C. to obtain 32.8 g of SiO ₂ -supported methylaluminoxane. Again, dehydrated heptane was added and the slurry was stored. SiO ₂ / methylaluminoxane (weight ratio) was 1 / 0.43.

(3) Preparation of metallocene-supported catalyst After 200 ml of Schlenk tube was dried and purged with nitrogen, 8 mmol of SiO ₂ -supported methylaluminoxane prepared in (2) above was sampled in terms of aluminum atoms, and stirring was started. To this, 8 μmol of rac-SiMe ₂ [2-Me-4,5-BenzoInd] ₂ ZrCl ₂ (racemic-dimethylsilanediyl-bis-1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride) was added. 4 ml of the toluene solution was slowly added and reacted at 25 ° C. for 15 minutes to prepare a metallocene supported catalyst.

(4) Production of polypropylene resin After a stainless steel pressure-resistant autoclave having an internal volume of about 13 L was sufficiently dried, 7 L of dehydrated heptane and 7 mmol of triisobutylaluminum heptane were added in terms of aluminum atoms in a nitrogen atmosphere, and for 20 minutes. Stir at room temperature. To this, the entire amount of the metallocene supported catalyst prepared in (3) above was added. Subsequently, for preactivation of the catalyst, 10 minutes was applied at 25 ° C., the propylene pressure was increased to 0.3 MPa (gauge pressure), and prepolymerization was performed at a constant pressure for 30 minutes. Thereafter, unreacted propylene was removed by depressurization and nitrogen blowing, 16 ml of hydrogen was injected, and the temperature was raised to 60 ° C. over 10 minutes. Thereafter, propylene was introduced over 20 minutes, and the pressure was increased to 0.65 MPa. While maintaining the pressure and temperature constant, propylene was continuously introduced and polymerization was carried out for 95 minutes.

Thereafter, the introduction of propylene was stopped, 50 ml of a heptane solution containing 4 ml of 1,7-octadiene was added, and the polymerization temperature was lowered to 50 ° C. During this time, the diene component was uniformly dispersed in the reaction system. Then, the introduction of propylene was resumed, and polymerization was carried out for 65 minutes while maintaining 50 ° C. and a pressure of 0.6 MPa. After completion of the polymerization, 50 ml of ethanol was added to stop the reaction. The inside of the system was depressurized and the polypropylene resin was recovered and found to be 2,830 g. The amount of diene used was 1.4 × 10 ⁻⁵ mol with respect to 1 g of polypropylene of the first polymerization reactor. This polymerization operation was repeated 7 batches to produce 21.2 kg of polypropylene resin as a total yield.

(5) Preparation of pellets To the polypropylene resin obtained in (4) above, 750 ppm of P-EPQ (phosphorus antioxidant, manufactured by Sand Corp., trade name) and 1,500 ppm of Irganox 1010 are added and mixed thoroughly. After that, it was melt-kneaded with a 20 mm single-screw kneading extruder and granulated to produce pellets. The obtained pellet had an MFR of 5.4 g / 10 m and an MT ₂₃₀ of 25 g.

Production Example 3
[Polypropylene resin used as a raw material for component (B)]
(1) Preparation of solid catalyst component 160 g (1.4 mol) of diethoxymagnesium was added to a 5 L three-neck flask with a stirrer that was replaced with nitrogen, and 500 ml of dehydrated heptane was further added. The mixture was heated to 40 ° C., 28.5 ml (0.225 mol) of silicon tetrachloride was added, stirred for 20 minutes, and 0.127 mol of dibutyl phthalate was added. The temperature of the solution was raised to 80 ° C., and subsequently, 770 ml (7.0 mol) of titanium tetrachloride was dropped using a dropping funnel. The internal temperature was set to 110 ° C., and stirring was performed for 2 hours to perform the first loading treatment. Thereafter, it was thoroughly washed with dehydrated heptane. Further, 1,220 ml (11.2 mol) of titanium tetrachloride was added, the internal temperature was set to 110 ° C., and the mixture was stirred for 2 hours to carry out a second loading treatment. Thereafter, the solid catalyst component was obtained by sufficiently washing with dehydrated heptane. The solid catalyst component contained 2.2% by weight of titanium.

(2) Preparation of prepolymerization catalyst component 1500 mL of dehydrated heptane was added to a 2 L three-neck flask with a stirrer substituted with nitrogen, and further 6.9 mmol of triethylaluminum and 12.4 mmol of dicyclopentyldimethoxysilane. Then, 15 g (6.9 mmol as titanium) of the solid catalyst component prepared in the above (1) was added. While stirring at room temperature, propylene was introduced to obtain a prepolymerized catalyst component. 6.4 g of polypropylene resin was produced.

(3) Polymerization of propylene A stainless steel autoclave with a stirrer with an internal volume of 10 L was sufficiently dried, and after substitution with nitrogen, 6 L of dehydrated heptane was added. While stirring, the temperature was raised until the internal temperature reached 80 ° C., and 12 mmol of triethylaluminum was added followed by 0.6 mmol of dicyclopentyldimethoxysilane. Next, nitrogen in the system was replaced with propylene, hydrogen was introduced at 0.02 MPa, and propylene was introduced until the total pressure reached 0.79 MPa. After confirming that the internal temperature and pressure were stable, 0.5 mmol of the prepolymerized catalyst component prepared in the above (2) was added as titanium to initiate polymerization. Thereafter, when 1 hour had elapsed, 50 mL of methanol was added to terminate the polymerization. Thereafter, the temperature was lowered and the pressure was removed, the contents were taken out, the solvent was removed with an evaporator, and vacuum drying was performed to obtain a polypropylene resin. The yield of the obtained resin was 2.5 kg. The intrinsic viscosity [η] measured in tetralin at 135 ° C. of this resin was 2.04 dl / g.

Production Example 4
[Polypropylene resin (component (B))]
With respect to 100 parts by weight of the polypropylene resin obtained in Production Example 3, 0.1 part by weight of Irganox 1010, 0.1 part by weight of Irgafos 168 as an antioxidant, and 0.1 part by weight of calcium stearate as a neutralizing agent After the addition of 0.013 parts by weight of Kayahexa AD (5-di- (t-butylperoxy) hexane, manufactured by Kayaku Akzo, trade name) as an organic peroxide, sufficient stirring and mixing were performed. . Next, using a TEM35B twin screw extruder (trade name, manufactured by Toshiba Machine Co., Ltd.), melt kneading was performed at a cylinder temperature of 200 ° C. and an extrusion rate of 30 kg / hr. The obtained polypropylene resin had an MFR of 4.8 g / 10 min, a relaxation time (τ) of 1.3 seconds, a molecular weight distribution of 3.4, and MT ₁₉₀ of 1.4 g.

Production Example 5
[Polypropylene resin (component (B))]
Production Example 4 was carried out in the same manner as Production Example 4 except that the amount of the organic peroxide was changed to 0.017 parts by weight. The obtained polypropylene resin had an MFR of 7.1 g / 10 min, a relaxation time (τ) of 1.0 second, a molecular weight distribution of 3.5, and MT ₁₉₀ of 1.0 g.

Production Example 6
[Polypropylene resin (component (B))]
After the stainless steel pressure-resistant autoclave having an internal volume of about 13 L was sufficiently dried, 7 L of nitrogen-dehydrated heptane and 7 mmol of triisobutylaluminum in a nitrogen atmosphere were added in a nitrogen atmosphere and stirred at room temperature for 20 minutes. To this, the entire amount of the metallocene supported catalyst prepared in Production Example 2 (3) was added. Next, for preactivation of the catalyst, 10 minutes was applied at 25 ° C., the pressure was increased to a propylene pressure of 0.3 MPa (gauge pressure), and prepolymerization was performed at a constant pressure for 30 minutes. Thereafter, unreacted propylene was removed by depressurization and nitrogen blowing, and the temperature was raised to 60 ° C. over 10 minutes. Thereafter, propylene was introduced over 20 minutes, and the pressure was increased to 0.65 MPa. While maintaining the pressure and temperature constant, propylene was continuously introduced and polymerized for 150 minutes. After completion of the polymerization, 50 ml of ethanol was added to stop the reaction. The inside of the system was depressurized and the polypropylene resin was recovered and found to be 3,250 g. This polymerization operation was repeated 7 batches to produce 22.9 kg of polypropylene resin as a total yield. The MFR of this resin was 4.5 g / 10 minutes, the relaxation time (τ) was 0.6 seconds, the molecular weight distribution was 2.1, and MT ₁₉₀ was 0.6 g.

Production Example 7
[Random copolymerized polypropylene (component (C))]
(1) Preparation of magnesium compound The reaction tank with a stirrer (internal volume 500 L) was sufficiently replaced with nitrogen gas, and 97.2 kg of ethanol, 640 g of iodine, and 6.4 kg of magnesium metal were added and the mixture was stirred under reflux conditions. The reaction was continued until no hydrogen gas was generated from the system to obtain a solid reaction product. The reaction solution containing the solid reaction product was dried under reduced pressure to obtain the target magnesium compound (solid catalyst carrier).

(2) Preparation of solid catalyst component In a reaction tank with a stirrer (internal volume 500 L) sufficiently substituted with nitrogen gas, 30 kg of the magnesium compound (not pulverized), 150 L of purified heptane (n-heptane), silicon tetrachloride 4.5 L and 5.4 L di-n-butyl phthalate were added. The system was maintained at 90 ° C., and 144 L of titanium tetrachloride was added while stirring and reacted at 110 ° C. for 2 hours. Then, the solid component was separated and washed with purified heptane at 80 ° C. Further, 228 L of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours, and then sufficiently washed with purified heptane to obtain a solid catalyst component.

(3) Pre-treatment 230 L of purified heptane is charged into a reaction vessel equipped with a stirrer with an internal volume of 500 L, 25 kg of the above solid catalyst component, 1.0 mol / mol of triethylaluminum with respect to titanium atoms in the solid catalyst component, dicyclopentyl Dimethoxysilane was supplied at a rate of 1.8 mol / mol. Thereafter, propylene was introduced until the partial pressure of propylene reached 0.3 kg / cm ² G and reacted at 25 ° C. for 4 hours. After completion of the reaction, the solid catalyst component was washed several times with purified heptane, and further carbon dioxide was supplied and stirred for 24 hours.
(4) Polymerization In a polymerization apparatus with a stirrer having an internal volume of 200 L, the treated solid catalyst component was converted to 3 mmol / hr in terms of titanium atom in the component, triethylaluminum at 4 mmol / kg-PP, and dicyclopentyldimethoxysilane at 1 mmol / hr. Each was supplied as kg-PP, and propylene and ethylene were reacted at a polymerization temperature of 80 ° C. and a polymerization pressure (total pressure) of 28 kg / cm ² G. At this time, the ethylene concentration in the polymerization apparatus was 3.2 mol% and the hydrogen concentration was 3.1 mol%, so that the desired ethylene content and molecular weight were obtained. The ethylene concentration and the hydrogen concentration are composition analysis values of the gas part in the polymerization apparatus by gas chromatogram.

(5) Additive formulation The following additives were formulated into the random copolymerized polypropylene powder thus obtained and extruded and granulated with a kneader.
1) Antioxidant: Irganox 1010: 1000 ppm by Ciba Geigy and Irgaphos 168: 1000 ppm by Ciba Geigy
2) Neutralizing agent: calcium stearate: 1000 ppm
3) Anti-blocking agent: silica-based: 2000 ppm
4) Slip agent: erucic acid amide: 1000 ppm
The random copolymerized polypropylene had an ethylene unit content of 4.2% by weight and an MFR of 2.4 g / 10 min.

Production Example 8
[Random copolymerized polypropylene (component (C))]
All were carried out in the same manner as in Production Example 7 except that the ethylene concentration during polymerization was set to 2.9 mol% and the hydrogen concentration was set to 1.6 mol% to adjust the ethylene content and MFR.
The random copolymerized polypropylene had an ethylene unit content of 4.0% by weight and an MFR of 1.8 g / 10 min.

Example 1
[Polypropylene resin composition and foamed molded article]
As component (A), polypropylene (manufactured by Sun Allomer, PF-814) is 10 wt%, as component (B), polypropylene prepared in Production Example 4 is 50 wt%, and as Component (C), produced in Production Example 7 above. The obtained random copolymer polypropylene was used in an amount of 40 wt%, and these were mixed to form a pellet blend.
To 100 parts by weight of this pellet blend, 0.4 part by weight of a foaming agent (EE205 manufactured by Eiwa Chemical Industries) was dry blended.
This blend was subjected to foam molding using a foam molding machine (TEM-41SS, manufactured by Toshiba Machine Co., Ltd.) to obtain a sheet-like molded product (thickness: 1 mm). The conditions at this time were a screw rotation speed of 60 rpm, a cylinder temperature of 210 ° C., a die temperature of 170 ° C., and a carbon dioxide injection amount of 200 g / hr.

With respect to the foamed sheet obtained at a low take-off speed (2.5 m / min) that does not come into contact with the die, the open cell ratio and cell morphology were observed.
Next, when the take-up speed was gradually increased to find the speed at which drawing breakage started, it was 7 m / min.
Moreover, thermoforming was performed using the foamed sheet obtained at a low take-off speed (2.5 m / min), and the mold reproducibility and drawdown performance were grasped.
Table 1 shows the ratios and parameters of the components of the resin compositions obtained in Example 1 and Examples 2 to 8 and Comparative Examples 1 to 7 shown below. Table 1 shows the moldability of the resin composition and the evaluation results of the foam molded body. Is shown in Table 2. In addition, the addition amount of the talc in a table | surface is the quantity with respect to 100 weight part of resin compositions.

Examples 2 and 3
The same procedure as in Example 1 was performed except that the component (B) in Example 1 was changed to the polypropylene of Production Example 5 and the blending ratio was changed as shown in Table 1.

Example 4
The same as Example 1 except that the component (B) in Example 1 was changed to the polypropylene of Production Example 5, the component (C) was changed to the polypropylene of Production Example 8, and the blending ratio was changed as shown in Table 1. I went to.

Example 5
The same procedure as in Example 1 was performed except that the component (B) in Example 1 was changed to the polypropylene of Production Example 5 and talc was added to change the blending ratio as shown in Table 1.

Example 6
Example 1 was carried out in the same manner as in Example 1 except that the component (B) was changed to the polypropylene of Production Example 6 and the blending ratio was changed as shown in Table 1.

Example 7
The same procedure as in Example 1 was performed except that the component (A) in Example 1 was changed to the polypropylene of Production Example 2 and the blending ratio was changed as shown in Table 1.

Example 8
The same procedure as in Example 1 was performed except that the component (A) in Example 1 was changed to the polypropylene of Production Example 1 and the blending ratio was changed as shown in Table 1.

Comparative Examples 1 and 2
Example 2 was carried out in the same manner as Example 2 except that the component (C) was not used and the blending ratio was changed as shown in Table 1.

Comparative Example 3
Example 6 was carried out in the same manner as Example 6 except that the component (C) was not used and the blending ratio was changed as shown in Table 1.

Comparative Example 4
Example 7 was carried out in the same manner as Example 7 except that the component (C) was not used and the blending ratio was changed as shown in Table 1.

Comparative Example 5
Example 8 was carried out in the same manner as Example 8 except that the component (C) was not used and the blending ratio was changed as shown in Table 1.

Comparative Example 6
Example 1 was carried out in the same manner as Example 1 except that the component (B) was not used and the blending ratio was changed as shown in Table 1.

Comparative Example 7
The same procedure as in Example 2 was performed except that the blending ratio in Example 2 was changed as shown in Table 1.

A molded body formed by foam molding of the resin composition of the present invention, for example, a foam sheet, is excellent in heat insulation, heat resistance, and oil resistance, so that it is a food container, particularly a microwave oven container (tray, bowl, cup, etc. ). It can also be used as stationery, containers, returnable boxes, and the like.

Claims (8)

A polypropylene resin composition comprising the following (A), (B) and (C).
(A) Polyolefin component having a branched structure with a melt tension at 230 ° C. of 5 to 30 g: 10 to 50% by weight
(B) Polypropylene resin satisfying the following (B-1) to (B-4): 20 to 70% by weight
(B-1) The melt tension at 190 ° C. is 0.5 to 5 g.
(B-2) Melt flow rate is 1 to 10 g / min (B-3) Ratio of weight molecular weight to number average molecular weight is 2 to 4.5
(B-4) In melt viscoelastic behavior measured using a rotary rheometer, the relaxation time (τ) at an angular frequency ω = 0.1 rad / sec is 0.5 to 2.0 seconds (C) (C) -1) and random copolymer polypropylene satisfying (C-2): 20 to 70% by weight
(C-1) Melt flow rate is 1 to 8 g / 10 min. (C-2) Ethylene unit content is 1 to 5% by weight.   The polypropylene resin composition according to claim 1, wherein the component (A) is a polypropylene into which long-chain branches have been introduced by irradiation with ionizing radiation.   The polypropylene resin composition according to claim 1, wherein the component (A) is a propylene polymer composition obtained by bringing polypropylene, an organosilicon compound and a high molecular weight acid-modified α-olefin polymer into contact with each other.   The component (A) is a polymer or copolymer of one or more monomers selected from ethylene, propylene, α-olefins having 4 to 20 carbon atoms, styrenes and cyclic olefins by a two-stage polymerization method in the presence of polyene. The polypropylene resin composition according to claim 1, which is a polyolefin resin obtained by polymerization.   The polypropylene resin composition according to any one of claims 1 to 4, wherein the polypropylene resin (B) is a polypropylene resin obtained by melt-kneading a polypropylene resin in the presence of an organic peroxide.   In the presence of a catalyst in which the polypropylene resin (B) is a combination of a catalyst component selected from the group 4 transition metal compounds having a cyclopentadienyl skeleton and a promoter component, propylene is added. It is a polypropylene resin obtained by superposition | polymerization, The polypropylene resin composition as described in any one of Claims 1-4.   Furthermore, 1-100 weight part of inorganic fillers are contained as a (D) component with respect to 100 weight part of said polypropylene resin composition, The polypropylene resin composition as described in any one of Claims 1-6. The foaming molding which satisfy | fills the following (1)-(4) obtained by foam-molding the polypropylene resin composition as described in any one of Claims 1-7.
(1) Average cell diameter is 500 μm or less (2) Open cell ratio is 1 to 30%
(3) Stretchability is 5 m / min or more (4) Foaming ratio is 1 to 5 times