JP2007268776A - Manufacturing method of stretched film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a polypropylene stretched film not almost causing bleed-out and having high transparency and high strength. <P>SOLUTION: The manufacturing method of the stretched film is characterized by the stretch molding of a mixture containing polypropylene with an MI of 0.01-100 g/10 min and polyethylene wax with a density of 890-950(kg/m<SP>3</SP>), a number average molecular weight (Mn) of 700-4,000 and satisfying the relation of the formula (I): B≤0.0075×K and the formula (II): A≤230×K<SP>(-0.537)</SP>wherein B is the content ratio (%) of the component with a molecular weight of 20,000 or above in polyethylene wax, A is the content ratio (%) with a molecular weight of 1,000 or below in polyethylene wax and K is the melt viscosity (mPa s) of polyethylene wax at 140°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a film by stretch molding, and more particularly, to a method for producing a film by stretch molding using polypropylene having a MI in a specific range and a specific polyethylene wax as raw materials.

  Conventionally, polypropylene films obtained by stretch molding have been developed for various uses. In recent years, improvement in productivity of this stretch molding has been increasingly demanded. As a general method for improving productivity at the time of molding such as stretch molding, a method of molding by adding a molding aid is known. For example, a method of molding a thermoplastic resin by applying a molding aid such as oil or polyethylene wax has been studied (for example, Patent Documents 1 and 2).

However, even if a film such as polyethylene is stretched and molded using a conventional molding aid, the moldability itself tends to improve, but the physical properties of the resulting film, such as mechanical properties, transparency, In some cases, optical properties such as glossiness may decrease, and even if it is used as a film, it may cause a problem depending on the application.
Japanese Patent Publication No. 5-80492 Special table 2003-528948 gazette

  An object of the present invention is to provide a method for producing a polypropylene film which improves the productivity during stretch molding and does not impair optical properties such as transparency and gloss and mechanical properties.

  The inventors of the present invention have studied the above-mentioned problems, and when stretch molding is performed using polypropylene having a MI in a specific range and a specific polyethylene wax as raw materials, the productivity is improved. Found that the optical properties such as transparency and gloss inherently possessed by the material are not impaired and the mechanical properties are not impaired, and the present invention has been completed.

That is, the method for producing the film of the present invention comprises:
Polypropylene having an MI measured in the range of 0.01 to 100 g / 10 min at 230 ° C. and a test load of 21.18 N in accordance with JIS K7210, and a density measured in accordance with the density gradient tube method in JIS K7112 is 890 to 950 (kg) / m ³⁾ is in the range of, there a number average molecular weight in terms of polyethylene as measured by gel permeation chromatography (GPC) (Mn) is in the range of 700～4,000, and the following formula (I) and formula (II This is a method for producing a film by stretching a mixture containing polyethylene wax that satisfies the relationship represented by
B ≦ 0.0075 × K (I)
(In the above formula (I), B is the content (%) of the component in which the polyethylene-converted molecular weight in the polyethylene wax is 20,000 or more when measured by gel permeation chromatography, and K is (It is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)
A ≦ 230 × K ^(-0.537) (II)
(In the above formula (II), A is measured by gel permeation chromatography.
It is a content ratio (% by weight) of a component having a polyethylene molecular weight of 1,000 or less in the polyethylene wax, and K is a melt viscosity (mPa · s) of the polyethylene wax at 140 ° C. )
In the method for producing the film, it is preferable to use a raw material in which polyethylene wax is 0.01 to 10 parts by weight per 100 parts by weight of polypropylene in the mixture.

  According to the method for producing a film of the present invention, the productivity at the time of stretch molding of polypropylene is excellent. Further, the polypropylene film obtained by stretch molding does not impair the optical properties such as transparency and glossiness inherent to the polypropylene itself, and also does not impair the mechanical properties.

Hereinafter, the present invention will be described in detail.
First, the raw materials used for the stretch molding of the present invention will be described.
〔polypropylene〕
Specifically, the polypropylene used in the present invention is a propylene homopolymer or propylene having an MI measured in the range of 0.01 to 100 g / 10 min at 230 ° C. and a test load of 21.18 N according to JIS K7210. And a copolymer 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.
The density of the polypropylene is usually in the range of 900 to 910 (kg / m ³ ).

[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 700 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 890 to 950 (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 resulting film tends not to impair the mechanical properties inherent to polypropylene, and the optical properties of the resulting film tend not to be impaired. is there.

  Usually, when a polyethylene wax having a low melt viscosity is mixed with polypropylene and stretch-molded, the viscosity of the entire mixture is lowered, and thus the productivity at the time of molding tends to be improved. However, even if the productivity is improved in this way, there are cases where the resulting film has insufficient mechanical properties or optical properties may be impaired.

  As a result of investigations by the present inventors, the mechanical properties and optical properties of the film obtained by stretch molding are extremely important because the proportion of the component having a molecular weight of 20,000 or more in the polyethylene wax used is related to the melt viscosity. I found out. Although the detailed mechanism is not clear, when melt-kneading polyethylene wax and polypropylene, among the entire polyethylene wax, the component having a molecular weight of 20,000 or more has a specific melting behavior in the entire wax, From the viewpoint of the melt viscosity of the entire polyethylene wax, unless the component having a molecular weight of 20,000 or more is kept below a certain ratio, the polyethylene wax cannot be dispersed well in polypropylene, and the mechanical properties of the final film It is also presumed that the optical properties will be affected.

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 satisfying the condition of the above formula (II) is used, the resulting film tends not to impair the mechanical and optical properties inherent to polypropylene, and there is little bleed out from the surface of the molded product. Tend to be.

  As described above, usually, when polyethylene wax having a low melt viscosity is applied to polypropylene and stretch-molded, the viscosity of the entire mixture is lowered, so that the productivity at the time of molding tends to be improved. However, even if productivity can be improved, the resulting film may lose the mechanical properties inherent to polypropylene, and may also lose optical properties, and bleeding out from the film surface is also a problem. There was a case.

  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 to be used is extremely related to the melt viscosity in the mechanical properties and optical properties of the film obtained by stretch molding. I found it important. Although the detailed mechanism is not clear, when polyethylene wax and polypropylene are melt-kneaded in a molded product, among the whole polyethylene wax, components having a molecular weight of 1,000 or less are easily melted, and the melting behavior thereof is the whole wax. From the viewpoint of the melt viscosity of the entire polyethylene wax, if the component with a molecular weight of 1,000 or less is not less than a certain ratio, it will ooze out to the surface, possibly causing deterioration, etc., and final molding It is presumed to affect the physical properties, optical properties, and bleed out of the body.

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 700 to 4,000. When the number average molecular weight (Mn) of the polyethylene wax is in the above range, the dispersion of the polyethylene wax with respect to polypropylene tends to be good during molding. Moreover, there exists a tendency for the amount of extrusion to improve and the load at the time of extrusion to reduce, and it exists in the tendency for productivity to improve more. Furthermore, even if compared with a molded article obtained without adding polyethylene wax, the mechanical properties of the obtained molded article tend not to be impaired. The number average molecular weight (Mn) of the polyethylene wax is preferably in the range of 800 to 3,800. When the number average molecular weight (Mn) of the polyethylene wax is in the above preferred range, not only the mechanical properties of the resulting molded article are not impaired, but also the mechanical properties may be improved.

  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.

Further, the density (D (kg / m ³ )) of the polyethylene wax is in the range of 890 to 950 (kg / m ³ ). When the density (D) of the polyethylene wax is within the above range, the dispersion of the polyethylene wax in the polypropylene tends to be good during molding. In addition, the extrusion amount tends to increase, the load during extrusion tends to decrease, and the productivity tends to improve. Furthermore, even if compared with a molded article obtained without adding polyethylene wax, the mechanical properties of the obtained molded article tend not to be impaired. When the density of the polyethylene wax exceeds the above range, the optical properties tend to be deteriorated, and bleed out may occur. Although the detailed mechanism is not clear, if the density of the polyethylene wax exceeds the above range, the density difference between the polyethylene wax and the polypropylene increases, and the compatibility between the polyethylene wax and the polypropylene deteriorates, so the optical characteristics tend to deteriorate. It is estimated that bleed out may occur. Moreover, it is preferable that the density (D) of a polyethylene wax is the range of 895-945 (kg / m < ³ >). When the density (D) of the polyethylene wax is in the above preferred range, the optical physical properties of the resulting molded product tend to be less impaired.

  Further, when the number average molecular weight (Mn) of the polyethylene wax is in the above preferred range and the density (D) of the polyethylene wax is in the above preferred range, the mechanical properties and optical properties of the resulting molded product are not impaired.

  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.

  The α-olefin used in the production of the copolymer of ethylene and α-olefin is preferably in the range of 0 to 20 mol%, preferably in the range of 0.1 to 15 mol%, based on the total monomers used. More preferably, it is in the range of 0.1 to 10 mol%.

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 ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (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
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, a cyclopentadienyl group, a fluorenyl group, a bridge portion, and other characteristics which are characteristics of the chemical structure of the bridged metallocene compound according to the present invention will be described in order, and then 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 R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
Any one or more of ¹⁰ , R ¹¹ and R ¹² is a hydrocarbon group (f1), preferably a hydrocarbon group having 1 to 20 carbon atoms (f1 ′), or a silicon-containing group (f2), preferably It means a fluorenyl group substituted with a silicon-containing group (f2 ′) having a total carbon number of 1 to 20. 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, An anionic ligand or a neutral ligand capable of coordinating with a lone pair is selected in the same or different combination. Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone 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 nonconjugated diene, anionic ligand and neutral ligand capable of coordinating with a lone pair of electrons. 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 types 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 (16) below.

(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, etc., 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>.
The shape of the polyethylene wax of the present invention is not particularly limited, but is usually pellet-like or tablet-like particles.

[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 degabromo diphenyl ether and octabromo diphenyl ether, halogen compounds such as halogenated polycarbonates; antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, aluminum hydroxide, etc. Inorganic compounds; phosphorus compounds and the like.

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

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

[Raw material composition ratio]
The composition ratio of polypropylene and polyethylene wax used as a raw material of the present invention is not particularly limited as long as the physical properties of the obtained stretched molded product are not impaired, but is usually 0.01 to 10 weights with respect to 100 parts by weight of polypropylene. Parts, preferably 0.1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight.

  When polypropylene and polyethylene wax are used at a composition ratio in the above range, the effect of improving the fluidity at the time of stretch molding is large, and the molding speed tends to be further improved to improve the productivity. Furthermore, the mechanical properties and optical properties inherent to polypropylene tend not to be impaired. Furthermore, compared with the case where it is stretch-molded 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.

  In the above range, polyethylene wax is particularly preferably in the range of 0.5 to 2 parts by weight with respect to 100 parts by weight of polypropylene. In the said range, since an optical physical property is not impaired more, it is especially preferable.

[Extension molding]
In the method for producing a film of the present invention, the raw material is stretch-molded.
There is no particular limitation on the stretch molding method. Examples of the stretch molding method include a uniaxial stretching method and a biaxial stretching method. Examples of the biaxial stretching method include a tenter method and a tube method.

  In the case of the tenter method, usually, a mixture containing the polypropylene and polyethylene wax of the present invention is melt-kneaded with an extruder and extruded from a T die, and the obtained melt-kneaded product is cooled and solidified on a casting drum, and then slowly. Introduced between the (front) drive roll and the speed (rear) drive roll, stretched to a predetermined magnification in the longitudinal direction, and then put the film stretched in the longitudinal direction into a tenter, holding both lateral ends A stretched film can be produced by further stretching in the transverse direction while heating. At that time, heat treatment may be performed for the purpose of fixing the molecular orientation of the film in the tenter. The means for obtaining an unstretched film is usually based on a T-die molding method, but an unstretched film may be obtained by other known methods.

In the case of the tube method, usually, a mixture containing the polypropylene and polyethylene wax of the present invention is melt-kneaded with an extruder, the molten polymer is extruded from a ring die into a tube shape, rapidly cooled in a cooling bath, and then the tube shape. By heating the thing, introducing air into the inside and pressurizing, or reducing the outside of the tube, stretching in the transverse direction, applying tension in the longitudinal direction and stretching in the longitudinal direction, A stretched film can be produced.

  In the case of the uniaxial method, an unstretched film obtained by T-die molding or inflation molding is usually cooled and then introduced between a slow (front) driving roll and a fast (rear) driving roll. And a stretched film can be manufactured by extending | stretching to a predetermined magnification in the vertical direction. Furthermore, heat treatment may be further performed for the purpose of fixing the molecular orientation of the film.

  When producing by the tenter method using an extruder equipped with a T die, the temperature on the inlet side of the extruder is usually in the temperature range of 130 to 200 ° C, and the temperature on the outlet side of the extruder is 200 to 280 ° C. It is obtained by setting the temperature range and the die temperature in a temperature range of 200 to 260 ° C., extruding from a T-die so that the resin temperature is in the range of 200 to 260 ° C., and stretching to a desired aspect ratio.

  When manufacturing by a tube method, the temperature on the inlet side of the extruder is usually in a temperature range of 120 to 180 ° C, the temperature on the outlet side of the extruder is in a temperature range of 140 to 220 ° C, and the temperature of the die is 140 to 210 ° C. It is set by a temperature range of ° C., and is obtained by extruding from a ring die and stretching to a desired aspect ratio so that the resin temperature is in a range of 140 to 210 ° C.

  When uniaxially stretching an unstretched film obtained by T-die molding, the temperature on the inlet side of the extruder is usually in the temperature range of 130 to 200 ° C, and the temperature on the outlet side of the extruder is in the temperature range of 200 to 280 ° C. The temperature of the die is set in a temperature range of 200 to 260 ° C., and is extruded from a T die so that the resin temperature is in a range of 200 to 260 ° C. and stretched to have a desired longitudinal magnification.

  When uniaxially stretching an unstretched film obtained by inflation molding, the temperature on the inlet side of the extruder is usually in a temperature range of 120 to 180 ° C, the temperature on the outlet side of the extruder is in a temperature range of 140 to 220 ° C, It is obtained by setting the die temperature in a temperature range of 140 to 210 ° C., extruding from a ring die so that the resin temperature is in a range of 140 to 210 ° C., and stretching to a desired longitudinal magnification.

  In the present invention, a film is obtained by the stretch molding described above. The film may be a single layer film or a multilayer film. A single layer film is obtained by the above-mentioned stretch molding. The multilayer film is obtained, for example, by melt-kneading the resin composition forming each layer of the film with separate extruders, pressing the melt-kneaded product into a die for co-extrusion, and further melting and kneading these through the slits of the die. It can manufacture by extruding a thing simultaneously and extending | stretching by the uniaxial stretching method mentioned above and the biaxial stretching method.

  In the multilayer film obtained by the present invention, at least one layer is formed from a resin composition using the above-described polypropylene and polyethylene wax as raw materials, but the other layers are other thermoplastic resin compositions. May be formed. As the above-mentioned melt-kneading and extrusion conditions for the other thermoplastic resin compositions, the extrusion molding conditions usually used for the thermoplastic resin can be applied.

〔Example〕
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
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. Moreover, the number average molecular weight (Mn) calculated | required the molecular weight based on the following conversion method, creating a calibration curve using the 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
(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.
/ Min.

(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. The ratio of ethylene to the total amount of monomers used in polyethylene wax (hereinafter, also referred to as ethylene content) was 90 mol%. 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 with an internal volume of 2 L, sufficiently purged with nitrogen and kept at 25 ° C., was charged with 930 ml of hexane and 35 g of propylene. 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 40 g of polyethylene wax (2). The obtained polyethylene wax (2) has a number average molecular weight (Mn) of 1,300, a weight average molecular weight (Mw) of 3,300, a melt viscosity of 90 mPa · s, a density of 948 kg / m ³ and a melting point of The ethylene content was 115.4 ° C. and 96 mol%. Moreover, A value was 19.8 weight% and B value was 0.3 weight%. The results are shown in Table 1.
The physical properties of the wax used in the present invention are summarized in Table 1.

In the following examples, film physical properties were measured as follows.
(transparency)
According to JIS K7105, the haze of the film formed into the same film thickness was measured.

(productivity)
Productivity was evaluated by maximum stretching stress.
[Maximum stretching stress]
The maximum stress applied when the sheet was simultaneously biaxially stretched using a film biaxial stretching machine (BIX-703, manufactured by Iwamoto Seisakusho) was evaluated.

(Mechanical properties)
The mechanical properties were evaluated by impact resistance.
[Shock resistance]
A film impact tester manufactured by Toyo Seiki Seisakusho is equipped with a hemispherical hammer with a tip diameter of 1.0 inch and a capacity of 3.0 J, and the film sample surface mounted on the testing machine at a temperature condition of 23 ° C. is perpendicular to the above hemispherical hammer. The energy required for breaking (kJ / m) was determined.

Polypropylene resin (Prime Polypro F113G; manufactured by Prime Polymer) (Polypropylene homopolymer) MI = 3.0 g / 10 min (JIS K7210) 100 parts by mass, metallocene polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc.) Density = 913 (kg / m3), Mn = 2,000, A value = 9.3 (% by weight), B value = 2.2 (% by weight), melt viscosity = 300 (mPa · s), ethylene content = 95 (mol%)) 3 parts by mass are mixed with a 65 mmφ single-screw extruder and a T die having a lip width of 600 mm.
A sheet having a thickness of μm was produced. Using a batch type simultaneous biaxial stretching apparatus, preheating 140 ° C. × 5 min, stretching speed 300 mm / sec. A biaxially stretched film having a thickness of 20 μm was produced under a stretching ratio of 5 times (both in the MD direction and TD direction) under annealing conditions of 140 ° C. × 1 min. The maximum stretching stress during biaxial stretching was 3.9 MPa, and there was no unevenness in film thickness, indicating good moldability. Moreover, the impact resistance of the biaxially stretched film was 72.2 kJ / m, and the haze was 0.74%. Moreover, the haze of the sheet prepared in an air oven at 120 ° C. for 24 hours was 0.98%. The results are shown in Table 2.

In Example 1, the polyethylene wax was changed to 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), ethylene content = 92 (mol%)) Then, stretch molding was performed. The results are shown in Table 2.

In Example 1, the polyethylene wax was changed to polyethylene wax (1) (density = 897 (kg / m ³ ), Mn = 800, A value = 23.5 (wt%), B value = 0.01 (wt%).
Stretch molding was performed in the same manner except that the melt viscosity was changed to 40 (mPa · s) and the ethylene content was 90 (mol%). The results are shown in Table 2.

In Example 1, polyethylene wax was changed to polyethylene wax (2) (density = 948 (kg / m ³ ), Mn = 1,300, A value = 19.8 (wt%), B value = 0.3 (wt%)
), Melt viscosity = 90 (mPa · s), ethylene content = 96 (mol%)). The results are shown in Table 2.

  Stretch molding was performed in the same manner as in Example 1 except that the amount of polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc.) was changed to 1 part by mass in Example 1. The results are shown in Table 2.

  Stretch molding was performed in the same manner as in Example 1 except that the amount of polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc.) was changed to 5 parts by mass in Example 1. The results are shown in Table 2.

[Comparative Example 1]
Polypropylene resin (Prime Polypro F113G; manufactured by Prime Polymer Co., Ltd.) (polypropylene homopolymer) MI = 3.0 g / 10 min (JIS K7210) with a 65 mmφ single screw extruder and a 500 μm thick sheet using a T die with a lip width of 600 mm Produced. Using a batch type simultaneous biaxial stretching apparatus, preheating 140 ° C. × 5 min, stretching speed 300 mm / sec. A biaxially stretched film having a thickness of 20 μm was produced under a stretching ratio of 5 times (both in the MD direction and TD direction) under annealing conditions of 140 ° C. × 1 min. The maximum stretching stress during biaxial stretching was 4.3 MPa. Moreover, the impact resistance of the biaxially stretched film was 66.9 kJ / m, and the haze was 0.70%. Moreover, the haze of the sheet prepared in an air oven at 120 ° C. for 24 hours was 0.84%. The results are shown in Table 2.

[Comparative Example 2]
In Example 1, polyethylene wax was changed to polyethylene wax (Excellex 10500; manufactured by Mitsui Chemicals, Inc., density = 960 (kg / m ³ ), Mn = 700, A value = 47.
. Extensive molding was performed in the same manner except that 8 (wt%), B value = 0 (wt%), melt viscosity = 18 (mPa · s), ethylene content = 100 (mol%)). The results are shown in Table 2.

[Comparative Example 3]
In Example 1, the polyethylene wax was changed to polyethylene wax (Excellex 40800T; manufactured by Mitsui Chemicals, Inc., density = 980 (kg / m ³ ), Mn = 2,400, A value = 7.3, B value = 4. 2. Stretch molding was performed in the same manner except that the melt viscosity was changed to 600 (mPa · s) and the ethylene content was set to 100 (mol%). The results are shown in Table 2.

[Comparative Example 4]
In Example 1, the polyethylene wax was changed to 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), ethylene content = 97 (mol%)). The results are shown in Table 2.

[Comparative Example 5]
In Example 1, the polyethylene wax was changed to polyethylene wax (A-C6; manufactured by Honeywell, density = 913 (kg / m ³ ), Mn = 1,800, A value = 6.5 (% by weight), B
Stretch molding was performed in the same manner except that the value was changed to 3.3 (wt%) and melt viscosity = 420 (mPa · s). The results are shown in Table 2.

Polypropylene resin (Prime Polypro F219DA; manufactured by Prime Polymer) (polypropylene random copolymer) MI = 8.0 g / 10 min (JIS K7210) 100 parts by mass, 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 parts by weight (2% by weight), melt viscosity = 300 (mPa · s), ethylene content = 95 (mol%)) were mixed. Using a 65mmφ single screw extruder, 5 with a T die with a lip width of 600mm
A sheet having a thickness of 00 μm was prepared. Using a batch type simultaneous biaxial stretching apparatus, preheating 140 ° C. × 5 min, stretching speed 300 mm / sec. A biaxially stretched film having a thickness of 20 μm was produced under a stretching ratio of 5 times (both in the MD direction and TD direction) under annealing conditions of 140 ° C. × 1 min. The maximum stretching stress during biaxial stretching was 2.7 MPa, and there was no unevenness in the thickness of the film, indicating good moldability. Moreover, the impact resistance of the biaxially stretched film was 91.7 kJ / m, and the haze was 0.67%. Moreover, the haze of the produced sheet was cured in an air oven at 120 ° C. for 24 hours, and the haze was 0.88%. The results are shown in Table 3.

In Example 7, the polyethylene wax was changed to 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), ethylene content = 92 (mol%)) Then, stretch molding was performed. The results are shown in Table 3.

In Example 7, the polyethylene wax was changed to polyethylene wax (1) (density = 897 (kg / m ³ ), Mn = 800, A value = 23.5 (wt%), B value = 0.01 (wt%).
Stretch molding was performed in the same manner except that the melt viscosity was changed to 40 (mPa · s) and the ethylene content was 90 (mol%). The results are shown in Table 3.

In Example 7, the polyethylene wax was changed to polyethylene wax (2) (density = 948 (kg / m ³ ), Mn = 1,300, A value = 19.8 (wt%), B value = 0.3 (wt%).
), Melt viscosity = 90 (mPa · s), ethylene content = 96 (mol%)). The results are shown in Table 3.

  Extensive molding was performed in the same manner as in Example 1 except that the amount of polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc.) was changed to 1 part by mass in Example 7. The results are shown in Table 3.

  Stretch molding was performed in the same manner as in Example 1 except that the amount of polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc.) was changed to 5 parts by mass in Example 7. The results are shown in Table 3.

[Comparative Example 6]
Polypropylene resin (Prime Polypro F219DA; manufactured by Prime Polymer Co., Ltd.) (polypropylene random copolymer) MI = 8.0 g / 10 min (JIS K7210) is produced with a 65 mmφ single screw extruder and a T die with a lip width of 600 mm to produce a 500 μm thick sheet. did. Using a batch type simultaneous biaxial stretching apparatus, preheating 140 ° C. × 5 min, stretching speed 300 mm / sec. A biaxially stretched film having a thickness of 20 μm was produced under a stretching ratio of 5 times (both in the MD direction and TD direction) under annealing conditions of 140 ° C. × 1 min. Maximum stretching stress during biaxial stretching is 2
. It was 9 MPa. Moreover, the impact resistance of the biaxially stretched film was 85.0 kJ / m, and the haze was 0.63%. Moreover, the haze of the sheet prepared in an air oven at 120 ° C. for 24 hours was 0.76%. The results are shown in Table 3.

[Comparative Example 7]
In Example 7, the polyethylene wax was changed to polyethylene wax (Excellex 10500; manufactured by Mitsui Chemicals, Inc., density = 960 (kg / m ³ ), Mn = 700, A value = 47.
. Extensive molding was performed in the same manner except that 8 (wt%), B value = 0 (wt%), melt viscosity = 18 (mPa · s), ethylene content = 100 (mol%)). The results are shown in Table 3.

[Comparative Example 8]
In Example 7, the polyethylene wax was changed to polyethylene wax (Excellex 40800T; manufactured by Mitsui Chemicals, Inc., density = 980 (kg / m ³ ), Mn = 2,400, A value = 7.3, B value = 4. 2. Stretch molding was performed in the same manner except that the melt viscosity was changed to 600 (mPa · s) and the ethylene content was set to 100 (mol%). The results are shown in Table 3.

[Comparative Example 9]
In Example 7, the polyethylene wax was changed to polyethylene wax (High Wax 420P; manufactured by Mitsui Chemicals, density = 930 (kg / m ³ ), Mn = 2,000, A value = 8.3 (wt%), B value = 6. .2 (% by weight), melt viscosity = 700 (mPa · s), ethylene content = 97 (mol%)). The results are shown in Table 3.

[Comparative Example 10]
In Example 7, the polyethylene wax was changed to polyethylene wax (A-C6; manufactured by Honeywell, density = 913 (kg / m ³ ), Mn = 1,800, A value = 6.5 (% by weight), B
Stretch molding was performed in the same manner except that the value was changed to 3.3 (wt%) and melt viscosity = 420 (mPa · s). The results are shown in Table 3.

  According to the present invention, by adding a specific polyolefin wax to the thermoplastic resin, it is possible to reduce the load applied to the screw of the extruder, so that the productivity of extrusion molding can be improved.

Claims (2)

Polypropylene having an MI measured in the range of 0.01 to 100 g / 10 min at 230 ° C. and a test load of 21.18 N according to JIS K7210, and a density measured according to the density gradient tube method of JIS K7112 is 890 to 950 (kg) / m ³⁾ is in the range of, there a number average molecular weight in terms of polyethylene as measured by gel permeation chromatography (GPC) (Mn) is in the range of 700～4,000, and the following formula (I) and formula (II The method of manufacturing a film by extending | stretching the mixture containing the polyethylene wax which satisfy | fills the relationship represented by.
B ≦ 0.0075 × K (I)
(In the above formula (I), B is the content (%) of the component in which the polyethylene-converted molecular weight in the polyethylene wax is 20,000 or more when measured by gel permeation chromatography, and K is (It is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)
A ≦ 230 × K ^(-0.537) (II)
(In the above formula (II), A is a content ratio (% by weight) of a component having a polyethylene conversion molecular weight of 1,000 or less 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 film according to claim 1, wherein a raw material in which polyethylene wax is 0.01 to 10 parts by weight per 100 parts by weight of polypropylene in the mixture is used.