JP4846503B2 - Method for producing blow molded article - Google Patents

Description

  The present invention relates to a method for producing a molded body, and more particularly to a method for producing a molded body by blow molding by melting a mixture containing a thermoplastic resin and a polyolefin wax.

Blow molding is one of the methods for producing molded bodies from resin materials. Not only containers such as bottles and tanks, but also building materials such as outer walls, automobile parts such as automobile exterior parts, industrial machine parts, electrical / It has also been used in the manufacture of electronic parts and the like.

Particularly in recent years, there has been a demand for a method for improving the productivity of blow molding itself without impairing the physical properties of the molded product.
For example, a molding machine for performing blow molding and a method for improving productivity by improving molding conditions have been studied (see, for example, Patent Documents 1 and 2).

However, there is a need for a method for improving productivity without impairing the physical properties of the molded body itself without using special molding machines and molding conditions as described above. Still had room for improvement.
Japanese Patent Laid-Open No. 11-254512 WO97 / 45246 pamphlet

  An object of the present invention is to provide a method for efficiently producing a molded body by improving the moldability in blow molding without impairing the physical properties of the molded body.

  The inventors of the present invention have studied the above-mentioned problems, and when a mixture containing a thermoplastic resin and a specific polyolefin wax is melted to produce a molded product by blow molding, the moldability of blow molding is improved, and the molded product It has been found that a molded product can be produced efficiently without impairing physical properties, and the present invention has been completed.

That is, the method for producing the molded article of the present invention includes:
A thermoplastic resin (A);
The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 400 to 5,000, and the melting point measured by differential scanning calorimeter (DSC) is in the range of 65 to 120 ° C. It is characterized by melting and blow molding a mixture containing a certain polyolefin wax (B).

The method for producing the molded article of the present invention includes:
A thermoplastic resin (A);
The number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) is in the range of 200 to 5,000, and the melting point measured by differential scanning calorimeter (DSC) is in the range of 65 to 120 ° C. It is characterized by melting and blow molding a mixture containing a certain polyolefin wax (B).

  The polyolefin wax (B) is preferably polyethylene wax, more preferably metallocene polyethylene wax.

  According to the present invention, a molded product can be produced efficiently by blow forming without impairing the physical properties of the molded product, and this production method is also excellent in moldability.

Hereinafter, the present invention will be described in detail.
[Thermoplastic resin (A)]
In the present invention, the thermoplastic resin (A) is a thermoplastic polymer having a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 8,000 or more, or a blend thereof. Say.

The thermoplastic resin (A) used in the present invention is not particularly limited, and examples thereof include low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, cyclic olefin polymer, and ethylene-propylene copolymer. , Polyolefins such as cyclic olefin copolymers;
Styrene polymers such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer;
Polyvinyl chloride, polyvinylidene chloride;
Ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer;
Polycarbonate, polymethacrylate;
Polyesters such as polyethylene terephthalate and polybutylene terephthalate;
Polyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon MXD6, wholly aromatic polyamide, semi-aromatic polyamide;
Examples include polyacetals and blends of these resins.

  Among these thermoplastic resins, polyolefin is preferable, low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, and ethylene-propylene copolymer are more preferable, and high density polyethylene and polypropylene are more preferable. .

When the thermoplastic resin (A) is the above resin, a polyolefin wax (B
), And an excellent molded product having no stickiness on the surface can be obtained.
The MI (JIS K7210; 190 ° C test load 2.16 kgf) of the high-density polyethylene is preferably in the range of 0.01 to 1.0 g / 10 minutes, more preferably in the range of 0.01 to 0.80 g / 10 minutes. .

When the MI of the high-density polyethylene is in the above range, a molded article excellent in texture, rigidity, impact strength, chemical resistance, etc. can be obtained.
As the density of the high density polyethylene is preferably in the range of 942~970kg / m ^3, the range of 944~965kg / m ³ and more preferably.

When the density of the high-density polyethylene is in the above range, a molded article having excellent texture, rigidity, impact strength, chemical resistance, and the like can be obtained.
The polypropylene has a MI (JIS K7210; 230 ° C. test load of 2.16 kgf) preferably in the range of 0.1 to 3.5 g / 10 minutes, more preferably in the range of 0.4 to 1.5.

When the MI of polypropylene is in the above range, a molded article having excellent heat resistance, chemical resistance, and the like can be obtained.
[Polyolefin wax (B)]
In the present invention, a polyolefin wax is mixed with the thermoplastic resin (A). The polyolefin wax in the present invention has a crystallization temperature measured with a differential scanning calorimeter (DSC) at a temperature drop rate of 2 ° C./min in the range of 65 to 120 ° C., and gel permeation chromatography (GPC). The number average molecular weight (Mn) in terms of polystyrene measured in (1) is in the range of 400 to 5,000. When a mixture of such polyolefin wax added to the thermoplastic resin (A) is melted and blow-molded, the melt viscosity of the resin is reduced, which not only reduces the motor load during extrusion, but also improves fluidity. As a result, the molding speed is improved. Moreover, the surface of the molded body is modified, and a molded body having a smooth surface can be obtained. Furthermore, since molding can be performed at a low molding temperature, not only the cooling time is shortened and the molding cycle is improved, but also thermal degradation of the resin, scorching of the resin, and black spots can be suppressed, and the mechanical strength of the molded body is excellent. Become.

  The polyolefin wax (B) used in the present invention is not particularly limited, and examples thereof include polyethylene wax, polypropylene wax, α-olefin homopolymer wax, ethylene / α-olefin copolymer wax, and ethylene / α-olefin. / Non-conjugated diene copolymer wax.

  Among these polyolefin waxes, polyethylene wax and wax of ethylene / α-olefin copolymer are preferable, and polyethylene wax and wax of copolymer of ethylene and α-olefin having 3 to 20 carbon atoms are more preferable. Polyethylene wax, ethylene / propylene copolymer wax, ethylene / 1-butene copolymer wax, ethylene / 1-pentene copolymer wax, ethylene / 1-hexene copolymer wax, ethylene / 4- Methyl-1-pentene copolymer wax, ethylene / 1-octene copolymer wax are more preferable, polyethylene wax, ethylene / propylene copolymer wax, ethylene / 1-butene copolymer wax, ethylene / 1-hexene copolymer wax, A wax of ethylene / 4-methyl-1-pentene copolymer is particularly preferred.

  When the polyolefin wax (B) is the above-mentioned polyolefin wax, a good molded article having excellent dispersibility with the thermoplastic resin (A), particularly the polyolefin resin, and having no stickiness on the surface, for example, can be obtained.

  The polystyrene-equivalent number average molecular weight (Mn) of the polyolefin wax (B) measured by gel permeation chromatography (GPC) is preferably in the range of 400 to 5,000, more preferably in the range of 700 to 4,500. The range of 800 to 4,000 is even more preferable. In addition, the polystyrene-equivalent number average molecular weight (Mn) being in the range of 400 to 5,000 is synonymous with the polyethylene equivalent number average molecular weight (Mn) being in the range of 200 to 2,500.

The molecular weight in terms of polyethylene is obtained by converting the molecular weight in terms of polystyrene by a general calibration method using a coefficient of the Mark-Houwink viscosity equation.
The coefficients of the Mark-Houwink viscosity equation are as follows.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70
When the Mn of the polyolefin wax (B) is in the above range, the effect of improving fluidity is great and the molding speed is greatly improved.

In the present invention, as the polyolefin wax (B), a polyolefin wax having a polyethylene-equivalent number average molecular weight (Mn) in the range of more than 2,500 and 5,000 or less can also be used.

  Therefore, in a further aspect of the present invention, the polyethylene wax number average molecular weight (Mn) of the polyolefin wax (B) is preferably in the range of 200 to 5,000, more preferably in the range of 400 to 5,000.

When the Mn of the polyolefin wax (B) is in the above range, the effect of improving fluidity is great and the molding speed is greatly improved.
The ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight and number average molecular weight of the polyolefin wax (B) measured by gel permeation chromatography (GPC) is preferably in the range of 1.5 to 4.0. The range of 1.5 to 3.5 is more preferable.

When Mw / Mn of the polyolefin wax (B) is in the above range, a molded product having no stickiness on the surface can be obtained.
The crystallization temperature of the polyolefin wax (B) measured with a differential scanning calorimeter (DSC) at a temperature drop rate of 2 ° C./min is preferably in the range of 65 to 120 ° C., more preferably in the range of 70 to 120 ° C. , Particularly preferably in the range of 70-118 ° C.

When the crystallization temperature of the polyolefin wax (B) is in the above range, a molded product having no stickiness on the surface can be obtained.
The polyolefin wax (B), a density measured by the density gradient tube method in compliance with JIS K7112, preferably from 850~980kg / m ^3, more preferably in the range of 870~980kg / m ^3, 890~980kg The range of / m ³ is more preferable.

When the density of the polyolefin wax is in the above range, the molding shrinkage of the molded product can be easily controlled.
Furthermore, the polyolefin wax (B) has the crystallization temperature [Tc (° C.)] measured by a differential scanning calorimeter (DSC) and the density (D (kg / m ³ )) measured by the density gradient method.
Preferably the following formula (I)
0.501 × D-366 ≧ Tc (I)
More preferably, the following formula (Ia)
0.501 × D-366.5 ≧ Tc (Ia)
More preferably, the following formula (Ib)
0.501 × D-367 ≧ Tc (Ib)
Satisfy the relationship.

  When the crystallization temperature (Tc) and the density (D) satisfy the relationship of the above formula in the polyolefin wax (B), for example, the polyolefin wax (B) is an ethylene / α-olefin copolymer wax. If so, the composition distribution of the copolymer becomes more uniform, and the tack of the molded product obtained by blow molding tends to be reduced from the mixture containing the thermoplastic resin (A) and the polyolefin wax (B).

  Further, the penetration of the polyolefin wax (B) measured in accordance with JIS K2207 is usually 30 dmm or less, preferably 25 dmm or less, more preferably 20 dmm or less, and even more preferably 15 dmm or less.

When the penetration of the polyolefin wax (B) is in the above range, a molded product having sufficient strength can be obtained.
The amount of acetone extracted from the polyolefin wax (B) is preferably in the range of 0 to 20% by weight, and more preferably in the range of 0 to 15% by weight.

The amount of acetone extracted is measured as follows.
Using a filter (manufactured by ADVANCE, No. 84) in a Soxhlet extractor (made of glass), 200 ml of acetone is placed in a lower round bottom flask (300 ml), and extraction is performed in a 70 ° C. hot water bath for 5 hours. The initial wax is set to 10 g on the filter.

The polyolefin wax (B) is solid at room temperature and becomes a low-viscosity liquid at 65 to 130 ° C. or higher.
When the amount of acetone extracted from the polyolefin wax (B) is within the above range, the sticky component is reduced, and not only the mold contamination is suppressed, but also a molded product having no sticky surface can be obtained.

  The method for producing the above-described polyolefin wax (B) is not particularly limited. For example, the polyolefin wax (B) can be obtained by polymerizing monomers such as ethylene and α-olefin using a Ziegler / Natta catalyst or a metallocene catalyst. Among these catalysts, metallocene catalysts are preferable.

Examples of such metallocene catalysts include:
(A) a metallocene compound of a transition metal selected from Group 4 of the periodic table, and (B) (b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and
(b-3) An olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds.
These will be described in detail below.

<Metalocene compounds>
(A) Metallocene compound of transition metal selected from Group 4 of the periodic table The metallocene compound forming the metallocene catalyst is a metallocene compound of transition metal selected from Group 4 of the periodic table. The compound represented by Formula (1) is mentioned.
M ¹ Lx (1)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, x is a valence of the transition metal M ¹ , and L is a ligand. Examples of the transition metal represented by M ¹ include zirconium, titanium, hafnium and the like. L is a ligand coordinated to the transition metal M ^1, and at least one of the ligands L is a ligand having a cyclopentadienyl skeleton, and the ligand having this cyclopentadienyl skeleton. The ligand may have a substituent. Examples of the ligand L having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, n-, alkyl such as i-, sec- or t-butylcyclopentadienyl group, dimethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylbenzylcyclopentadienyl group, An alkyl-substituted cyclopentadienyl group; and an indenyl group, 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and the like. The hydrogen of the ligand having a cyclopentadienyl skeleton may be substituted with a halogen atom or a trialkylsilyl group.

When the metallocene compound has two or more ligands having a cyclopentadienyl skeleton as the ligand L, the ligands having two cyclopentadienyl skeletons are ethylene, propylene. An alkylene group such as isopropylidene and diphenylmethylene; a silylene group or a dimethylsilylene group, a diphenylsilylene group,
It may be bonded via a substituted silylene group such as a methylphenylsilylene group.

Examples of ligands other than ligands having a cyclopentadienyl skeleton (ligands having no cyclopentadienyl skeleton) L include hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, sulfones. Acid-containing group (—SO ₃ R ¹ ), halogen atom or hydrogen atom (where R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an alkyl group) A substituted aryl group).

<Example 1 of metallocene compound>
When the metallocene compound represented by the general formula (1) has a transition metal valence of 4, for example, it is more specifically represented by the following general formula (2).
R ² _k R ³ _l R ⁴ _m R ⁵ _n M ¹ (2)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are each independently cyclopentadienyl. A group (ligand) having or not having a skeleton. k is an integer of 1 or more, and k + l + m + n = 4.

Examples of metallocene compounds in which M ¹ is zirconium and contains at least two ligands having a cyclopentadienyl skeleton are given below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride and the like.

Among the above compounds, compounds in which the 1,3-position substituted cyclopentadienyl group is replaced with a 1,2-position substituted cyclopentadienyl group can also be used.
Another example of the metallocene compound is R ² , R ³ , R ^{4 in the} general formula (2).
And at least two of R ⁵ , for example, R ² and R ³ are groups having a cyclopentadienyl skeleton (
A bridge type metallocene compound in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like. At this time, R ⁴ and R ⁵ are each independently the same as the ligand L other than the ligand having the cyclopentadienyl skeleton described above.

  Examples of such bridge-type metallocene compounds include ethylene bis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconium dichloride, methyl Examples include phenylsilylene bis (indenyl) zirconium dichloride.

<Example 2 of metallocene compound>
Moreover, as an example of a metallocene compound, the metallocene compound of Unexamined-Japanese-Patent No. 4-268307 represented by following General formula (3) is mentioned.

Here, M ¹ is a Group 4 transition metal of the periodic table, and specifically includes titanium, zirconium, and hafnium.
R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; Aryloxy group having 6 to 10 carbon atoms; alkenyl group having 2 to 10 carbon atoms; arylalkyl group having 7 to 40 carbon atoms; alkylaryl group having 7 to 40 carbon atoms; arylalkenyl group having 8 to 40 carbon atoms Or a halogen atom, and R ¹¹ and R ¹² are preferably chlorine atoms.

R ¹³ and R ¹⁴ may be the same or different from each other, and are a hydrogen atom; a halogen atom; an optionally halogenated alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; (R ²⁰ ) ₂ , —SR ²⁰ , —OSi (R ²⁰ ) ₃ , —Si (R ²⁰ ) ₃ or —P (R ²⁰ ) ₂ groups. R ²⁰ is a halogen atom, preferably a chlorine atom; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. R ¹³ and R ¹⁴ are particularly preferably hydrogen atoms.

R ¹⁵ and R ¹⁶ are the same as R ¹³ and R ¹⁴ except that they do not contain a hydrogen atom, and may be the same or different from each other, preferably the same. R ¹⁵ and R ¹⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. Particularly preferred is methyl.

In the general formula (3), R ¹⁷ is selected from the following group.

= BR ²¹ , = AlR ²¹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , = N
R ²¹ , = CO, = PR ²¹ , = P (O) R ^{21 and the} like. M ² is silicon, germanium or tin,
Silicon or germanium is preferred. Here, R ²¹ , R ²² and R ²³ may be the same or different from each other, and are hydrogen atom; halogen atom; alkyl group having 1 to 10 carbon atoms; fluoroalkyl group having 1 to 10 carbon atoms; carbon atom An aryl group having 6 to 10 carbon atoms; a fluoroaryl group having 6 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an arylalkyl group having 7 to 40 carbon atoms; An arylalkenyl group having 8 to 40 carbon atoms; or an alkylaryl group having 7 to 40 carbon atoms. “R ²¹ and R ²² ” or “R ²¹ and R ²³ ” may form a ring together with the atoms to which they are bonded. R ¹⁷ may be = CR ²¹ R ²² , = SiR ²¹ R ²² , = GeR ²¹ R ²² , -O-, -S-, = SO, = PR ²¹ or = P (O) R ^21. preferable. R ¹⁸ and R ¹⁹ may be the same as or different from each other, and examples thereof include the same as R ²¹ . m and n may be the same or different and are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

Examples of the metallocene compound represented by the general formula (3) include the following compounds. rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium dichloride,
rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium dichloride and the like. These metallocene compounds can be produced, for example, by the method described in JP-A-4-268307.

<Example 3 of metallocene compound>
Moreover, as a metallocene compound, the metallocene compound represented by following General formula (4) can also be used.

In Formula (4), M ³ represents a transition metal atom of Group 4 of the periodic table, and specifically, titanium, zirconium, hafnium, and the like. R ²⁴ and R ²⁵ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated 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; R ²⁴ is preferably a hydrocarbon group, and particularly preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. R ²⁵ is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Indicates a group. Among these, a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group is preferable. At least one of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , and R ²⁸ and R ²⁹ may form a monocyclic aromatic ring together with the carbon atoms to which they are bonded. Good. When there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming the aromatic ring, they may be bonded to each other to form a ring. When R ²⁹ is a substituent other than an aromatic group, it is preferably a hydrogen atom. X ¹
And X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, or a carbon atom of 1
Y representing -20 hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen atom-containing group or sulfur atom-containing group is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon atom A divalent halogenated hydrocarbon group of 1 to 20, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-, -SO- ^{_{, -SO 2 -, - NR 30}} -,
^{-P (R 30) -, -} P (O) (R 30) -, - BR 30 - or -AlR ³⁰ - (provided that, R ³⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms , Halogenated hydrocarbon groups having 1 to 20 carbon atoms).

In the formula (4), at least one pair of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ is bonded to each other, and is coordinated to M ³ Examples of the ligand include those represented by the following formula.

(In the formula, Y is the same as that shown in the previous formula.)
<Example 4 of metallocene compound>
As the metallocene compound, a metallocene compound represented by the following general formula (5) can also be used.

In the formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same as those in the general formula (4). Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , two groups including R ²⁶ are preferably alkyl groups, and R ²⁶ and R ²⁸ , or R ²⁸ and R ²⁹ are alkyl groups. preferable. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and silicon-containing group include the substituents exemplified for R ²⁴ and R ²⁵ . Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , the group other than the alkyl group is preferably a hydrogen atom. R ²⁶ , R ²⁷ , R ^28, and R ²⁹ may form a monocyclic ring or a polycyclic ring other than an aromatic ring by combining two groups selected from these groups. Examples of the halogen atom are the same as those described above for R ²⁴ and R ²⁵ . Examples of X ¹ , X ² and Y are the same as those described above.

Specific examples of the metallocene compound represented by the general formula (5) are shown below. rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, and the like.

  In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used. The transition metal compound is usually used as a racemate, but can also be used in the R-type or S-type.

<Examples of metallocene compounds-5>
As the metallocene compound, a metallocene compound represented by the following general formula (6) can also be used.

In the formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are the same as those in the general formula (4). R ²⁴ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl. R ²⁵ represents an aryl group having 6 to 16 carbon atoms. R ²⁵ is preferably phenyl or naphthyl. The aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  Specific examples of the metallocene compound represented by the general formula (6) are shown below. rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl) -4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 -Methyl-4- (1-anthryl) -1-indenyl) zirconium dichloride and the like. In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

<Examples of metallocene compounds-6>
As the metallocene compound, a metallocene compound represented by the following general formula (7) can also be used.
LaM ⁴ X ³ ₂ (7)
Here, M ⁴ is a periodic table group 4 or lanthanide series metal. La is a derivative of a delocalized π bond group, and is a group imparting a constraining geometry to the metal M ⁴ active site. X ³ may be the same or different from each other, and is a hydrogen atom, a halogen atom, a hydrocarbon group having 20 or less carbon atoms, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium.

  Among these compounds, a compound represented by the following formula (8) is preferable.

In the formula (8), M ⁴ is titanium, zirconium or hafnium. X ³ is the same as that described in the general formula (7). Cp is a substituted cyclopentadienyl group having a π bond to M ⁴ and having a substituent Z. Z is oxygen, sulfur, boron or an element belonging to Group 4 of the periodic table (for example, silicon, germanium or tin). Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may form a condensed ring. Specific examples of the metallocene compound represented by the formula (8) are shown below. (Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium Dichloride etc. In the metallocene compound, a compound in which titanium is replaced with zirconium or hafnium can be exemplified.

<Examples of metallocene compounds-7>
Moreover, as a metallocene compound, the metallocene compound represented by following General formula (9) can also be used.

In formula (9), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³¹ may be the same as or different from each other, and at least one of them is an aryl group having 11 to 20 carbon atoms, an arylalkyl group having 12 to 40 carbon atoms, an arylalkenyl group having 13 to 40 carbon atoms, carbon An alkylaryl group having 12 to 40 atoms or a silicon-containing group, or at least two adjacent groups among the groups represented by R ³¹ , together with the carbon atoms to which they are bonded, one or more aromatic rings Or an aliphatic ring is formed. In this case, the ring formed by R ^31, it is 4 to 20 carbon atoms in all including carbon atoms to which R ³¹ is bonded. Aryl group, arylalkyl group, arylalkenyl group, an alkylaryl group and an aromatic ring, R ³¹ other than R ³¹ that forms an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms Or a silicon-containing group. R ³² may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 carbon atoms.
-20 aryl group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, silicon A containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Further, at least two adjacent groups among the groups represented by R ³² may form one or more aromatic rings or aliphatic rings together with the carbon atoms to which they are bonded. In this case, the ring formed by R ³² has 4 to 20 carbon atoms in all including carbon atoms to which R ³² is bonded, an aromatic ring, other than R ³² that forms an aliphatic ring R ³² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group. The group in which the two groups represented by R ^{32 form} one or more aromatic rings or aliphatic rings includes an embodiment in which the fluorenyl group has a structure represented by the following formula.

R ³² is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. A suitable example of such a fluorenyl group having R ³² as a substituent is a 2,7-dialkyl-fluorenyl group. In this case, the 2,7-dialkyl alkyl group includes 1 to 1 carbon atoms. 5 alkyl groups. R ³¹ and R ³² may be the same as or different from each other. R ³³ and R ³⁴ may be the same as or different from each other, and are the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. 10 alkenyl groups, arylalkyl groups having 7 to 40 carbon atoms, arylalkenyl groups having 8 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, A nitrogen-containing group or a phosphorus-containing group. Of these, at least one of R ³³ and R ³⁴ is preferably an alkyl group having 1 to 3 carbon atoms. X ¹ and X ² may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . As the conjugated diene residue formed from X ¹ and X ² , residues of 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene and 1,4-diphenylbutadiene are preferable. These residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms. X ¹ and X ² are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing group. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, —O—, —CO—, —S—, —SO—, —SO ₂ —, —
^{NR 35 -, - P (R} 35) -, - P (O) (R 35) -, - BR 35 - or -AlR ³⁵ - (provided that, R ³⁵ is a hydrogen atom, a halogen atom, carbon atom 20 And a halogenated hydrocarbon group having 1 to 20 carbon atoms). Among these divalent groups, those in which the shortest linking portion of -Y- is composed of one or two atoms are preferable. R ³⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, more preferably a divalent silicon-containing group. Particularly preferred is silylene, alkylarylsilylene or arylsilylene.

<Examples of metallocene compounds-8>
As the metallocene compound, a metallocene compound represented by the following general formula (10) can also be used.

In formula (10), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³⁶ may be the same as or different from each other, and includes a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and silicon-containing Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group. The alkyl group and alkenyl group may be substituted with a halogen atom. Of these, R ³⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, particularly a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and i-propyl, phenyl, α-naphthyl. And an aryl group such as β-naphthyl or a hydrogen atom. R ³⁷ may be the same or different from each other, and may be a hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, carbon atom An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group It is. Note that the alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group, and alkylaryl group may be substituted with halogen. Of these, R ³⁷ is preferably a hydrogen atom or an alkyl group, and particularly a hydrogen atom or a carbon atom having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl. A hydrogen group is preferred. R ³⁶ and R ³⁷ may be the same as or different from each other. One of R ³⁸ and R ³⁹ is an alkyl group having 1 to 5 carbon atoms, and the other is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Among these, it is preferable that any one of R ³⁸ and R ³⁹ is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, and propyl, and the other is a hydrogen atom. X ¹ and X ² may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . Among these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, —O—, —CO—, —S—, —SO—, —SO ₂ —, —NR ⁴⁰ —, —P (R ⁴⁰ ) —
^{, -P (O) (R 40} ) -, - BR 40 - or -AlR ⁴⁰ - (provided that, R ⁴⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms from 1 to 20 A halogenated hydrocarbon group). Among these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group, or a divalent germanium-containing group, and more preferably a divalent silicon-containing group. An alkylsilylene, an alkylarylsilylene or an arylsilylene is particularly preferable.

<Examples of metallocene compounds-9>
Further, as the metallocene compound, a metallocene compound represented by the following general formula (11) can also be used.

In the formula (11), Y is selected from carbon, silicon, germanium and tin atoms, M is Ti, Zr or Hf, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different, and adjacent substituents from R ⁵ to R ¹² are R ¹³ and R ¹⁴ may be selected from a hydrocarbon group and a silicon-containing group and may be the same or different from each other, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. It may be formed. Q may be selected from a halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is an integer of 1 to 4. )
Hereinafter, after describing sequentially the cyclopentadienyl group, the fluorenyl group, the crosslinked part, and other characteristics that are the chemical structure characteristics of the bridged metallocene compound according to the present invention, a preferable bridged metallocene compound having these characteristics will be described. .

Cyclopentadienyl group The cyclopentadienyl group may or may not be substituted. The cyclopentadienyl group which may or may not be substituted means that R ¹ , R ² , R ³ and R ⁴ possessed by the cyclopentadienyl group moiety in the general formula (11) are all hydrogen atoms. Or any one or more of R ¹ , R ² , R ³ and R ⁴ is a hydrocarbon group (f1), preferably a hydrocarbon group having 1 to 20 carbon atoms (f1 ′), or silicon-containing It means a cyclopentadienyl group substituted by a group (f2), preferably a silicon-containing group (f2 ′) having a total carbon number of 1 to 20. When two or more of R ¹ , R ² , R ³ and R ⁴ are substituted, these substituents may be the same as or different from each other. Further, the hydrocarbon group having 1 to 20 carbon atoms in total is an alkyl, alkenyl, alkynyl, or aryl group composed of only carbon and hydrogen. These include those in which any two adjacent hydrogen atoms are simultaneously substituted to form an alicyclic or aromatic ring. The hydrocarbon group having 1 to 20 carbon atoms in total (f1 ′) includes, in addition to alkyl, alkenyl, alkynyl and aryl groups composed only of carbon and hydrogen, some of the hydrogen atoms directly connected to these carbon atoms are halogen atoms. , An oxygen-containing group, a nitrogen-containing group, a heteroatom-containing hydrocarbon group substituted with a silicon-containing group, or a group in which any two adjacent hydrogen atoms form an alicyclic group. Such a group (f1 ')
As methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, linear hydrocarbon group such as n-decanyl group; isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl- Branched hydrocarbon groups such as 1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, Cyclic saturated hydrocarbon groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; cyclic unsaturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group and their nuclei Alkyl substitution A saturated hydrocarbon group substituted with an aryl group such as benzyl group or cumyl group; methoxy group, ethoxy group, phenoxy group, N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, pentafluorophenyl And a heteroatom-containing hydrocarbon group such as a group.
The silicon-containing group (f2) is, for example, a group in which a ring carbon of a cyclopentadienyl group is directly covalently bonded to a silicon atom, and specifically an alkylsilyl group or an arylsilyl group. Examples of the silicon-containing group (f2 ′) having a total carbon number of 1 to 20 include a trimethylsilyl group and a triphenylsilyl group.

Fluorenyl group The fluorenyl group may or may not be substituted. The fluorenyl group which may or may not be substituted is R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² possessed by the fluorenyl group moiety in the general formula (11). Are all hydrogen atoms, or at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is a hydrocarbon group (f1), preferably Means a fluorenyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms (f1 ′) or a silicon-containing group (f2), preferably a silicon-containing group having 1 to 20 carbon atoms (f2 ′) To do. When two or more of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are substituted, the substituents may be the same or different from each other. Good. Further, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be bonded to each other to form a ring. In view of the ease of production of the catalyst, those in which R ⁶ and R ¹¹ and R ⁷ and R ¹⁰ are the same are preferably used.
A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a preferable example of the silicon-containing group (f2) is the above-described total number of carbon atoms of 1 to 20. It is a silicon-containing group (f2 ′).

Covalent bond bridge The main chain part of the bond connecting the cyclopentadienyl group and the fluorenyl group is a divalent covalent bond containing one carbon, silicon, germanium and tin atom. The important point in the high-temperature solution polymerization of the present invention is that the bridging atom Y of the covalent bond bridging portion has R ¹³ and R ¹⁴ which may be the same or different from each other. A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a preferable example of the silicon-containing group (f2) is the above-described total number of carbon atoms of 1 to 20. It is a silicon-containing group (f2 ′).

Other characteristics of the bridged metallocene compound In the general formula (11), Q is halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, They are selected from the same or different combinations from anionic ligands or neutral ligands that can coordinate with a lone pair of electrons. Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Specific examples of neutral, conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis-
Or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-diphenyl-
1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3- butadiene, s- cis - or s- trans eta ^{4-2,4-hexadiene,} s- cis - or s- trans eta ^{4-1,3-pentadiene,} s- cis - or s- trans eta ⁴ - Examples include 1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.

<Example of metallocene compound-10>
Moreover, as a metallocene compound, the metallocene compound represented by the following general formula (12) can also be used.

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are hydrogen or a hydrocarbon group Selected from silicon-containing groups, which may be the same or different, and adjacent substituents from R ¹ to R ¹⁴ may be bonded to each other to form a ring, and M represents Ti, Zr
Or Hf, Y is a Group 14 atom, Q can be coordinated by halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated diene, anionic ligand, and lone pair of electrons Selected from the group consisting of neutral ligands in the same or different combinations, n is an integer of 2 to 4, and j is an integer of 1 to 4.

  In the general formula (12), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. And may contain one or more ring structures.

Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-
Methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl- 1-cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl Etc.

  In the general formula (12), the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples thereof include trimethylsilyl and tert-butyldimethyl. Examples thereof include silyl and triphenylsilyl.

In the present invention, R ¹ to R ^{14 in} the general formula (12) are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above.

The adjacent substituents from R ¹ to R ¹⁴ on the cyclopentadienyl ring of the general formula (12) may be bonded to each other to form a ring.
M in the general formula (12) is a group 4 element of the periodic table, that is, zirconium, titanium or hafnium, preferably zirconium.

Y is a Group 14 atom, preferably a carbon atom or a silicon atom. n is an integer of 2 to 4, preferably 2 or 3, particularly preferably 2.
Q is the same or different combination from the group consisting of halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated diene, anionic ligand and neutral ligand capable of coordinating with a lone pair. To be elected. When Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to 10 carbon atoms.

Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. When j is an integer greater than or equal to 2, several Q may be the same or different.

In the formula (12), there are a plurality of Ys of 2 to 4, but the Ys may be the same as or different from each other. The plurality of R ¹³ and the plurality of R ¹⁴ bonded to Y may be the same as or different from each other. For example, a plurality of R ¹³ bonded to the same Y may be different from each other, or a plurality of R ¹³ bonded to different Y may be the same as each other. R ¹³ or R ¹⁴ may form a ring.

  Preferable examples of the Group 4 transition metal compound represented by the formula (12) include a compound represented by the following formula (13).

In formula (13), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms, hydrocarbon groups, silicon R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each a hydrogen atom or a hydrocarbon group, n is an integer of 1 to 3, and n = 1 In some cases, R ¹ to R ¹⁶ are not hydrogen atoms and may be the same or different. Adjacent substituents from R ⁵ to R ¹² may combine with each other to form a ring, and R
¹³ and R ¹⁵ may be bonded to each other to form a ring, and R ¹³ and R ¹⁵ may be bonded to each other to form a ring, and at the same time, R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring. , Y ¹ and Y ² are group 14 atoms which may be the same or different from each other, M is Ti, Zr or Hf, Q is a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons You may choose from the neutral ligand which can be coordinated by the same or different combination, and j is an integer of 1-4.
Examples of such metallocene compounds such as Examples-9 and 10 are listed in JP-A-2004-175707, WO2001 / 027124, WO2004 / 029062, WO2004 / 083265, and the like.

The metallocene compounds described above are used alone or in combination of two or more. The metallocene compound may be diluted with a hydrocarbon or a halogenated hydrocarbon.
The catalyst component comprises (A) the bridged metallocene compound represented above, and (B) (b-1) an organoaluminum oxy compound, (b-2) reacts with the bridged metallocene compound (A) to form an ion pair. And at least one compound selected from (b-3) organoaluminum compounds.

Hereinafter, the component (B) will be specifically described.
<(B-1) Organoaluminum oxy compound>
As the (b-1) organoaluminum oxy compound used in the present invention, a conventionally known aluminoxane can be used as it is. Specifically, the following general formula (14)

  And / or general formula (15)

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more). In particular, R is a methylaluminoxane in which methyl is a methyl group, and n is 3 More preferably, 10 or more are used. These aluminoxanes may be mixed with some organoaluminum compounds. A characteristic property in the high temperature solution polymerization of the present invention is that a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be applied. In addition, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, and JP-A-3-103407, etc. It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound used in the high-temperature solution polymerization of the present invention means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 5% or less. Is 2% or less, and is insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound used in the present invention include modified methylaluminoxane as shown in the following (16).

(Here, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n represent an integer of 2 or more.)
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound [V] is generally called MMAO. Such MMAO can be prepared by the methods listed in US4960878 and US5041584. In addition, Tosoh Finechem Co., Ltd., etc., which are prepared using trimethylaluminum and triisobutylaluminum and whose R is an isobutyl group, are commercially produced under the names MMAO and TMAO. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability, and specifically, it is different from those insoluble or hardly soluble in benzene such as the above (14) and (15). It is soluble in aliphatic hydrocarbons and alicyclic hydrocarbons.

Further, the organoaluminum oxy compound used in the present invention includes the following general formula (1
An organoaluminum oxy compound containing boron represented by 7) can also be mentioned.

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)
<(B-2) Compound that reacts with bridged metallocene compound (A) to form an ion pair>
Examples of the compound (b-2) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound”) include JP-A-1-501950, Lewis acids and ionic properties described in 1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Examples thereof include compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  In the present invention, the ionic compound preferably employed is a compound represented by the following general formula (18).

In the formula, R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are organic groups, preferably aryl groups.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Of these, Re ^{e +} is preferably a carbenium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-
Butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) Borate, tripropylammonium tetrakis (
Pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-tri Fluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, di Octadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethyl) Tilphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate And dioctadecylmethylammonium.

Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5- Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, etc. .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, ionic compounds disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can also be used without limitation.
The ionic compound (b-2) as described above can be used as a mixture of two or more.

<(B-3) Organoaluminum compound>
Examples of the organoaluminum compound that forms the olefin polymerization catalyst (b-3) include, for example, an organoaluminum compound represented by the following general formula [X], a group 1 metal represented by the following general formula (19), and aluminum. Examples thereof include complex alkylated products.
R ^a _m Al (OR ^b ) _n H _p X _q ------ (19)
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, Tri-tert-butylaluminum,
Tri-branched alkylaluminums such as tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triphenylaluminum, tritolylaluminum, etc. triaryl aluminum; diisopropyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; formula _{(iC 4 H 9) x Al} y (C 5 H 10) z ( wherein, x, y, z are positive numbers Yes, z ≦ 2x.)
Alkenyl aluminum alkoxide such as isobutylaluminum methoxide and isobutylaluminum ethoxide; Dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; Alkyl aluminum sesquialkoxides such as ethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _{0.5 and the} like; diethylaluminum phenoxide and diethylaluminum Alkyl aluminum aryloxides such as (2,6-di-t-butyl-4-methylphenoxide); dimethylal Dialkylaluminum halides such as nium chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride and other partially Hydrogenated alk Aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, etc. partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide and the like.
M ² AlR ^a ₄ ----------- (20)
(In the formula, M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
A complex alkylated product of a group 1 metal and aluminum in the periodic table represented by: Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

A compound similar to the compound represented by the general formula (20) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. Specifically, as such a compound, (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂
And so on.

From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
<Polymerization>
The polyolefin wax used in the present invention is obtained by homopolymerizing ethylene in a normal liquid phase or copolymerizing ethylene and an α-olefin in the presence of the metallocene catalyst. In the polymerization, the usage of each component, the order of addition is arbitrarily selected,
The following methods are exemplified.

[q1] A method of adding the component (A) alone to the polymerization vessel.
[q2] A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
In the method [q2], at least two or more of the catalyst components may be in contact with each other in advance. At this time, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. The monomers used here are as described above.

  The polymerization method includes suspension polymerization in which polyolefin wax is polymerized in the presence of particles in a solvent such as hexane, gas phase polymerization in which a solvent is not used, and polymerization temperature of 140 ° C. or higher. Solution polymerization that polymerizes in the coexistence or melted state is possible, and among these, solution polymerization is preferable in terms of both economy and quality.

The polymerization reaction may be performed by either a batch method or a continuous method. When the polymerization is carried out by a batch method, the above catalyst components are used in the concentrations described below.
When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol per liter of reaction volume. It is used in such an amount that it becomes a mole.

Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) to all transition metal atoms (M) in component (A) of usually 0.01 to 5, 000, preferably 0.05 to 2,000. In the component (b-2), the molar ratio [(b-2) / M] of the ionic compound in the component (b-2) and the total transition metal (M) in the component (A) is usually 0. 0.01 to 5,000, preferably 1 to 2,000. The component (b-3) has a molar ratio [(b-3) / M] of the component (b-3) and the transition metal atom (M) in the component (A) of usually 1-1.
The amount used is 0000, preferably 1 to 5000.

In the polymerization reaction, the temperature is usually 10 g of wax set on a filter, -20 to + 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 180 ° C., and the pressure usually exceeds 0. It is performed under conditions of 8 MPa (80 kgf / cm ² , gauge pressure) or less, preferably more than 0 and 4.9 MPa (50 kgf / cm ² , gauge pressure) or less.

  In the polymerization, ethylene and the α-olefin used as necessary are supplied to the polymerization system in such an amount that the polyolefin wax having the specific composition described above can be obtained. In the polymerization, a molecular weight regulator such as hydrogen can be added.

When polymerized in this manner, the produced polymer is usually obtained as a polymerization solution containing the polymer, so that a polyolefin wax can be obtained by treatment by a conventional method.
In the present invention, it is particularly preferable to use a catalyst containing the metallocene compound shown in <Example 6 of metallocene compound>.

  When such a catalyst is used, a polyolefin wax (B) having the above-mentioned Mn, Mw / Mn, melting point range, and other preferable physical properties can be easily obtained, and a polyolefin wax (B) obtained using such a catalyst ( B) has a great effect of improving the fluidity and not only greatly increases the molding speed but also reduces the sticky component and can provide a molded body having no stickiness on the surface.

As the thermoplastic resin (A), polyolefin, preferably low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, ethylene-propylene copolymer, more preferably high density polyethylene, polypropylene,
Is used, the dispersibility of the thermoplastic resin (A) and the polyolefin wax (B) is improved, the effect of improving the fluidity is greater, the molding speed can be further improved, and the surface is improved. A molded product with less stickiness can be obtained.

  The blending amount of the polyolefin wax (B) thus obtained is usually in the range of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). The range is more preferably 0.3 to 5 parts by weight.

  When polyolefin wax (B) is mix | blended in the said range, the improvement effect of fluidity | liquidity will be large and a shaping | molding speed will improve greatly. Further, since molding is possible at a low molding temperature, the cooling time is shortened and the molding cycle is improved. Furthermore, by lowering the molding temperature, it is possible not only to suppress the thermal deterioration of the resin and the resin strength, but also to suppress the scorching and black spots of the resin.

〔Additive〕
In the present invention, to the mixture before blow molding, in addition to the thermoplastic resin (A) and the polyolefin wax (B), if necessary, stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, You may add additives, such as a metal soap, a filler, and a flame retardant.

Examples of the stabilizer include antioxidants such as fendered phenol compounds, phosphite compounds, and thioether compounds;
UV absorbers such as benzotriazole compounds and benzophenone compounds;
Examples thereof include light stabilizers such as hindered amine compounds.

Examples of the metal soap include stearates such as magnesium stearate, calcium stearate, barium stearate, and zinc stearate.
Examples of the filler include calcium carbonate, titanium oxide, barium sulfate, talc, clay, and carbon black.

  Examples of the flame retardant include halogenated diphenyl ethers such as degabrom diphenyl ether and octabromodiphenyl ether, halogen compounds such as halogenated polycarbonates; antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, aluminum hydroxide, etc. Inorganic compounds; phosphorus compounds and the like.

Moreover, a compound such as tetrafluoroethylene can be added as a flame retardant aid for preventing drip.
Examples of the antibacterial and antifungal agents include organic compounds such as imidazole compounds, thiazole compounds, nitrile compounds, haloalkyl compounds, and pyridine compounds;
Examples include inorganic substances such as silver, silver compounds, zinc compounds, copper compounds, and titanium compounds, and inorganic compounds.
Among these compounds, thermally stable silver and silver-based compounds are preferable.

As said silver type compound, silver salts, such as a silver complex, a fatty acid, and phosphoric acid, can be mentioned.
When silver and silver-based compounds are used as antibacterial and antifungal agents, these substances can be used in porous structures such as zeolite, silica gel, zirconium phosphate, calcium phosphate, hydrotalcite, hydroxyapatite, and calcium silicate. In some cases, it is used while being supported.

Examples of other additives include colorants, plasticizers, anti-aging agents, and oils.
[Blow molding]
The molded article of the present invention can be obtained by melting a mixture containing the thermoplastic resin (A) and the polyolefin wax (B) and performing blow molding.

Examples of the blow molding method include extrusion blow molding and injection blow molding.
For example, when the molded article of the present invention is obtained by extrusion blow molding, the thermoplastic resin (A
) And polyolefin wax (B) are melted, and the resin temperature is usually 170-24.
After extruding as a tubular parison from a die in the range of 0 ° C., and holding the parison in the mold of the shape to be imparted, air is blown into the mold, and the molded product is usually mounted on the mold at a resin temperature range of 160 to 230 ° C. can get. Further, when extrusion blow molding, the film may be stretched at an appropriate magnification.

  When extrusion blow molding is performed using high-density polyethylene as the thermoplastic resin (A), the resin temperature is usually in the range of 170 to 220 ° C., preferably 180 to 210 ° C., and the resin temperature is usually 160. A molded body is obtained by mounting on a mold in a range of ˜210 ° C., preferably in a range of 170 ° C. to 200 ° C. Further, it may be stretched during extrusion blow molding.

  When extrusion blow molding is performed using polypropylene as the thermoplastic resin (A), the resin temperature is usually in the range of 190 to 230 ° C, preferably in the range of 200 to 220 ° C, and the resin temperature is usually 180 to 220. A molded body is obtained by wearing the mold in the range of ° C, preferably in the range of 190 to 210 ° C. Further, it may be stretched during extrusion blow molding.

These blow moldings can be performed by an appropriate molding machine corresponding to each blow molding method.
According to the present invention, a molded body can be obtained by blow molding under the above-mentioned conditions. However, according to the production method of the present invention, blow molding is performed from a mixture of thermoplastic resin (A) not containing polyolefin wax (B). Even if it shape | molds on the conditions of 0-30 degrees C or less normally, Preferably it is 10-20 degrees C or less compared with the case, the physical property of the molded object obtained is not impaired, and also a molded object can be manufactured with sufficient productivity.

  In this way, for example, bottles such as cosmetic bottles, detergent bottles, bath detergent bottles, industrial chemical cans, drums, tanks, building materials such as tanks, exterior walls, automobile parts such as automobile exterior parts, industrial machine parts, electric / electronic A molded body that can be used for parts and the like is obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.
[Examples 1-2]
Primelopro B221WA (MI = 0.5 g / 10 min; 230 ° C. 2.16 kgf, density: 910 kg / m ³ ) (manufactured by Prime Polymer Co., Ltd.), a metallocene PE wax (Excelex (registered trademark)), is a polypropylene resin. ) 30200BT, manufactured by Mitsui Chemicals, Inc., ethylene content 95 mol%, density: 913 kg / m ³ , polyethylene-converted average molecular weight (Mn) = 2000, polyethylene-converted weight average molecular weight (Mw) = 5000, crystallization temperature (Tc): 86 ° C.) was added at a ratio shown in Table 1, and mixed well in a tumbler mixer to prepare a polyolefin resin mixture. The mixture of these polyolefin resins was blow-molded at a molding temperature of 180 ° C., and a bottle with an internal capacity of 1500 mL was molded and evaluated.

Molding conditions Molding machine JEB-15 blow molding machine manufactured by Nippon Steel Works Co., Ltd.
1 parison-2 mold system Mold temperature 25 ℃
Blowing air pressure 0.5 MPa
Product weight 80 ± 2.5g
In addition, the measuring method of a physical property is as follows.
[appearance]
The appearance of the bottle was visually observed and evaluated.
○ No thickness irregularity △ Thickness irregularity is slightly noticeable × Thickness irregularity is quite noticeable [full capacity]
Water was poured into the mouth of the molded bottle and its weight was measured.
[Drop strength]
800 mL of water was put into the bottle, the container was dropped from a height of 1.2 m, and the bottle was whitened or evaluated by the number of broken pieces.
[number of shots]
It was calculated as the number of product bottles produced per hour.
[Molding cycle]
Calculated as the time required to produce one bottle.

The evaluation results are shown in Table 1.
[Comparative Example 1]
Blow molding was performed in the same manner as in Example 1 except that the molding temperature was changed from 180 ° C. to 200 ° C. without adding the metallocene PE wax used in Example 1, and a bottle with an internal capacity of 1500 mL was molded and evaluated. . The evaluation results are shown in Table 1.

[Comparative Example 2]
Except that the metallocene PE wax used in Example 1 was not added, blow molding was performed in the same manner as in Example 1, and a bottle having an internal volume of 1500 mL was molded and evaluated. The evaluation results are shown in Table 1.

As is apparent from Table 1 above, according to the present invention, even when the molding temperature is lowered from 200 ° C. to 180 ° C., not only the appearance and drop strength are not impaired, but also the molding cycle is improved. I understand. Further, it can be seen that when the molding temperature is lowered from 200 ° C. to 180 ° C. without adding the polyolefin wax, the appearance and the drop strength are deteriorated, the molding cycle is lengthened, and the productivity is deteriorated.
[Examples 3 to 4]
Hiloex 5100B (MI = 0.27 g / 10 min; 190 ° C. N, density: 944 kg / m ³ ) (manufactured by Prime Polymer Co., Ltd.), a metallocene PE wax (Excellex (registered trademark) 40800T Mitsui) Chemical Co., Ltd., ethylene content 95 mol%, density: 980 kg / m ³ , polyethylene equivalent average molecular weight Mn = 22
00, polyethylene-converted weight average molecular weight (Mw) = 7000, crystallization temperature (Tc): 116 ° C.) were added in the proportions shown in Table 2, and mixed well in a tumbler mixer to prepare a polyolefin resin mixture. The mixture of these polyolefin resins was blow-molded, and a bottle with an internal volume of 1000 mL was molded and evaluated.
Molding conditions Molding machine 3B50 hollow molding machine manufactured by Plako Corporation
1 parison-1 mold method Mold temperature 25 ℃
Blowing air pressure 0.5 MPa
Product weight 67 ± 2g
In addition, the measuring method of a physical property is as follows.
[appearance]
The appearance of the bottle was visually observed and evaluated.
○ No thickness irregularity △ Thickness irregularity is slightly noticeable × Thickness irregularity is quite noticeable [full capacity]
Water was poured into the mouth of the molded bottle and its weight was measured.
[Drop strength]
600 mL of water was put into the bottle, the container was dropped from a height of 1.2 m, and the number of broken bottles was evaluated.
[number of shots]
It was calculated as the number of product bottles produced per hour.
[Molding cycle]
Calculated as the time required to produce one bottle.
The evaluation results are shown in Table 2.

[Comparative Example 3]
Blow molding was performed in the same manner as in Example 3 except that the molding temperature was changed from 150 ° C. to 170 ° C. without adding the metallocene PE wax used in Example 3, and a bottle with an internal volume of 1000 mL was molded and evaluated. . The evaluation results are shown in Table 1.

[Comparative Example 4]
Except that the metallocene PE wax used in Example 3 was not added, blow molding was performed in the same manner as in Example 3, and a bottle with an internal volume of 1000 mL was molded and evaluated. The evaluation results are shown in Table 1.

  As apparent from Table 2 above, according to the present invention, even when the molding temperature is lowered from 170 ° C. to 150 ° C., not only the appearance and drop strength are not impaired, but also the molding cycle is improved. I understand. Further, it can be seen that when the molding temperature is lowered from 170 ° C. to 150 ° C. without adding the polyolefin wax, the appearance and the drop strength are deteriorated, the molding cycle is lengthened, and the productivity is deteriorated.

Claims (5)

A thermoplastic resin (A);
The number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) is in the range of 200 to 5,000, and measured with a differential scanning calorimeter (DSC) at a temperature drop rate of 2 ° C./min. Melting a mixture containing a polyolefin wax (B) having a crystallization temperature in the range of 65 to 120 ° C .;
A method for producing a molded body by blow molding. A thermoplastic resin (A);
The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 400 to 5,000, and measured with a differential scanning calorimeter (DSC) at a temperature drop rate of 2 ° C./min. Melting a mixture containing a polyolefin wax (B) having a crystallization temperature in the range of 65 to 120 ° C .;
A method for producing a molded body by blow molding. The method for producing a molded article according to claim 1 or 2, wherein the polyolefin wax (B) is a polyethylene wax. The method for producing a molded article according to claim 1 or 2, wherein the polyolefin wax (B) is a polyethylene wax satisfying the following formula (I).
0.501 × D-366 ≧ Tc (I)
(In the above formula (I), Tc (° C.) represents a crystallization temperature measured by a differential scanning calorimeter (DSC), and D (kg / m ³ ) represents a density measured by a density gradient method.) 3. The molded product according to claim 1, wherein 0.01 to 20 parts by weight of the polyolefin wax (B) is blended with 100 parts by weight of the thermoplastic resin (A). how to.