JP5068028B2 - Manufacturing method of molded body by T-die molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a formed article of a polypropylene resin composition while improving productivity in T-die formation, without damaging dynamic characteristics and optical characteristics, and a method for producing a secondary processed, formed article by vacuum forming the formed article in a good shape-imparting property. <P>SOLUTION: This method of production is provided by performing a T-die formation of a raw material mixture obtained by adding 0.01 pt.wt. to 10 pts.wt. polyethylene wax having 880 to 920 (kg/m<SP>3</SP>) range density measured in accordance with the JIS K7112 density gradient tube method and 500 to 4,000 number-average molecular weight (Mn) based on polyethylene, measured by a gel permeation chromatography (GPC), to 100 pts.wt. resin mixture containing 55 to 95 wt.% range polypropylene and 5 to 45 wt.% range olefin-based elastomer based on 100 wt.% total amount of the polypropylene and olefin-based elastomer, to produce the formed article. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a molded product of a polypropylene resin composition by T-die molding, and more specifically, a molded product is produced by T-die molding using polypropylene, a polyolefin elastomer, and a specific polyethylene wax as raw materials. Regarding the method.

  Conventionally, a polypropylene resin composition obtained by adding an olefin-based elastomer to polypropylene has produced a molded body such as a film or a sheet by T-die molding, and the obtained molded body has been used for various applications. In recent years, improvement in productivity of such T-die molding has been increasingly demanded. As a general method for improving productivity at the time of molding such as T-die molding, a method of molding by adding a molding aid is known. For example, a method of molding by applying a molding aid such as oil or polyethylene wax to a thermoplastic resin to be molded has been studied (for example, Patent Documents 1 and 2).

  However, even if a resin composition such as a polypropylene resin composition is subjected to T-die molding using a conventional molding aid, although the productivity itself tends to be improved, the mechanical properties and optical properties of the resulting molded product are not improved. In some cases, even if an attempt is made to use a molded article such as a film or sheet, it may cause a problem depending on the application.

In addition, a molded body such as a film or a sheet obtained by the T-die molding is further subjected to processing such as vacuum molding and may be used for various applications as a secondary processed molded body. However, when the conventional molding aid as described above is added, not only the mechanical properties of the obtained secondary processed molded body may be deteriorated, but, for example, the formability during vacuum molding is a problem. There was also a case.
Japanese Patent Publication No. 5-80492 Special table 2003-528948 gazette

  An object of the present invention is to improve the productivity at the time of T-die molding, while maintaining the mechanical properties and optical properties, and to produce a molded product of a polypropylene resin composition, and to vacuum the molded product with good formability. An object of the present invention is to provide a method for producing a secondary processed molded body by molding.

  The inventors of the present invention have studied the above problems, and using polypropylene and olefinic elastomer-specific polyethylene wax as raw materials and performing T-die molding improves the productivity and allows molding without adding wax. The present invention is completed by finding that the mechanical properties and optical properties of the obtained molded product are not impaired even when compared with the obtained molded product, and that the obtained molded product can be vacuum-formed with good formability. It came to.

That is, the method for producing the molded article of the present invention includes
Based on 100% by weight of the total amount of polypropylene and olefinic elastomer, 100 parts by weight of resin mixture containing polypropylene in the range of 55 to 95% by weight and olefinic elastomer in the range of 5 to 45% by weight The density measured according to the density gradient tube method is in the range of 880 to 920 (kg / m ³ ), and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) is 500 to 4,000. The raw material mixture to which 0.01 to 10 parts by weight of polyethylene wax that is in the range and satisfies the relationship represented by the following formula (I) is added is characterized by T-die molding.
B ≦ 0.0075 × K (I)
(In the above formula (I), B is a content ratio (% by weight) of a component having a polyethylene conversion molecular weight of 20,000 or more in the polyethylene wax when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)
It is preferable that the polyethylene wax further satisfies the relationship represented by the following formula (II).
A ≦ 230 × K ^(-0.537) (II)
(In the above formula (II), A is a content ratio (% by weight) of a component in which the molecular weight in terms of polyethylene in the polyethylene wax is 1,000 or less when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)
Moreover, in this invention, the molded object obtained by the said T-die shaping | molding can be vacuum-molded, and a secondary-working molded object can be manufactured.

  According to the method for producing a molded article of the present invention, the polypropylene resin composition is excellent in productivity during T-die molding, and a polypropylene molded article obtained by the T-die molding is obtained by molding without adding wax. Even when compared with the molded article obtained, the mechanical properties and optical properties are not substantially impaired. Furthermore, since the said molded object is excellent in a shaping property, it can be used suitably for vacuum forming.

Hereinafter, the present invention will be described in detail.
First, raw materials used for the T-die molding of the present invention will be described.
〔polypropylene〕
Specifically, the polypropylene used in the present invention has an MI measured in the range of 0.01 to 100 g / 10 min in accordance with JIS K7210 at 230 ° C. and a test load of 21.18 N, and is a density gradient tube of JIS K7112. The density measured according to the method is 910 (kg / m ³ )
A homopolymer of propylene within the above range, a copolymer of propylene and a small amount of α-olefin (excluding propylene), or a blend thereof. Specific examples of the polypropylene include a propylene homopolymer, a polypropylene block copolymer obtained by copolymerizing propylene and an α-olefin (excluding propylene), a polypropylene random copolymer, or a blend thereof.

In the present invention, the measurement conditions for MI of polypropylene are as follows.
(MI)
The measurement was performed under the conditions of 230 ° C. and a test load of 21.18 N according to JIS K7210.
The shape of the polypropylene is not particularly limited, but is usually pellet-shaped or tablet-shaped particles.

[Olefin elastomer]
In the present invention, the olefin elastomer is
The MI measured in accordance with JIS K7210 at 190 ° C. and a test load of 21.18 N is in the range of 0.01 to 100 g / 10 minutes, and the density measured according to the density gradient tube method of JIS K7112 is 850 (kg / m ³ ). As described above, an ethylene / α-olefin random copolymer in a range of less than 900 (kg / m ³ ),
The MI measured under conditions of 230 ° C. and a test load of 21.18 N according to JIS K7210 is in the range of 0.01 to 100 g / 10 minutes, and the density measured according to the density gradient tube method of JIS K7112 is 850 (kg / m ³ ). As described above, a propylene / α-olefin random copolymer obtained by copolymerizing propylene and an α-olefin having 4 or more carbon atoms in a range of less than 910 (kg / m ³ ),
The MI measured in accordance with JIS K7210 at 190 ° C. and a test load of 21.18 N is in the range of 0.01 to 100 g / 10 minutes, and the density measured according to the density gradient tube method of JIS K7112 is 850 (kg / m ³ ). As described above, an ethylene / α-olefin / non-conjugated polyene random copolymer in a range of less than 900 (kg / m ³ ),
And mixtures thereof.

  The ethylene / α-olefin random copolymer is usually a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and is a rubber. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-decene, Examples include dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these α-olefins, propylene, 1-butene, 1-hexene and 1-octene are preferable. These α-olefins can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer is usually a polymer obtained by copolymerizing ethylene in the range of 90 to 50 mol% and α-olefin in the range of 10 to 50 mol%.
Moreover, as MI (JIS K7210: 190 degreeC, test load 21.18N), the range of 0.3-20 g / 10min is preferable. When MI is in the above range, a molded article having an excellent balance between molding processability and mechanical strength can be obtained.

  The propylene / α-olefin random copolymer is usually a random copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, and is a rubber. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, -Tetradecene, 1-hexadecene, 1-eicosene and the like. These α-olefins can be used alone or in combination of two or more.

  The propylene / α-olefin random copolymer is usually a polymer obtained by copolymerizing ethylene in the range of 90 to 55 mol% and α-olefin in the range of 10 to 45 mol%.

  Moreover, as MI (JIS K7210: 230 degreeC, test load 21.18N), the range of 0.3-20 g / 10min is preferable. When MI is in the above range, a molded article having an excellent balance between molding processability and mechanical strength can be obtained.

  The ethylene / α-olefin / non-conjugated polyene random copolymer is usually a random copolymer of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and is a rubber. The α-olefin is the same as in the case of the ethylene / α-olefin random copolymer.

Examples of the non-conjugated polyene include 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, and 5-isopropylidene-2- Acyclic dienes such as norbornene and norbornadiene;
1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl- Chain non-conjugated dienes such as 1,7-octadiene, 7-methyl-1,6-octadiene;
And triene such as 2,3-diisopropylidene-5-norbornene. Among these non-conjugated dienes, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used.

When the non-conjugated polyene is the above compound, a molded article excellent in impact resistance and mechanical strength can be obtained.
The ethylene / α-olefin / non-conjugated polyene random copolymer is usually 90 to 30 mol% of ethylene, 5 to 45 mol% of α-olefin, and 5 to 25 mol% of non-conjugated. It is a copolymer of polyene.

  Moreover, as MI (JIS K7210: 190 degreeC, test load 21.18N), the range of 0.05g / 10min-100g / 10min is preferable, and the range of 0.1-10g / 10min is more preferable. When MI is in the above range, a molded article having an excellent balance between molding processability and mechanical strength can be obtained.

Examples of the ethylene / α-olefin / non-conjugated polyene random copolymer include ethylene / propylene / diene terpolymer (EPDM).
[Polyethylene wax]
In the present invention, the polyethylene wax means an ethylene homopolymer or ethylene and α-olefin having a polyethylene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) in the range of 500 to 4,000. Or a blend thereof. The polyethylene-converted number average molecular weight (Mn) of the polyethylene wax is determined from gel permeation chromatography (GPC) measurement under the following conditions.

(Number average molecular weight (Mn))
The number average molecular weight was determined from GPC measurement. The measurement was performed under the following conditions. The number average molecular weight was determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PE conversion / General calibration method

In addition, the coefficient of the Mark-Houwink viscosity formula shown below was used for calculation of general-purpose calibration.
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 polyethylene wax has the composition and molecular weight as described above, the productivity during molding tends to be improved.

The polyethylene wax used in the present invention has a density in the range of 880 to 920 (kg / m ³ ). The density of the polyethylene wax is a value measured by the density gradient tube method of JISK7112. When the density of the polyethylene wax is in the above range, the productivity during molding tends to be improved.

The polyethylene wax of the present invention is characterized in that there is a specific relationship represented by the following formulas (I) and (II) between its molecular weight and melt viscosity.
B ≦ 0.0075 × K (I)
Here, in the above formula (I), B is a content ratio (weight%) of a component having a polyethylene conversion molecular weight of 20,000 or more in the polyethylene wax when measured by gel permeation chromatography. ). K is the melt viscosity (mPa · s) at 140 ° C. of the polyethylene wax measured with a Brookfield (B type) viscometer.

When polyethylene wax that satisfies the condition of the above formula (I) is used, the obtained molded product tends not to impair optical characteristics and mechanical characteristics.
Usually, when a polyethylene wax having a low melt viscosity is mixed with polypropylene and T-die molding is performed, the viscosity of the entire mixture is lowered, so that productivity at the time of molding tends to be improved. However, even if the productivity is improved in this way, the optical properties and mechanical properties of the resulting molded product may be deteriorated.

  As a result of investigations by the present inventors, the optical properties and mechanical properties of molded articles such as sheets and films obtained by T-die molding are such that the proportion of the component having a molecular weight of 20,000 or more in the polyethylene wax used is melt viscosity. It was found to be extremely important in relation to Although the detailed mechanism is not clear, when the polyethylene wax and polypropylene are melt-kneaded in the molded product, among the whole polyethylene wax, the component having a molecular weight of 20,000 or more has the melting behavior in the whole wax. From the viewpoint of the specific melt viscosity of the entire polyethylene wax, the polyethylene wax cannot be well dispersed in the polypropylene unless the component having a molecular weight of 20,000 or more is used in a certain proportion or less. It is presumed to affect the optical properties and mechanical properties of the molded body.

  A polyethylene wax having a B value in the above range can be prepared using a metallocene catalyst. Among the metallocene catalysts, metallocene catalysts whose ligands are non-crosslinked are preferable. As such a metallocene catalyst, a metallocene compound represented by the general formula (1) described later can be exemplified.

  Further, the B value can be controlled by the polymerization temperature. For example, when a polyethylene wax is produced by a metallocene catalyst described later, the polymerization temperature is usually in the range of 100 to 200 ° C., but from the viewpoint of producing the polyethylene wax having the B value described above, the polymerization temperature is preferably Is in the range of 100 to 180 ° C, more preferably in the range of 100 to 170 ° C.

The polyethylene wax of the present invention further has a specific relationship represented by the following formula (II) between its molecular weight and melt viscosity.
A ≦ 230 × K ^(-0.537) (II)
Here, in the above formula (II), A is the content ratio (weight%) of the component whose molecular weight in terms of polyethylene in the polyethylene wax is 1,000 or less when measured by gel permeation chromatography. ). K is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.

  When polyethylene wax that satisfies the condition of the above formula (II) is used, the obtained molded product tends to maintain the mechanical properties and optical properties, and the bleed out from the molded product surface tends to decrease. is there.

As described above, usually, when a polyethylene wax having a low melt viscosity is mixed with polypropylene and T-die molding is performed, the viscosity of the entire mixture is lowered, so that productivity at the time of molding tends to be improved. However, even if the productivity can be improved, the resulting molded article may have impaired mechanical properties and optical characteristics, and bleeding from the molded article surface may also be a problem.

  As a result of the study by the present inventors, the ratio of the component having a molecular weight of 1,000 or less in the polyethylene wax used in the mechanical properties, optical properties, etc. of molded products such as sheets and films obtained by T-die molding. It was found to be extremely important in relation to melt viscosity. Although the detailed mechanism is not clear, when polyethylene wax and polypropylene are melt-kneaded in a molded product, components having a molecular weight of 1,000 or less are easily melted in the entire polyethylene wax, and the melting behavior thereof is wax. From the viewpoint of the melt viscosity of polyethylene wax as a whole, if it is not less than a certain proportion of components with a molecular weight of 1,000 or less, it will ooze out to the surface, possibly causing deterioration, etc. It is estimated that it will also affect the body's mechanical properties, optical properties, and bleed-out.

  A polyethylene wax having an A value in the above range can be prepared using a metallocene catalyst. Among the metallocene catalysts, metallocene catalysts whose ligands are non-crosslinked are preferable. As such a metallocene catalyst, a metallocene compound represented by the general formula (1) described later can be exemplified.

Furthermore, the A value can be controlled by the polymerization temperature. For example, when a polyethylene wax is produced with a metallocene catalyst described later, the polymerization temperature is usually in the range of 100 to 200 ° C., but from the viewpoint of producing the polyethylene wax having the A value described above, the polymerization temperature is preferably Is in the range of 100 to 180 ° C, more preferably in the range of 100 to 170 ° C.

The polyethylene wax has a number average molecular weight (Mn) in the range of 500 to 4,000.
Mn of the polyethylene wax can be controlled by the polymerization temperature or the like. For example, when a polyethylene wax is produced with a metallocene catalyst described later, the polymerization temperature is usually in the range of 100 to 200 ° C., but from the viewpoint of producing a polyethylene wax having the above-mentioned preferred range of Mn, the polymerization temperature is , Preferably, it is the range of 100-180 degreeC, More preferably, it is the range of 100-170 degreeC.

The density (D (kg / m ³ )) of the polyethylene wax is in the range of 880 to 920 (kg / m ³ ).
When the density (D) of the polyethylene wax is in the above range and further satisfies the above B value or the relationship between the A value and the B value, the mechanical properties are also compared with the polypropylene resin composition to which no wax is added. However, the optical characteristics tend to be maintained or improved. Further, when the density (D) of the polyethylene wax is in the above range and further satisfies the above B value or the relationship between the A value and the B value, it is excellent in formation during vacuum forming.

The polyethylene wax has a density (D (kg / m ³ )) of 880 to 910 (k
The range of g / m ³ ) is preferred. When the density (D) of the polyethylene wax is in the above range, the mechanical properties and optical properties tend to be further improved.

The density of the polyethylene wax depends on the number average molecular weight (Mn) of the polyethylene wax when the polyethylene wax is a homopolymer of ethylene. For example, if the molecular weight of polyethylene wax is lowered, the density of the resulting polymer can be controlled low. When the polyethylene wax is a copolymer of ethylene and α-olefin, the density of the polyethylene wax depends on the number average molecular weight (Mn), and the amount of α-olefin used for ethylene during polymerization. , And its type. For example, when the amount of α-olefin used relative to ethylene is increased, the density of the resulting polymer can be lowered.

From the viewpoint of the density of the polyethylene wax, an ethylene homopolymer, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, or a mixture thereof is preferable.
The α-olefin used for producing the copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 10 carbon atoms, and propylene, 1-butene, 1-pentene. 1-hexene, 4-methyl-1-pentene and 1-octene are more preferable, and propylene, 1-butene, 1-hexene and 4-methyl-1-pentene are particularly preferable.

It is preferable that the α-olefin used in the production of the copolymer of ethylene and α-olefin is in the range of 0 to 20 mol% with respect to all monomers used.
The density of the polyethylene wax can also be controlled by the polymerization temperature. For example, when a polyethylene wax is produced by a metallocene catalyst described later, the polymerization temperature is usually in the range of 100 to 200 ° C., but from the viewpoint of producing a polyethylene wax having a density in the preferred range described above, the polymerization temperature is , Preferably, it is the range of 100-180 degreeC, More preferably, it is the range of 100-170 degreeC.

Such polyethylene wax is solid at normal temperature and becomes a low-viscosity liquid at 65 to 130 ° C.
Further, the polyethylene wax preferably 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. Formula (III) below
0.501 × D-366 ≧ Tc (III)
More preferably, the following formula (IIIa)
0.501 × D-366.5 ≧ Tc (IIIa)
More preferably, the following formula (IIIb)
0.501 × D-367 ≧ Tc (IIIb)
Satisfy the relationship.

  When the crystallization temperature (Tc) and the density (D) in the polyethylene wax satisfy the relationship of the above formula, the dispersibility of the polyethylene wax in polypropylene tends to be good.

  A polyethylene wax that satisfies the relationship of the above formula can be prepared using a metallocene catalyst. Among the metallocene catalysts, metallocene catalysts whose ligands are non-crosslinked are preferable. As such a metallocene catalyst, a metallocene compound represented by the general formula (1) described later can be exemplified.

  Furthermore, the polyethylene wax satisfying the relationship of the above formula can also be produced by controlling the polymerization temperature. For example, when a polyethylene wax is produced by a metallocene catalyst described later, the polymerization temperature is usually in the range of 100 to 200 ° C., but from the viewpoint of producing the polyethylene wax having the B value described above, the polymerization temperature is preferably Is in the range of 100 to 180 ° C, more preferably in the range of 100 to 170 ° C.

Suitable metallocene catalysts in the present invention include, for example,
(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. Or a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or 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 number of 1 to 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, the number of carbon atoms 1-20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups, -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, A halogenated hydrocarbon group 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, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a 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. 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 —, —N
^{R 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, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a 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, or 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 — (wherein R ⁴⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms. 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 may be bonded to each other to form a ring, R ¹³ , R ¹⁴ is selected from a hydrocarbon group and a silicon-containing group, and may be the same or different, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. 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 eta ⁴ -1,3-butadiene, s- cis - or s- trans eta ^{4-1,4-diphenyl-1,3-butadiene,} s- cis - or s- trans eta 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 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 the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or 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 No. 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. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like 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 method of using each component and the order of addition are arbitrarily selected, and 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 ratio that a 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 1 of metallocene compound>.

When such a catalyst is used, a polyethylene wax having the above-described characteristics can be easily obtained.
The shape of the polyethylene wax of the present invention is not particularly limited, but is usually a pellet-like or tablet-like particle.

[Other ingredients]
In the present invention, in addition to the above polypropylene and polyethylene wax, additives such as antioxidants, ultraviolet absorbers, light stabilizers, metal soaps, fillers, flame retardants, etc., as necessary, are added as necessary. May be used in addition to.

Examples of the stabilizer include antioxidants such as hindered 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.

Furthermore, when manufacturing a foaming molding, you may add a foaming agent. When producing a foamed molded article in the present invention, an organic or inorganic chemical foaming agent is preferred as the foaming agent.
Examples of the chemical foaming agent include azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), N, N′-dinitrosopentamethylenetetramine (DPT), 4,4′-oxybis (benzenesulfonylhydrazide) ( OBSH), sodium hydrogen carbonate (bicarbonate), ammonium carbonate, and mixtures of two or more thereof. Moreover, you may use the masterbatch of the foaming agent which improved the handleability.

In addition to the foaming agent, a foaming aid may be used. Examples of the foaming aid include zinc compounds, urea compounds, acidic substances, and amines.
Examples of other additives include colorants, plasticizers, anti-aging agents, colorants, plasticizers, and oils.

[Raw material composition ratio]
The weight ratio of polypropylene and olefin elastomer used as a raw material of the present invention is based on the total amount of polypropylene and olefin elastomer of 100% by weight, with polypropylene in the range of 55 to 95% by weight, and olefin thermoplastic elastomer. It is in the range of 5 to 45% by weight.

  The weight ratio is preferably such that the polypropylene content is in the range of 60 to 90% by weight and the olefin elastomer content is in the range of 10 to 40% by weight, based on the total amount of polypropylene and olefin elastomer of 100% by weight. More preferably, the polypropylene content is in the range of 70 to 90% by weight and the olefin elastomer content is in the range of 10 to 30% by weight.

When the content ratio of polypropylene and olefin-based elastomer is in the above range, a molded article having an excellent balance between impact resistance and transparency can be obtained.
The composition ratio of the above-mentioned resin mixture composed of polypropylene and olefin elastomer and polyethylene wax used as the raw material of the present invention is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component. The composition ratio is preferably in the range of 1 to 5 parts by weight, more preferably in the range of 1 to 4 parts by weight, and particularly preferably in the range of 1 to 2 parts by weight.

  When polyethylene wax is used for a resin mixture composed of polypropylene and an olefin elastomer at a composition ratio in the above range, the effect of improving fluidity at the time of T-die molding is great, and the moldability is good. There is a tendency that the speed is further improved and the productivity is improved. Furthermore, it is formed from polypropylene and an olefin-based elastomer and tends to be less impaired in the mechanical properties inherent to the polypropylene resin composition. Further, as compared with the case of injection molding without adding polyethylene wax, molding can be performed at a lower molding temperature, and the cooling time may be shortened. 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. Further, when the polyethylene wax is used in an amount of less than 5 parts by weight with respect to 100 parts by weight of the resin component (polypropylene and olefin elastomer), it may be compared with a polypropylene resin composition to which no wax is added. The optical characteristics tend to be almost equal or better.

[T-die molding]
In the method for producing a molded body of the present invention, the raw material is T-die molded.
There is no particular limitation on the method of T-die molding. Usually, raw materials such as polypropylene, olefinic elastomer, and polyethylene wax added from a hopper are melt-kneaded in an extruder, and the melt-kneaded product is extruded from a T-die installed at the tip of the extruder and is cooled with a cooling roll or the like. A molded body (sheet, film) can be produced by cooling and winding with a winding device or the like.

  The method for adding polypropylene, olefinic elastomer, and polyethylene wax to the extruder is not particularly limited. For example, polypropylene, olefin elastomer, and polyethylene wax may be added separately to the extruder as they are, or these raw materials may be dry blended and the blended product added to the extruder. Alternatively, the raw material may be melt-kneaded in advance to obtain a master batch, and the master batch may be added to the extruder. Examples of the apparatus used for dry blending include a high-speed mixer such as a Henschel mixer, and a tumbler. Examples of the apparatus used for melt kneading include a plast mill, a kneader, a roll mixer, a Banbury mixer, a Brabender, a single screw extruder, a twin screw extruder, and the like.

In the present invention, a film or a sheet-like molded body is obtained by the above-described T-die molding. The film (sheet) obtained by T-die molding may be a single layer film (sheet) or a multilayer film (sheet). A single layer film (sheet) is obtained by the T-die molding described above. The multilayer film (sheet) is obtained by, for example, melt-kneading the resin composition forming each layer of the film (sheet) with a separate extruder, and using the melt-kneaded product for co-extrusion T
It can be manufactured by press-fitting into a die, further extruding these melt-kneaded materials simultaneously from the slits of this die, cooling them with a cooling roll or the like, and winding them with a winding device or the like.

  In the multilayer film obtained by the present invention, at least one layer is formed from the resin composition using the above-described polypropylene, olefin elastomer, and polyethylene wax as raw materials. It may be formed of a plastic resin composition. As the extrusion conditions for the other thermoplastic resin compositions, the T-die molding conditions used for the thermoplastic resin are usually applicable.

  The resin temperature when extruding the melt-kneaded product from the die is preferably in the range of 180 to 250 ° C. When the resin temperature at the time of extruding from the die is in the above range, a molded product having excellent gloss and excellent resin strength can be stably produced.

  In the present invention, when a foaming agent, or a foaming agent and a foaming auxiliary agent are added when kneading polypropylene, an olefinic elastomer, and polyethylene wax in an extruder, a foamed molded product is obtained.

  In the present invention, the molded body (film, sheet) obtained by the T-die molding may be further stretched. Examples of the stretching method include a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), simultaneous biaxial stretching method, uniaxial stretching method, and other known stretching methods.

The other layers may be laminated via a layer formed from an adhesive.
Examples of the adhesive include isocyanate adhesives, polyester adhesives, urethane adhesives, and organic titanium compounds.

When the other layer is formed by bonding, the other layer may be formed from the above-described thermoplastic resin composition, but may be formed from paper, metal, an inorganic substance, a woody material, or the like.
The molded body obtained by such T-die molding can be used as a molded body such as the obtained sheet or film, and further subjected to vacuum molding or the like as a secondary processed molded body.

[Vacuum forming]
The molded body obtained by the T-die molding can be further vacuum molded.
There is no particular limitation on the vacuum forming method. Usually, a sheet or film-like molded body is heated and softened to be in close contact with the mold, air is exhausted from an exhaust port provided in the mold, the molded body is brought into close contact with the mold, and then cooled. Subprocessed compacts can be manufactured.

Examples of the vacuum forming method include other known methods such as straight forming, drape forming, plug-assist forming, and air blow forming.
The surface temperature of the molded body during vacuum forming is usually in the range of 150 to 250 ° C, preferably in the temperature range of 160 to 220 ° C, more preferably in the temperature range of 160 to 200 ° C. When the surface temperature is in the above range, the drawdown property and the shapeability are good, and the thickness is uniform.

  The molded body thus obtained can be further processed as necessary to be used for various purposes.

In the following examples, the physical properties of polyethylene wax were measured as follows.
(Number average molecular weight (Mn))
The number average molecular weight (Mn) is obtained from GPC measurement. The measurement was performed under the following conditions. The number average molecular weight (Mn) was determined by preparing a calibration curve using commercially available monodisperse standard polystyrene and calculating the molecular weight based on the following conversion method.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PE conversion / General calibration method

In addition, the coefficient of the Mark-Houwink viscosity formula shown below was used for calculation of general-purpose calibration.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70
(A value, B value)
From the GPC measurement results described above, the proportion of components having a molecular weight of 1,000 or less was determined by weight%, and was designated as A value. Further, from the measurement result of GPC, the ratio of the component having a molecular weight of 20,000 or more was determined by weight%, and the B value was obtained.

(Melt viscosity)
Measurements were made at 140 ° C. using a Brookfield viscometer.
(density)
It was measured according to the density gradient method of JIS K7112.

(Melting point)
It measured using the differential scanning calorimeter (DSC) [DSC-20 (made by Seiko Denshi Kogyo Co., Ltd.)]. First, the measurement sample was once heated to 200 ° C. and held for 5 minutes, and then immediately cooled to room temperature. About 10 mg of this sample was subjected to DSC measurement in the temperature range from −20 ° C. to 200 ° C. under the temperature rising rate of 10 ° C./min. The endothermic peak value of the curve obtained from the measurement results was taken as the melting point.

(Crystallization temperature)
The crystallization temperature (Tc, ° C.) is 2 ° C. in accordance with ASTM D 3417-75.
It measured on condition of / min.

In the following examples, the physical properties of polypropylene were measured as follows.
(MI)
The measurement was performed under the conditions of 230 ° C. and a test load of 21.18 N according to JIS K7210.

(density)
It was measured according to the density gradient method of JIS K7112.
In the following examples, the physical properties of the olefin elastomer were measured as follows.

(MI)
For ethylene / α-olefin random copolymer:
The measurement was performed in accordance with JIS K7210 at 190 ° C. and a test load of 21.18 N.

For propylene / α-olefin random copolymer:
The measurement was performed under the conditions of 230 ° C. and a test load of 21.18 N according to JIS K7210.
(density)
It was measured according to the density gradient method of JIS K7112.

(Synthesis of polyethylene wax (1))
Polyethylene wax (1) was synthesized using a metallocene catalyst as follows.
770 ml of hexane and 115 g of propylene were charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen and kept at 25 ° C. Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.04 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate, and bis (cyclopentadienyl) zirconium dichloride were added. Polymerization was initiated by press-fitting with 0.0005 mmol ethylene. Thereafter, by continuously supplying only ethylene, the total pressure was kept at 3.0 MPa (gauge pressure), and polymerization was carried out at 155 ° C. for 30 minutes.

After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was dried overnight at 100 ° C. under reduced pressure to obtain 46 g of polyethylene wax (1). The obtained polyethylene wax (1) has a number average molecular weight (Mn) of 800, a weight average molecular weight (Mw) of 1,500, a melt viscosity of 40 mPa · s, a density of 897 kg / m ³ , and a melting point of 78. It was 8 ° C. Moreover, A value was 31.7 weight% and B value was 0.01 weight%. The results are shown in Table 1.

(Synthesis of polyethylene wax (2))
Polyethylene wax (2) was synthesized as follows using a metallocene catalyst.
A stainless steel autoclave having an internal volume of 2 L, sufficiently purged with nitrogen and kept at 25 ° C., was charged with 700 ml of hexane and 150 g of propylene. Next, after raising the temperature in the system to 140 ° C., 0.3 mmol of triisobutylaluminum, 0.04 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate, and bis (cyclopentadienyl) zirconium dichloride were added. Polymerization was initiated by press-fitting with 0.0002 mmol ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 3.0 MPa (gauge pressure), and polymerization was performed at 140 ° C. for 30 minutes.

After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was dried overnight at 100 ° C. under reduced pressure to obtain 40 g of polyethylene wax (2). The obtained polyethylene wax (2) has a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 7,000, a melt viscosity of 600 mPa · s, a density of 880 kg / m ³ , and a melting point. It was 68.2 ° C. Moreover, A value is 7.0 weight%,
The B value was 4.1% by weight. The results are shown in Table 1.

(Synthesis of polyethylene wax (3))
Polyethylene wax (2) was synthesized as follows using a metallocene catalyst.
920 ml of hexane and 50 g of propylene were charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen and kept at 25 ° C. Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.04 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate, and bis (cyclopentadienyl) zirconium dichloride were added. Polymerization was initiated by press-fitting with 0.0002 mmol ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 3.0 MPa (gauge pressure), and polymerization was performed at 150 ° C. for 30 minutes.

After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was dried overnight at 100 ° C. under reduced pressure to obtain 40 g of polyethylene wax (2). The obtained polyethylene wax (3) has a number average molecular weight (Mn) of 3,000, a weight average molecular weight (Mw) of 8,200, a melt viscosity of 1,000 mPa · s, and a density of 932 kg / m ³ , The melting point was 105.0 ° C. Moreover, A value was 4.6 weight% and B value was 6.7 weight%. The results are shown in Table 1.
Table 1 summarizes the physical properties of the polyethylene wax used in the present invention.

In the following examples, the physical properties of the molded products were evaluated as follows.
(productivity)
Evaluation was carried out based on the resin pressure (MPa) and the load power (A) during T-die molding.

(transparency)
According to JIS K7105, the haze of the film formed into the same film thickness was measured.
(Mechanical properties)
A test specimen No. 4 defined in ASTM D638 was prepared, and a tensile test was performed under the conditions of 23 ° C. and a speed of 50 mm / min, and the tensile yield stress was measured.

[Example 1]
Polypropylene resin (Prime Polypro F219DA; manufactured by Prime Polymer, polypropylene random polymer, density = 910 (kg / m ³ ), MI = 8.0 g / 10 min)
80 parts by mass, ethylene / α-olefin random copolymer [olefin elastomer] (Toughmer A1050; Mitsui Chemicals, Inc., density = 860 (kg / m ³ ), MI = 1.2 g
/ 10 minutes (190 ° C., test load 21.18 N)) 20 parts by mass, and polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc., density = 913 (kg / m ³ )
, Mn = 2,000, A value = 9.3 (wt%), B value = 2.2 (wt%), melt viscosity = 300 (mPa · s), ethylene content = 95 (mol%)) 2 mass The parts were mixed. Next, the cylinder temperature of a 20 mmφ single screw extruder equipped with a T die having a lip width of 240 mm was set to 200 ° C. and the die temperature was set to 210 ° C., and the resulting mixture was added to this extruder and melted at a rotational speed of 60 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a film having a thickness of 40 μm. The resin pressure at the time of melt-kneading was 8.9 MPa, the load voltage was 7.4 A, the discharge was stable, and the resulting film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 24.8 MPa and a haze of 25.2%. The results are shown in Table 2.

[Example 2]
Polyethylene wax is a metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc., density = 902 (kg / m ³ ), Mn = 3,400, A value =
T-die molding was performed in the same manner as in Example 1 except that 4.7 (wt%), B value = 8.7 (wt%), and melt viscosity = 1,350 (mPa · s). . The resin pressure at the time of melt kneading was 9.2 MPa, the load voltage was 7.8 A, the discharge was stable, the obtained film had no thickness unevenness, and the moldability was good. The obtained film had a tensile yield stress of 25.2 MPa and a haze of 23.6%. The results are shown in Table 2.

Example 3
Polyethylene wax (1) (density = 897 (kg / m ³ )),
T in the same manner as in Example 1 except that Mn = 800, A value = 23.5 (% by weight), B value = 0.01 (% by weight), and melt viscosity = 40 (mPa · s). Die molding was performed. The resin pressure during melt-kneading was 8.6 MPa, the load voltage was 7.2 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 25.5 MPa and a haze of 22.7%. The results are shown in Table 2.

Example 4
Polyethylene wax to polyethylene wax (2) (density = 880 (kg / m ³ )),
The same method as in Example 1 except that Mn = 2500, A value = 7.0 (% by weight), B value = 4.1 (% by weight), and melt viscosity = 600 (mPa · s). T-die molding was performed. The resin pressure at the time of melt-kneading was 9.0 MPa, the load voltage was 7.5 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 25.4 MPa and a haze of 22.1%. The results are shown in Table 2.

Example 5
T-die molding was performed in the same manner as in Example 1 except that the amount of metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc.) was changed to 1 part by mass. The resin pressure at the time of melt kneading was 10.1 MPa, the load voltage was 7.9 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 25.2 MPa and a haze of 24.1%. The results are shown in Table 2.

Example 6
T-die molding was performed in the same manner as in Example 1 except that the amount of metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc.) was changed to 5 parts by mass. The resin pressure at the time of melt kneading was 8.1 MPa, the load voltage was 6.9 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 24.7 MPa and a haze of 24.1%. The results are shown in Table 2.

[Comparative Example 1]
Polypropylene resin (F219DA; manufactured by Prime Polymer Co., Ltd., polypropylene random polymer, density = 910 (kg / m ³ ), MI = 8.0 g / 10 min) 80 parts by mass, and ethylene / α-olefin random copolymer [olefin system Elastomer] (Tuffmer A1050; Mitsui Chemicals, density = 860 (kg / m ³ ), MI = 1.2 g / 10 min (
190 ° C., test load 21.18 N)) 20 parts by mass were mixed. Next, the cylinder temperature of a 20 mmφ single screw extruder equipped with a T die having a lip width of 240 mm was set to 200 ° C. and the die temperature was set to 210 ° C., and the resulting mixture was added to this extruder and melted at a rotational speed of 60 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a film having a thickness of 40 μm. The results are shown in Table 2.

[Comparative Example 2]
Polyethylene wax (3) (density = 932 (kg / m ³ )),
The same method as in Example 1 except that Mn = 3,000, A value = 4.6 (% by weight), B value = 6.7 (% by weight), and melt viscosity = 1000 (mPa · s). T-die molding was performed. The results are shown in Table 2. Compared with the polypropylene resin composition to which the wax of Comparative Example 1 is not added, the tensile yield stress is decreased and the haze is increased.

[Comparative Example 3]
Polyethylene wax is polyethylene wax (High Wax 420P; manufactured by Mitsui Chemicals, density = 930 (kg / m ³ ), Mn = 2,000, A value = 8.3 (% by weight), B value = 6
. 2 (% by weight) and melt viscosity = 700 (mPa · s)) T-die molding was performed in the same manner as in Example 1. The results are shown in Table 2. Compared with the polypropylene resin composition to which the wax of Comparative Example 1 is not added, the tensile yield stress is decreased and the haze is increased.

[Comparative Example 4]
Polyethylene wax is polyethylene wax (A-C6; manufactured by Honeywell, density = 913 (kg / m ³ ), Mn = 1,800, A value = 6.5 (wt%), B value = 3.3 (wt%) ), T-die molding was performed in the same manner as in Example 1 except that the melt viscosity was changed to 420 (mPa · s). The results are shown in Table 2. Compared with the polypropylene resin composition to which the wax of Comparative Example 1 is not added, the tensile yield stress is decreased and the haze is increased.

Example 7
Polypropylene resin (Prime Polypro F219DA; manufactured by Prime Polymer, polypropylene random polymer, density = 910 (kg / m ³ ), MI = 8.0 g / 10 min)
80 parts by mass, propylene / α-olefin random copolymer [olefin elastomer] (Toughmer XM7070; Mitsui Chemicals, Inc., density = 900 (kg / m ³ ), MI = 7.
20 parts by mass of 0 g / 10 min (230 ° C., test load 21.18 N)) and polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc., density = 913 (kg / m ³ ), Mn = 2,000 , A value = 9.3 (% by weight), B value = 2.2 (% by weight), melt viscosity = 300 (mPa · s), ethylene content = 95 (% by mol)) were mixed. Next, the cylinder temperature of a 20 mmφ single screw extruder equipped with a T die having a lip width of 240 mm was set to 200 ° C. and the die temperature was set to 210 ° C., and the resulting mixture was added to this extruder and melted at a rotational speed of 60 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a film having a thickness of 40 μm. The resin pressure at the time of melt kneading was 7.0 MPa, the load voltage was 6.6 A, the discharge was stable, the obtained film had no thickness unevenness, and the molding processability was good. The obtained film had a tensile yield stress of 21.9 MPa and a haze of 22.1%. The results are shown in Table 3.

Example 8
Polyethylene wax is a metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc., density = 902 (kg / m ³ ), Mn = 3,400, A value =
T-die molding was performed in the same manner as in Example 7 except that 4.7 (wt%), B value = 8.7 (wt%), and melt viscosity = 1,350 (mPa · s). . The resin pressure at the time of melt-kneading was 7.3 MPa, the load voltage was 7.0 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 22.2 MPa and a haze of 20.6%. The results are shown in Table 3.

Example 9
Polyethylene wax (1) (density = 897 (kg / m ³ )),
T in the same manner as in Example 7 except that Mn = 800, A value = 23.5 (% by weight), B value = 0.01 (% by weight), and melt viscosity = 40 (mPa · s). Die molding was performed. The resin pressure at the time of melt kneading was 6.8 MPa, the load voltage was 6.2 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 22.5 MPa and a haze of 20.4%. The results are shown in Table 3.

Example 10
Polyethylene wax to polyethylene wax (2) (density = 880 (kg / m ³ )),
The same method as in Example 7 except that Mn = 2500, A value = 7.0 (wt%), B value = 4.1 (wt%), melt viscosity = 600 (mPa · s)) T-die molding was performed. The resin pressure at the time of melt kneading was 7.1 MPa, the load voltage was 6.7 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 22.7 MPa and a haze of 19.7%. The results are shown in Table 3.

Example 11
T-die molding was performed in the same manner as in Example 7 except that the addition amount of the metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc.) was changed to 1 part by mass. The resin pressure at the time of melt kneading was 8.2 MPa, the load voltage was 7.3 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 22.2 MPa and a haze of 21.1%. The results are shown in Table 3.

Example 12
T-die molding was performed in the same manner as in Example 7 except that the addition amount of metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc.) was changed to 5 parts by mass. The resin pressure at the time of melt-kneading was 6.3 MPa, the load voltage was 6.0 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 21.7 MPa and a haze of 21.1%. The results are shown in Table 3.

[Comparative Example 5]
Polypropylene resin (Prime Polypro F219DA; manufactured by Prime Polymer, polypropylene random polymer, density = 910 (kg / m ³ ), MI = 8.0 g / 10 min)
80 parts by mass, and propylene / α-olefin random copolymer [olefin elastomer] (Tuffmer XM7070; Mitsui Chemicals, density = 900 (kg / m ³ ), MI
= 7.0 g / 10 min (230 ° C., test load 21.18 N)) 20 parts by mass were mixed. Next, the cylinder temperature of a 20 mmφ single screw extruder equipped with a T die having a lip width of 240 mm was set to 200 ° C. and the die temperature was set to 210 ° C., and the resulting mixture was added to this extruder and melted at a rotational speed of 60 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a film having a thickness of 40 μm. The results are shown in Table 3.

[Comparative Example 6]
Polyethylene wax (3) (density = 932 (kg / m ³ )),
Mn = 3,000, A value = 4.6 (% by weight), B value = 6.7 (% by weight), melt viscosity = 1000 (mPa · s)) T-die molding was performed. The results are shown in Table 3. Compared with the polypropylene resin composition to which no wax is added in Comparative Example 5, the tensile yield stress is reduced and the haze is increased.

[Comparative Example 7]
Polyethylene wax is polyethylene wax (High Wax 420P; manufactured by Mitsui Chemicals, density = 930 (kg / m ³ ), Mn = 2,000, A value = 8.3 (% by weight), B value = 6
. 2 (% by weight), melt viscosity = 700 (mPa · s)) T-die molding was performed in the same manner as in Example 7, except that it was changed. The results are shown in Table 3. Compared with the polypropylene resin composition to which no wax is added in Comparative Example 5, the tensile yield stress is reduced and the haze is increased.

[Comparative Example 8]
Polyethylene wax is polyethylene wax (A-C6; manufactured by Honeywell, density = 913 (kg / m ³ ), Mn = 1,800, A value = 6.5 (wt%), B value = 3.3 (wt%) ), T-die molding was performed in the same manner as in Example 7 except that the melt viscosity was changed to 420 (mPa · s). The results are shown in Table 3. Compared with the polypropylene resin composition to which no wax is added in Comparative Example 5, the tensile yield stress is reduced and the haze is increased.

The physical properties of the sheets prepared in Examples 13 to 24 and Comparative Examples 10 to 16 were measured as follows.
(productivity)
Evaluation was carried out based on the resin pressure (MPa) and the load power (A) during T-die molding.

(Mechanical properties)
A test specimen No. 4 defined in ASTM D638 was prepared, and a tensile test was performed under the conditions of 23 ° C. and a speed of 50 mm / min, and the tensile yield stress was measured.

(Drawdown)
The resulting sheet was vacuum-formed using a pressure-air vacuum forming machine (manufactured by Asano Laboratory Co., Ltd.) with a heater temperature set at 600 ° C. under the conditions of a sheet surface temperature of 190 ° C. and a heating time of 20 seconds.

The shapeability (drawdown) at the time of vacuum forming was evaluated by visually observing the sag of the heat-softened sheet at the time of vacuum forming.
○: The sheet did not sag excessively and could be vacuum-formed without any problems. ×: The sheet slid excessively and contacted the heater (appearance)
The glossiness of the surface of the obtained molded body was visually observed, and compared with a molded body of polyethylene alone, and judged.
○: No change in glossiness ×: The glossiness deteriorated

Example 13
Polypropylene resin (Prime Polypro E111G; manufactured by Prime Polymer Co., Ltd., polypropylene homopolymer, density = 910 (kg / m ³ ), MI = 0.5 g / 10 min) 80 parts by mass, ethylene / α-olefin random copolymer [olefin Elastomer] (Tuffmer A1050; Mitsui Chemicals, density = 860 (kg / m ³ ), MI = 1.2 g / 10
20 parts by weight (190 ° C., test load 21.18 N)) and polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc., density = 913 (kg / m ³ ), Mn
= 2,000, A value = 9.3 (% by weight), B value = 2.2 (% by weight), melt viscosity = 300 (mPa · s), ethylene content = 95 (mol%)) 2 parts by mass Mixed. Next, the cylinder temperature of a 65 mmφ single screw extruder equipped with a T die having a lip width of 600 mm was set to 210 ° C. and the die temperature was set to 220 ° C., and the resulting mixture was added to this extruder and melted at a rotation speed of 70 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a sheet having a thickness of 0.5 mm. The resin pressure at the time of melt-kneading was 8.6 MPa, the load voltage was 56.1 A, the discharge was stable, the obtained film had no thickness unevenness, and the moldability was good. The resulting sheet had a tensile yield stress of 35.1 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4.

Example 14
Polyethylene wax is a metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc., density = 902 (kg / m ³ ), Mn = 3,400, A value =
T-die molding was performed in the same manner as in Example 13 except that 4.7 (wt%), B value = 8.7 (wt%), and melt viscosity = 1,350 (mPa · s). . The resin pressure at the time of melt kneading was 8.8 MPa, the load voltage was 57.2 A, the discharge was stable, and the obtained sheet had no thickness unevenness and the molding processability was good. The obtained sheet had a tensile yield stress of 36.5 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4.

Example 15
Polyethylene wax (1) (density = 897 (kg / m ³ )),
T in the same manner as in Example 13 except that Mn = 800, A value = 23.5 (% by weight), B value = 0.01 (% by weight), and melt viscosity = 40 (mPa · s). Die molding was performed. The resin pressure at the time of melt kneading was 8.5 MPa, the load voltage was 54.9 A, the discharge was stable, and the obtained sheet had no thickness unevenness and good moldability. The obtained sheet had a tensile yield stress of 36.4 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4.

Example 16
Polyethylene wax to polyethylene wax (2) (density = 880 (kg / m ³ )),
Mn = 2,500, A value = 7.0 (wt%), B value = 4.1 (wt%), melt viscosity = 600 (mPa · s)) T-die molding was performed. The resin pressure during melt-kneading was 8.7 MPa, the load voltage was 56.4 A, the discharge was stable, and the obtained sheet had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 36.8 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4.

Example 17
T-die molding was performed in the same manner as in Example 13 except that the amount of metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc.) was changed to 1 part by mass. The resin pressure at the time of melt-kneading was 9.0 MPa, the load voltage was 60.3 A, the discharge was stable, the thickness of the obtained sheet was not uneven, and the molding processability was good. The obtained sheet had a tensile yield stress of 36.2 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4.

Example 18
T-die molding was performed in the same manner as in Example 13 except that the amount of metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc.) was changed to 5 parts by mass. The resin pressure at the time of melt kneading was 8.1 MPa, the load voltage was 52.2 A, the discharge was stable, and the obtained sheet had no thickness unevenness and the molding processability was good. The obtained sheet had a tensile yield stress of 34.9 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4.

[Comparative Example 9]
Polypropylene resin (Prime Polypro E111G; manufactured by Prime Polymer, polypropylene homopolymer, density = 910 (kg / m ³ ), MI = 0.5 g / 10 min) 80 parts by mass, and ethylene / α-olefin random copolymer [ Olefin-based elastomer] (Toughmer A1050; Mitsui Chemicals, density = 860 (kg / m ³ ), MI = 1.2 g
/ 10 minutes (190 ° C., test load 21.18 N)) 20 parts by mass were mixed. Next, the cylinder temperature of a 65 mmφ single screw extruder equipped with a T die having a lip width of 600 mm was set to 210 ° C. and the die temperature was set to 220 ° C., and the resulting mixture was added to this extruder and melted at a rotation speed of 70 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a sheet having a thickness of 0.5 μm. Furthermore, the obtained sheet was vacuum-formed under the above conditions. The results are shown in Table 4.

[Comparative Example 10]
Polyethylene wax (3) (density = 932 (kg / m ³ )),
Mn = 3,000, A value = 4.6 (% by weight), B value = 6.7 (% by weight), melt viscosity = 1000 (mPa · s)) T-die molding was performed.

Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4. Compared with the polypropylene resin composition to which no wax is added in Comparative Example 9, the tensile yield stress is reduced and the haze is increased. Moreover, the drawdown property at the time of vacuum forming is impaired, and the appearance of the obtained molded product is not excellent.

[Comparative Example 11]
Polyethylene wax is polyethylene wax (High Wax 420P; manufactured by Mitsui Chemicals, density = 930 (kg / m ³ ), Mn = 2,000, A value = 8.3 (% by weight), B value = 6
. T-die molding was performed in the same manner as in Example 13 except that the viscosity was changed to 2 (% by weight) and melt viscosity = 700 (mPa · s).

Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4. Compared with the polypropylene resin composition to which no wax is added in Comparative Example 9, the tensile yield stress is reduced and the haze is increased. Moreover, the drawdown property at the time of vacuum forming is impaired, and the appearance of the obtained molded product is not excellent.

[Comparative Example 12]
Polyethylene wax is polyethylene wax (A-C6; manufactured by Honeywell, density = 913 (kg / m ³ ), Mn = 1,800, A value = 6.5 (wt%), B value = 3.3 (wt%) ), T-die molding was performed in the same manner as in Example 13 except that the melt viscosity was changed to 420 (mPa · s).

Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 4. Compared with the polypropylene resin composition to which no wax is added in Comparative Example 9, the tensile yield stress is reduced and the haze is increased. Moreover, the drawdown property at the time of vacuum forming is also impaired.

Example 19
Polypropylene resin (Prime Polypro E111G; manufactured by Prime Polymer Co., Ltd., polypropylene homopolymer, density = 910 (kg / m ³ ), MI = 0.5 g / 10 min) 80 parts by mass, propylene / α-olefin random copolymer [olefin Elastomer] (Tuffmer XM7070; Mitsui Chemicals, density = 900 (kg / m ³ ), MI = 7.0 g /
10 parts (230 ° C., test load 21.18 N)) 20 parts by mass, and polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc., density = 913 (kg / m ³ ),
Mn = 2,000, A value = 9.3 (% by weight), B value = 2.2 (% by weight), melt viscosity = 300 (mPa · s), ethylene content = 95 (mol%)) 2 parts by mass Were mixed. Next, the cylinder temperature of a 65 mmφ single screw extruder equipped with a T die having a lip width of 600 mm was set to 210 ° C. and the die temperature was set to 220 ° C., and the resulting mixture was added to this extruder and melted at a rotation speed of 70 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a sheet having a thickness of 0.5 mm. The resin pressure at the time of melt-kneading was 7.9 MPa, the load voltage was 52.2 A, the discharge was stable, and the obtained film had no thickness unevenness and good moldability. The resulting sheet had a tensile yield stress of 33.2 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5.

Example 20
Polyethylene wax is a metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc., density = 902 (kg / m ³ ), Mn = 3,400, A value =
4.7 (wt%), B value = 8.7 (wt%), melt viscosity = 1,350 (mPa · s)) T-die molding was performed in the same manner as in Example 19. . The resin pressure at the time of melt kneading was 8.1 MPa, the load voltage was 53.6 A, the ejection was stable, and the obtained sheet had no thickness unevenness and the molding processability was good. The obtained sheet had a tensile yield stress of 33.8 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5.

Example 21
Polyethylene wax (1) (density = 897 (kg / m ³ )),
T in the same manner as in Example 19 except that Mn = 800, A value = 23.5 (% by weight), B value = 0.01 (% by weight), and melt viscosity = 40 (mPa · s). Die molding was performed. The resin pressure at the time of melt kneading was 7.8 MPa, the load voltage was 50.5 A, the discharge was stable, and the obtained sheet had no thickness unevenness and the molding processability was good. The obtained sheet had a tensile yield stress of 34.1 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5.

[Example 22]
Polyethylene wax to polyethylene wax (2) (density = 880 (kg / m ³ )),
Mn = 2500, A value = 7.0 (wt%), B value = 4.1 (wt%), melt viscosity = 600 (mPa · s)) T-die molding was performed. The resin pressure at the time of melt kneading was 8.0 MPa, the load voltage was 51.5 A, the discharge was stable, and the obtained sheet had no thickness unevenness and good moldability. The obtained film had a tensile yield stress of 34.8 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5.

Example 23
Metallocene polyethylene wax (Excellex 48070BT; Mitsui Chemicals, Inc.)
T-die molding was performed in the same manner as in Example 19 except that the amount added was 1 mass part. The resin pressure at the time of melt-kneading was 8.3 MPa, the load voltage was 54.6 A, the discharge was stable, and the obtained sheet had no thickness unevenness and the molding processability was good. The obtained sheet had a tensile yield stress of 33.3 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5.

Example 24
T-die molding was performed in the same manner as in Example 19 except that the addition amount of the metallocene polyethylene wax (Excellex 48070BT; manufactured by Mitsui Chemicals, Inc.) was changed to 5 parts by mass. The resin pressure at the time of melt kneading was 7.5 MPa, the load voltage was 48.3 A, the discharge was stable, and the obtained sheet had no uneven thickness, and the molding processability was good. The obtained sheet had a tensile yield stress of 32.7 MPa.
Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5.

[Comparative Example 13]
Polypropylene resin (Prime Polypro E111G; manufactured by Prime Polymer Co., Ltd., polypropylene homopolymer, density = 910 (kg / m ³ ), MI = 0.5 g / 10 min) 80 parts by mass, and propylene / α-olefin random copolymer [ Olefin-based elastomer] (Tafmer XM7070; Mitsui Chemicals, Inc., density = 900 (kg / m ³ ), MI = 7.
20 parts by mass of 0 g / 10 min (230 ° C., test load 21.18 N)) was mixed. Next, the cylinder temperature of a 65 mmφ single screw extruder equipped with a T die having a lip width of 600 mm was set to 210 ° C. and the die temperature was set to 220 ° C., and the resulting mixture was added to this extruder and melted at a rotation speed of 70 rpm. The melted and kneaded product was extruded from a T-die and cooled with a cooling roll to prepare a sheet having a thickness of 0.5 μm. Furthermore, the obtained sheet was vacuum-formed under the above conditions. The results are shown in Table 5.

[Comparative Example 14]
Polyethylene wax (3) (density = 932 (kg / m ³ )),
The same method as in Example 19 except that Mn = 3,000, A value = 4.6 (% by weight), B value = 6.7 (% by weight), and melt viscosity = 1000 (mPa · s). T-die molding was performed.

Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5. Compared with the polypropylene resin composition to which the wax of Comparative Example 13 is not added, the tensile yield stress is decreased and the haze is increased. Moreover, the drawdown property at the time of vacuum forming is impaired, and the appearance of the obtained molded product is not excellent.

[Comparative Example 15]
Polyethylene wax is polyethylene wax (High Wax 420P; manufactured by Mitsui Chemicals, density = 930 (kg / m ³ ), Mn = 2,000, A value = 8.3 (% by weight), B value = 6
. 2 (% by weight), melt viscosity = 700 (mPa · s)) T-die molding was performed in the same manner as in Example 19, except that it was changed.

Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5. Compared with the polypropylene resin composition to which the wax of Comparative Example 13 is not added, the tensile yield stress is decreased and the haze is increased. Moreover, the drawdown property at the time of vacuum forming is impaired, and the appearance of the obtained molded product is not excellent.

[Comparative Example 16]
Polyethylene wax is polyethylene wax (A-C6; manufactured by Honeywell, density = 913 (kg / m ³ ), Mn = 1,800, A value = 6.5 (wt%), B value = 3.3 (wt%) ), T-die molding was performed in the same manner as in Example 19 except that the melt viscosity was changed to 420 (mPa · s).

Furthermore, the obtained sheet | seat was vacuum-formed and the shapeability at the time of vacuum forming and an external appearance were evaluated.
The results are shown in Table 5. Compared with the polypropylene resin composition to which the wax of Comparative Example 13 is not added, the tensile yield stress is decreased and the haze is increased. Moreover, the drawdown property at the time of vacuum forming is also impaired.

Claims (3)

Based on 100% by weight of the total amount of polypropylene and olefinic elastomer, 100 parts by weight of resin mixture containing polypropylene in the range of 55 to 95% by weight and olefinic elastomer in the range of 5 to 45% by weight The density measured according to the density gradient tube method is in the range of 880 to 920 (kg / m ³ ), and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) is 500 to 4,000. A method for producing a molded body by T-die molding a raw material mixture to which 0.01 to 10 parts by weight of a polyethylene wax satisfying the relationship represented by the following formula (I) is present.
B ≦ 0.0075 × K (I)
(In the above formula (I), B is a content ratio (% by weight) of a component having a polyethylene conversion molecular weight of 20,000 or more in the polyethylene wax when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.) The method for producing a molded body by T-die molding according to claim 1, wherein the polyethylene wax further satisfies a relationship represented by the following formula (II).
A ≦ 230 × K ^(-0.537) (II)
(In the above formula (II), A is a content ratio (% by weight) of a component in which the molecular weight in terms of polyethylene in the polyethylene wax is 1,000 or less when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)   A method for producing a secondary processed molded article by vacuum molding using the molded article obtained by the production method according to claim 1 or 2.