JP5100660B2 - Manufacturing method of spacer for optical fiber cable - Google Patents

Description

  The present invention relates to an optical fiber cable spacer and a method for manufacturing the same.

  Fiber optic cables can be used for data communication over ultra-long distances with less signal attenuation compared to metal cables that communicate using electrical signals, and the communication speed is significantly higher than metal cables. Widely used as a cable.

  In particular, a spacer type optical fiber cable in which an optical fiber core wire is housed in a groove portion of a spacer is widely used because it is excellent in external pressure and impact characteristics. The spacer groove is generally formed in a spiral shape along the optical transmission direction of the optical fiber.

  In addition, a so-called tape slot type cable in which a tape core made of a plurality of optical fibers is housed in one groove of a spacer for the purpose of easily branching in the middle of the optical fiber cable is widely used. It has come to be used. In this tape slot type cable, the spiral direction of the groove is periodically reversed in the SZ shape.

  In order to reduce the optical loss of the optical fiber, for example, the microbending loss, it is necessary to control the shape and size of the groove formed in the spacer with high accuracy. In addition, when transmitting using light in a long wavelength region for long-distance transmission, it is necessary to reduce the surface roughness of the spacer groove as much as possible in order to reduce optical loss.

  Particularly in recent years, optical fiber cables have been required to have higher optical density, smaller diameter, and lighter weight from the viewpoint of cost reduction. There is a need for more control over shape, dimensions, and surface roughness.

  For example, a method of manufacturing a spacer for an optical fiber cable having such characteristics using specific polyethylene has been studied (for example, see Patent Document 1).

In addition, a method of forming a spacer under specific molding conditions using a crystalline thermoplastic resin made of a specific high-density polyethylene as a raw material on the outer periphery of a tensile strength line on which a preliminary coating layer is formed (for example, Patent Document 2). However, in these methods, the molding speed is not always sufficient, and there are problems in terms of productivity and cost reduction.
Japanese Patent No. 3725617 Japanese Patent No. 3579092

  It is an object of the present invention to accurately control the shape, size, and surface roughness of an optical fiber cable spacer, and to improve the molding speed without impairing the mechanical properties required as an optical fiber cable spacer. An object of the present invention is to provide an optical fiber cable spacer manufacturing method and an optical fiber cable spacer obtained by the manufacturing method.

  The inventors of the present invention have studied the above-mentioned problems, and can accurately control the shape, dimensions, and surface roughness of the spacer by melting and extruding a mixture containing a specific polyethylene and a specific polyethylene wax, and are necessary as a spacer. As a result, the present inventors have found that the mechanical properties that are assumed to be obtained are not impaired and that the molding speed of the spacer can be improved, and the present invention has been completed.

That is, the method for producing the optical fiber cable spacer of the present invention,
The density measured according to the density gradient tube method of JIS K7112 is in the range of 940-980 (kg / m ³ ), and the MI measured under the conditions of 190 ° C. and test load 21.18 N according to JIS K7210 is 0.01-0. Polyethylene (1) in the range of 3 g / 10 min;
The density measured according to the density gradient tube method of JIS K7112 is in the range of 890 to 980 (kg / m ³ ), and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) is 500 to 4 It is characterized by melting and extruding a mixture containing polyethylene wax (2) in the range of 1,000 and satisfying the relationship represented by the following formula (I).
B ≦ 0.0075 × K (I)
(In the above formula (I), B is a content ratio (mass%) of a component having a polyethylene conversion molecular weight of 20,000 or more in the polyethylene wax when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)
The polyethylene wax (2) preferably further satisfies the relationship represented by the following formula (II).
A ≦ 230 × K ^(-0.537) (II)
(In the above formula (II), A is the content (mass%) of the component having a molecular weight in terms of polyethylene in the polyethylene wax of 1,000 or less when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)
Moreover, as a method of manufacturing the spacer for optical fiber cable of the present invention,
A method for producing a wax masterbatch (3) containing the above-described polyethylene wax (2) and polyethylene (1), and melting and extruding a mixture containing the wax masterbatch (3) and polyethylene (1). preferable.

  By the above method, a spacer for an optical fiber cable can be manufactured.

  According to the present invention, it is possible to improve the molding speed when manufacturing an optical fiber cable spacer, and to accurately control the shape, size, and surface roughness of the obtained optical fiber cable spacer, and the optical fiber cable. The mechanical properties required as a spacer for use are not impaired.

  Hereinafter, the present invention will be described in detail.

  First, the raw material of the spacer for optical fiber cables obtained by this invention is demonstrated.

〔polyethylene〕
In the present invention, polyethylene refers to an ethylene homopolymer or ethylene and α- with an MI measured in the range of 0.01 to 0.3 g / 10 min at 190 ° C. and a test load of 21.18 N according to JIS K7210. A copolymer with olefin or a blend thereof.

The polyethylene used in the present invention is not particularly limited as long as the density is in the range of 940 to 980 (kg / m ³ ). Specific examples include high-density polyethylene or a blend thereof.

  In the present invention, the measurement conditions for the MI and density of polyethylene are as follows.

(MI)
The measurement was performed in accordance with JIS K7210 at 190 ° C. and a test load of 21.18 N.

(density)
It was measured according to the density gradient tube method of JIS K7112.

As described above, the polyethylene has a density of 940 to 980 (kg / m ³ ), preferably 950 to 980 (kg / m ³ ).

  When the density of polyethylene is in the above range, the obtained spacer is excellent in rigidity and impact resistance.

  Moreover, as MI (190 degreeC) of the said polyethylene, the range of 0.01-0.27 g / 10min is preferable, and the range of 0.01-0.15 g / 10min is more preferable. When the MI of polyethylene is in the above range, the balance between molding processability and the mechanical strength of the obtained spacer is excellent.

  The shape of the polyethylene is not particularly limited, but is usually pellet-shaped or tablet-shaped particles.

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

(Number average molecular weight (Mn))
The number average molecular weight was determined from GPC measurement. The measurement was performed under the following conditions. The number average molecular weight was determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PE conversion / general-purpose calibration method The coefficient of the Mark-Houwink viscosity equation 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 980 (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 used in the present invention is characterized in that there is a specific relationship represented by the following formula (I) between its molecular weight and melt viscosity.
B ≦ 0.0075 × K (I)
Here, in the above formula (I), B is a content ratio (mass on a mass basis) of a component having a polyethylene equivalent 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 satisfying the above condition (I) is used, the molding speed when manufacturing the spacer can be improved, and the shape, dimensions, and surface roughness of the obtained spacer can be accurately controlled, And the mechanical physical property required as a spacer is not impaired.

  Usually, when a mixture of polyethylene and a polyethylene wax having a low melt viscosity is melted, the viscosity of the entire melt obtained is lowered, so that the productivity at the time of molding tends to be improved. However, even if the productivity is improved in this way, the mechanical properties of the resulting optical fiber cable spacer may be impaired. Moreover, the surface roughness of the spacer obtained may not be sufficiently small. Furthermore, there may be a problem in the accuracy of the shape and dimensions of the spacer obtained.

  As a result of investigations by the present inventors, the accuracy of mechanical properties, surface roughness, shape, and dimensions of the obtained spacer is such that the proportion of the component having a molecular weight of 20,000 or more in the polyethylene wax used is the melt viscosity. It turned out to be extremely important in the relationship. Although the detailed mechanism is not clear, when the polyethylene wax and polyethylene are melt-kneaded, among the whole polyethylene wax, the component having a molecular weight of 20,000 or more has a specific melting behavior in the whole wax. From the viewpoint of the melt viscosity of the entire polyethylene wax, if the component having a molecular weight of 20,000 or more is not made a certain ratio or less, the polyethylene wax cannot be dispersed well in the polyethylene, and the mechanical properties of the resulting spacer, Furthermore, it is estimated that the accuracy of surface roughness, shape, and dimensions is also 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 preferably 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 a content ratio (mass%) based on mass of a component having a molecular weight in terms of polyethylene in the polyethylene wax of 1,000 or less when measured by gel permeation chromatography. ). K is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.

  When polyethylene wax that satisfies the condition of the above formula (II) is used, the molding speed when manufacturing the spacer can be improved, and the shape, dimensions, and surface roughness of the obtained spacer can be accurately controlled, And the mechanical physical property required as a spacer is not impaired.

  As described above, usually, when a mixture of polyethylene and polyethylene wax having a low melt viscosity is melted, the viscosity of the entire melt obtained is lowered, so that the productivity at the time of molding tends to be improved. However, even if the productivity can be improved, the resulting spacer mechanical properties of the optical fiber cable may be impaired. Moreover, the surface roughness of the spacer obtained may not be sufficiently small. Furthermore, there may be a problem in the accuracy of the shape and dimensions of the spacer obtained.

  As a result of investigations by the present inventors, it has been found that the ratio of the component having a molecular weight of 1,000 or less in the polyethylene wax to be used is extremely important in relation to the melt viscosity for the mechanical properties of the obtained spacer. It was. Although the detailed mechanism is not clear, when polyethylene wax and polyethylene are melt-kneaded, among the whole polyethylene wax, components having a molecular weight of 1,000 or more are easy to melt and their melting behavior is unique among all waxes. From the viewpoint of the melt viscosity of the entire polyethylene wax, if the component having a molecular weight of 1,000 or less is not less than a certain ratio, the surface of the spacer can exude to the surface and possibly cause deterioration, etc. It is presumed to affect the mechanical properties.

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

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

The polyethylene wax has a number average molecular weight (Mn) in the range of 500 to 4,000, preferably in the range of 700 to 3,500, and particularly preferably in the range of 800 to 3,000.
When the number average molecular weight (Mn) of the polyethylene wax is in the above range, the dispersion of the polyethylene wax in the polyethylene tends to be better during molding. Moreover, since the tendency which the extrusion amount improves and the tendency which the load at the time of extrusion reduces decreases more, it exists in the tendency for productivity to improve more. Furthermore, even when compared with a molded article obtained without adding polyethylene wax, there is a tendency that the surface roughness can be further reduced without impairing the mechanical properties of the obtained spacer.

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

The density of the polyethylene wax ^{(D (kg / m 3)} ) is in the range of 890~980 (kg / m ^3), preferably in the range of ^{910~980 (kg / m 3),} 940~980 (kg / A range of m ³ ) is particularly preferred. When the density (D) of the polyethylene wax is within the above range, the dispersion of the polyethylene wax in the polyethylene tends to be better during molding. Moreover, since the tendency for the amount of extrusion to improve and the tendency for the load during extrusion to decrease during the spacer molding become more prominent, productivity tends to be further improved. Furthermore, even if it compares with the molded object obtained without adding polyethylene wax, the mechanical characteristic of the obtained molded object is 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.

  It is preferable that the α-olefin used in the production of the copolymer of ethylene and α-olefin is in the range of 0 to 20 mol% with respect to all monomers used.

  The density of the polyethylene wax can also be controlled by the polymerization temperature. For example, when a polyethylene wax is produced by a metallocene catalyst described later, the polymerization temperature is usually in the range of 100 to 200 ° C., but from the viewpoint of producing a polyethylene wax having a density in the preferred range described above, the polymerization temperature is , Preferably, it is the range of 100-180 degreeC, More preferably, it is the range of 100-170 degreeC.

  Such polyethylene wax is solid at normal temperature and becomes a low-viscosity liquid at 65 to 130 ° C.

Further, the polyethylene wax preferably has the crystallization temperature [Tc (° C.)] measured by a differential scanning calorimeter (DSC) and the density [D (kg / m ³ )] measured by the density gradient method. Formula (III) below
0.501 × D-366 ≧ Tc (III)
More preferably, the following formula (IIIa)
0.501 × D-366.5 ≧ Tc (IIIa)
More preferably, the following formula (IIIb)
0.501 × D-367 ≧ Tc (IIIb)
Satisfy the relationship.

  When the crystallization temperature (Tc) and the density (D) in the polyethylene wax satisfy the relationship of the above formula, the dispersibility of the polyethylene wax in polyethylene 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 a polyethylene wax that satisfies the relationship of the above formula, 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.

As another example of the metallocene compound, in the general formula (2), at least two of R ² , R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ are groups having a cyclopentadienyl skeleton ( A bridge type metallocene compound in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like. At this time, R ⁴ and R ⁵ are each independently the same as the ligand L other than the ligand having the cyclopentadienyl skeleton described above.

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

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

Here, M ¹ is a Group 4 transition metal of the periodic table, and specifically includes titanium, zirconium, and hafnium.

R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; Aryloxy group having 6 to 10 carbon atoms; alkenyl group having 2 to 10 carbon atoms; arylalkyl group having 7 to 40 carbon atoms; alkylaryl group having 7 to 40 carbon atoms; arylalkenyl group having 8 to 40 carbon atoms Or a halogen atom, and R ¹¹ and R ¹² are preferably chlorine atoms.

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

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

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

^{= BR 21, = AlR 21,} -Ge -, - Sn -, - O -, - S -, = SO, = SO 2, = NR 21, = CO, = PR 21, = P (O) R 21 , etc. . M ² is silicon, germanium or tin, preferably silicon or germanium. 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, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom-containing group or Y representing a sulfur atom-containing group 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, or divalent germanium. containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 30 -, - P (R 30) -, - P (O) ( R ³⁰ ) —, —BR ³⁰ — or —AlR ³⁰ — (wherein R ³⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Indicates.

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, rac-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 -, - NR 35 -, - P (R 35) -, - P (O) (R 35) -, - BR ³⁵ — or —AlR ³⁵ — (wherein R ³⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 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 halogenated hydrocarbon group having 1 to 20 carbon atoms). 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, and R ¹³ and R ¹⁴ may be selected from a hydrocarbon group and a silicon-containing group, and may be the same or different, and R ¹³ and R ¹⁴ are bonded to each other to form a ring. Q may be selected from the same or different combinations from a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair, and j is an integer of 1 to 4 .)
Hereinafter, after describing sequentially the cyclopentadienyl group, the fluorenyl group, the crosslinked part, and other characteristics that are the chemical structure characteristics of the bridged metallocene compound according to the present invention, a preferable bridged metallocene compound having these characteristics will be described. .
Cyclopentadienyl group The cyclopentadienyl group may or may not be substituted. The cyclopentadienyl group which may or may not be substituted means that R ¹ , R ² , R ³ and R ⁴ possessed by the cyclopentadienyl group moiety in the general formula (11) are all hydrogen atoms. Or any one or more of R ¹ , R ² , R ³ and R ⁴ is a hydrocarbon group (f1), preferably a hydrocarbon group having 1 to 20 carbon atoms (f1 ′), or silicon-containing It means a cyclopentadienyl group substituted by a group (f2), preferably a silicon-containing group (f2 ′) having a total carbon number of 1 to 20. When two or more of R ¹ , R ² , R ³ and R ⁴ are substituted, these substituents may be the same as or different from each other. Further, the hydrocarbon group having 1 to 20 carbon atoms in total is an alkyl, alkenyl, alkynyl, or aryl group composed of only carbon and hydrogen. These include those in which any two adjacent hydrogen atoms are simultaneously substituted to form an alicyclic or aromatic ring. The hydrocarbon group having 1 to 20 carbon atoms in total (f1 ′) includes, in addition to alkyl, alkenyl, alkynyl and aryl groups composed only of carbon and hydrogen, some of the hydrogen atoms directly connected to these carbon atoms are halogen atoms. , An oxygen-containing group, a nitrogen-containing group, a heteroatom-containing hydrocarbon group substituted with a silicon-containing group, or a group in which any two adjacent hydrogen atoms form an alicyclic group. Examples of such a group (f1 ′) include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Linear hydrocarbon group such as octyl group, n-nonyl group, n-decanyl group; isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1- Branching of dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, etc. Cyclic hydrocarbon group: Cyclic saturated hydrocarbon group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; Saturated hydrocarbon groups and these Saturated hydrocarbon group substituted with an aryl group such as benzyl group and cumyl group; methoxy group, ethoxy group, phenoxy group N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group And a heteroatom-containing hydrocarbon group such as a pentafluorophenyl group.
The silicon-containing group (f2) is, for example, a group in which a ring carbon of a cyclopentadienyl group is directly covalently bonded to a silicon atom, and specifically an alkylsilyl group or an arylsilyl group. Examples of the silicon-containing group (f2 ′) having a total carbon number of 1 to 20 include a trimethylsilyl group and a triphenylsilyl group.
Fluorenyl group The fluorenyl group may or may not be substituted. The fluorenyl group which may or may not be substituted is R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² possessed by the fluorenyl group moiety in the general formula (11). Are all hydrogen atoms, or at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is a hydrocarbon group (f1), preferably Means a fluorenyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms (f1 ′) or a silicon-containing group (f2), preferably a silicon-containing group having 1 to 20 carbon atoms (f2 ′) To do. When two or more of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are substituted, the substituents may be the same or different from each other. Good. Further, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be bonded to each other to form a ring. In view of the ease of production of the catalyst, those in which R ⁶ and R ¹¹ and R ⁷ and R ¹⁰ are the same are preferably used.
A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a preferable example of the silicon-containing group (f2) is the above-described total number of carbon atoms of 1 to 20. It is a silicon-containing group (f2 ′).
Covalent bond bridge The main chain part of the bond connecting the cyclopentadienyl group and the fluorenyl group is a divalent covalent bond containing one carbon, silicon, germanium and tin atom. For example, when performing high temperature solution polymerization, an important point is that the bridging atom Y of the covalent bond bridging portion has R ¹³ and R ¹⁴ which may be the same or different from each other. A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a preferable example of the silicon-containing group (f2) is the above-described total number of carbon atoms of 1 to 20. It is a silicon-containing group (f2 ′).
Other characteristics of the bridged metallocene compound In the general formula (11), Q is halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, They are selected from the same or different combinations from anionic ligands or neutral ligands that can coordinate with a lone pair of electrons. Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. 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 is Ti, Zr or Hf. , Y is a Group 14 atom, Q is a halogen, a hydrocarbon group, neutral having 10 or less carbon atoms, a conjugated or nonconjugated diene, an anionic ligand, and a neutral configuration capable of coordination with a lone pair of electrons. They are selected from the group consisting of 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- Such as cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl, etc. Can be mentioned.

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

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

The adjacent substituents from R ¹ to R ¹⁴ on the cyclopentadienyl ring of the general formula (12) may be bonded to each other to form a ring.

  M in the general formula (12) is a group 4 element of the periodic table, that is, zirconium, titanium or hafnium, preferably zirconium.

  Y is a Group 14 atom, preferably a carbon atom or a silicon atom. n is an integer of 2 to 4, preferably 2 or 3, particularly preferably 2.

  Q is the same or different combination from the group consisting of halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated diene, anionic ligand and neutral ligand capable of coordinating with a lone electron pair. To be elected. When Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to 10 carbon atoms.

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

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

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

In formula (13), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms, hydrocarbon groups, silicon R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each a hydrogen atom or a hydrocarbon group, n is an integer of 1 to 3, and n = 1 In some cases, R ¹ to R ¹⁶ are not hydrogen atoms and may be the same or different. Adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring, may be R ¹³ and R ¹⁵ are bonded to each other to form a ring, and R ¹³ and R ¹⁵ are each R ¹⁴ and R ¹⁶ may combine with each other to form a ring by bonding to form a ring, Y ¹ and Y ² are group 14 atoms, which may be the same or different from each other, and M is Ti, Zr or Hf, Q may be selected from halogen, hydrocarbon group, anionic ligand or neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is 1 to 4 It is an integer.
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. For example, when performing high temperature solution polymerization, a characteristic property is that a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be applied. In addition, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, and JP-A-3-103407, etc. It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound used in the above high-temperature solution polymerization means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2 in terms of Al atoms. % Or less, which means insoluble or hardly soluble in benzene.

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

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

  Furthermore, as the organoaluminum oxy compound used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula (17) can also be exemplified.

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

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

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

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

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

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

Among the above, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  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- Trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, Dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate Dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium Mo tetrakis (3,5-ditrifluoromethylphenyl) borate, such as dioctadecyl methyl ammonium.

  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-branched alkylaluminums such as tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triphenyl Triarylaluminum such as aluminum and tolylylaluminum; diisopropylaluminum hydride, diisobutyl Dialkylaluminum hydrides such as aluminum hydride; formula _{(iC 4 H 9) x Al} y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and 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. Specific examples of such a compound include (C2H5) 2AlN (C2H5) Al (C2H5) 2. From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.

<Polymerization>
The polyethylene wax used in the present invention can be 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 methods include suspension polymerization in which polyethylene wax is polymerized in the presence of particles in a solvent such as hexane, gas phase polymerization in which no solvent is used, and at a polymerization temperature of 140 ° C. or higher, polyethylene wax is mixed with the solvent. 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. 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 to 10,000, preferably It is used in an amount of 1 to 5000.

The polymerization reaction is usually at a temperature of −20 to + 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 180 ° C., and the pressure is usually greater than 0 to 7.8 MPa (80 kgf / cm ² , gauge pressure). Hereinafter, it is preferably carried out under the condition of 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 needed are supplied to the polymerization system in such a proportion that the polyethylene 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 polyethylene wax can be obtained by processing in a conventional manner.

  In the present invention, it is particularly preferable to use a catalyst containing the metallocene compound shown in <Example 1 of metallocene compound>.

  When such a catalyst is used, a polyethylene wax having the above-described characteristics can be easily obtained.

  The shape of the polyethylene wax of the present invention is not particularly limited, but is usually a pellet-like or tablet-like particle.

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

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

  Examples of the metal soap include stearates such as magnesium stearate, calcium stearate, barium stearate, and zinc stearate.

  Examples of the filler include calcium carbonate, titanium oxide, barium sulfate, talc, clay, and carbon black.

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

  Moreover, a compound such as tetrafluoroethylene can be added as a flame retardant aid for preventing drip.

Examples of the antibacterial and antifungal agents include organic compounds such as imidazole compounds, thiazole compounds, nitrile compounds, haloalkyl compounds, and pyridine compounds;
Examples include inorganic substances such as silver, silver compounds, zinc compounds, copper compounds, and titanium compounds, and inorganic compounds.

  Among these compounds, thermally stable silver and silver-based compounds are preferable. Examples of the silver compound include silver complexes and silver salts such as fatty acids and phosphoric acids. 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.

As the pigment, pigments conventionally used for coloring synthetic resins can be used. Specifically, metals such as aluminum, silver and gold; carbonates such as calcium carbonate and barium carbonate; oxides such as ZnO and TiO ₂ ; Al ₂ O ₃ .nH ₂ O, Fe ₂ O ₃ .nH ₂ hydroxides such as O; CaSO _4, sulfate such as BaSO _4; chlorides such as PbCl _2;; Bi (OH) nitrate such as ₂ NO ₃ CaCrO _4, such BaCrO ₄ chromate; such CoCrO ₄ Chromite, manganate and permanganate; borates such as Cu (BO) ₂ ; uranates such as Na ₂ U ₂ O ₇ · 6H ₂ O; K ₃ Co (NO ₂ ) ₆ · 3H Nitrites such as ₂ O; Silicates such as SiO ₂ ; Arsenates and arsenites such as CuAsO ₃ .Cu (OH) ₂ ; Cu (C ₂ H ₃ O ₂ ) ₂ .Cu (OH) _{2 and the} like acetate; phosphates such as _{(NH 4) 2 MnO 2 (} P 2 O 7) 2; a Mi salt, molybdate, zincate, antimonate, tungstate selenides, titanates, cyan Katetsushio, phthalates, CaS, ZnS, CdS, graphite, inorganic pigments such as carbon black,
Natural organic pigments such as Cochineal Lake and Madder Lake, nitroso pigments such as naphthol green Y and naphthol green B; nitro pigments such as naphthol yellow S and pigment chlorin 2G; permanent red 4R; 68, azo pigments such as Scarlet 2R; basic dye lakes such as maracaine green and rhodamine B; acid dye lakes such as acid, green lake and eosin lake; mally dye lakes such as alizarin lake and pullpurin lake; Organic pigments such as vat dyes such as Thio Indigo Red B and Inslenne Orange, and phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.

  Examples of other additives include plasticizers, anti-aging agents, and oils.

[Raw material composition ratio]
The composition ratio of polyethylene 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 optical fiber cable spacer are not impaired, but usually 0.01 to 100 parts by mass of polyethylene. The range is 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, and particularly preferably 0.5 to 2 parts by mass.

  When polyethylene and polyethylene wax are used at a composition ratio in the above range, the effect of improving the fluidity when molding the spacer is great, and the molding speed is further improved, and the productivity tends to be improved. Furthermore, the mechanical properties inherent to polyethylene tend not to be impaired. Furthermore, compared to the case where molding is performed without adding polyethylene wax, molding tends to be possible 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.

[Wax masterbatch]
In the present invention, a method for producing a spacer for an optical fiber cable by first producing a wax masterbatch containing the polyethylene wax and the polyethylene, melt-extruding a mixture containing the wax masterbatch and the polyethylene, This is a preferred embodiment. Thus, when a spacer is manufactured using a wax masterbatch, the shape, dimensions, and surface roughness of the obtained spacer can be accurately controlled, and the mechanical properties required as a spacer are not impaired, The molding speed can be further improved.

  The method for producing the wax masterbatch used in the present invention is not particularly limited. For example, the wax masterbatch can be produced by melt-kneading the polyolefin wax, the polyethylene, and, if necessary, the additives described above. The melt kneading can be performed, for example, with an extruder, a plast mill, a Brabender, a kneader, a roll mixer, a Banbury mixer, or the like.

  The temperature at the time of melt kneading is not particularly limited as long as it is a temperature at which polyethylene wax or polyethylene melts, but is usually in the range of 170 to 220 ° C, preferably in the range of 180 to 200 ° C.

  The wax masterbatch used in the present invention can also be obtained by mixing a solution containing polyethylene wax and a solution containing polyethylene and removing the solvent from this mixed solution.

  The blending amount of the polyethylene wax in the wax masterbatch used in the present invention is not particularly limited, but is usually in the range of 5 to 95 parts by mass, preferably 10 to 100 parts by mass of polyethylene contained in the wax masterbatch. It is the range of -90 mass parts, More preferably, it is the range of 20-80 mass parts.

  When a masterbatch blended with polyethylene wax in the above range is used, the effect of improving the fluidity during the molding of the spacer is great, and the molding speed tends to be further improved.

  The overall composition ratio of polyethylene and polyethylene wax and the preferred mode thereof when using a wax masterbatch are the same as those described in the above section “Raw material composition ratio”.

  In the present invention, a wax masterbatch, if necessary, stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, metal soaps, fillers, flame retardants, plasticizers, anti-aging agents, pigments, colorants An additive such as oil may be added.

[Spacer manufacturing method]
The spacer of the present invention can be produced by melt-extruding the mixture containing polyethylene and polyethylene wax or the mixture containing polyethylene and wax masterbatch so as to have a desired shape on the tensile strength line (tension member).

  Tensile wires used for spacers for optical fiber cables include single steel wires, steel stranded wires, FRP linear materials reinforced with various reinforcing fibers, coated tensile wires with a pre-coating layer made of resin, etc. Is mentioned.

  A more specific example of the manufacturing method will be described as follows. A crosshead and an extruder having a rotary die attached to the outlet of the crosshead are prepared. The rotating die has an opening corresponding to the cross-sectional shape of the spacer. The shape of the opening is usually an uneven gear shape, and the shape of the spacer groove is determined by this shape. The shape of the spacer groove is determined according to the number of optical fiber cores or tape cores stored, the purpose of use of the optical fiber, and the like, and examples of the shape include a square groove, a U groove, and a V groove. Further, the number of groove portions of the spacer is determined by the number of openings of the rotary die.

  In this extruder, the mixture containing polyethylene and polyethylene wax or the mixture containing polyethylene and wax masterbatch is melt-kneaded, and the resulting melt is extruded from a rotary die onto a tensile strength line introduced into a crosshead. . At the time of extrusion, the rotating die rotates, and the helical pitch of the spacer is determined by the rotation speed. Further, when manufacturing a tape slot type cable spacer in which the direction of the spiral is periodically reversed in the SZ shape, the rotating die is reversed according to a desired shape.

  The melt kneading temperature in the extruder is not particularly limited as long as it is a temperature at which the polyethylene and polyethylene wax can be melt kneaded, but is usually 180 to 250 ° C.

  Thus, the spacer for the optical fiber cable of the present invention can be manufactured. However, when manufacturing the spacer, other known techniques for manufacturing the spacer may be combined with the above method. Furthermore, you may manufacture with the manufacturing method of the other well-known optical fiber cable spacer which uses polyethylene as a spacer.

  By applying such a manufacturing method, the molding speed when manufacturing a spacer for an optical fiber cable can be improved, and the shape, dimensions, and surface roughness are accurately controlled, and the required mechanical properties are obtained. An optical fiber cable spacer can be obtained without damage.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

  In the following examples, the physical properties of polyethylene and polyethylene wax were measured as follows.

(Number average molecular weight (Mn))
The number average molecular weight (Mn) is obtained from GPC measurement. The measurement was performed under the following conditions. The number average molecular weight (Mn) was determined by preparing a calibration curve using commercially available monodisperse standard polystyrene and calculating the molecular weight based on the following conversion method.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PE conversion / general-purpose calibration method For the calculation of general-purpose calibration, the coefficient of the Mark-Houwink viscosity equation shown below was used.
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 in terms of mass%, and this was taken as the A value. Moreover, from the measurement result of GPC, the ratio of the component with a molecular weight of 20,000 or more was calculated | required in the mass%, and it was set as B value.

(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.) was measured under the condition of a temperature drop rate of 2 ° C./min according to ASTM D 3417-75.

  In the following examples, the physical properties of the polyethylene resin composition and the optical fiber cable spacer were measured as follows.

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

(productivity)
The take-up speed (m / min) when the resin was melt-extruded on the tensile strength line was evaluated.

(Surface roughness of spacer side surface)
According to JIS B0601, the average roughness (Ra; unit: μm) of the groove side surface of the manufactured spacer was measured.

○ Ra ≦ 1.0
△ 1.0 <Ra ≦ 1.5
× Ra> 1.5
(Spacer rib shape retention)
The rib shape retainability of the manufactured spacer was evaluated.

○ There is no rippling or falling of the ribs × Rippling or tumbling [Preparation of master batch]
Metallocene polyethylene wax (Excellex 40800T; prepared using 30 parts by mass of pellets of high-density polyethylene resin (Hi-Zex 5100B; manufactured by Prime Polymer Co., Ltd., MI = 0.27 (g / 10 min)) and a metallocene catalyst. Pellet made by Mitsui Chemicals, Inc., density = 980 (kg / m ³ ), Mn = 2,400, A value = 7.3, B value = 4.2, melt viscosity = 600 (mPa · s) 70 parts by mass are mixed using a mixer, and this mixture is melt-extruded using a twin-screw extruder set at a die temperature of 180 ° C., and the extrudate is pelletized to produce a master batch (1). did.

[Example 1]
High density polyethylene resin (Hi-Zex 6300M; manufactured by Prime Polymer Co., Ltd., MI = 0.11 (g / 10 min), density = 951 (kg / m ³ )) to 100 parts by mass of metallocene 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, melt viscosity = 600 (mPa · s)) 2 Mass parts were mixed. Then, using a φ45 mm extruder equipped with a cross head having a rotary die at its outlet, a pre-coated layer of modified polyethylene was provided on the outer periphery of a single steel wire having an outer diameter of 2.0 mm, and the outer diameter was 3.8 mm. The resulting mixture was melt extruded while rotating the die on the outer periphery of the coated tensile strength wire under the conditions of a take-up speed of 18 m / min and a die temperature of the rotary die of 180 ° C. to obtain a groove width of 1.45 mm and a groove depth. 3. A spacer having 5 spiral grooves of 20 mm and an outer diameter of 10.00 mm and a spiral pitch of 500 mm was obtained. The discharge was stable, and the obtained spacer had no uneven surface roughness on the groove side surface, and a good shape was obtained. The results are shown in Table 2.

[Example 2]
Except for changing the addition amount of metallocene polyethylene wax (Excellex 40800T; manufactured by Mitsui Chemicals, Inc.) to 1 part by mass, it was melt extruded at a take-up speed of 12 m / min in the same manner as in Example 1, and spacers Got. The results are shown in Table 2.

Example 3
Polyethylene wax is a metallocene polyethylene wax (Excellex 30200BT; manufactured by Mitsui Chemicals, Inc., density: 913 (kg / m ³ ), Mn = 2,000, A value = 9.3, B value = 2.2, Except for changing to melt viscosity = 300 (mPa · s), melt extrusion was performed in the same manner as in Example 1 to obtain a spacer. The results are shown in Table 2.

Example 4
Polyethylene wax is a metallocene polyethylene wax (Excellex 10500; manufactured by Mitsui Chemicals, Inc., density = 960 (kg / m ³ ), Mn = 700, A value = 47.8, B value = 0, melt viscosity = 18 Except for changing to (mPa · s)), melt extrusion was performed in the same manner as in Example 1 to obtain a spacer. The results are shown in Table 2.

Example 5
High-density polyethylene resin (Hi-zex 6300M; manufactured by Prime Polymer Co., Ltd., MI = 0.11 (g / 10 min), density = 951 (kg / m ³ )) 99.1 parts by mass in master batch (1)) 2.9 parts by mass were mixed. Then, using a φ45 mm extruder equipped with a cross head having a rotary die at its outlet, a pre-coated layer of modified polyethylene was provided on the outer periphery of a single steel wire having an outer diameter of 2.0 mm, and the outer diameter was 3.8 mm. The resulting mixture was melt extruded while rotating the die on the outer periphery of the coated tensile strength wire under the conditions of a take-up speed of 18 m / min and a die temperature of the rotary die of 180 ° C. to obtain a groove width of 1.45 mm and a groove depth. 3. A spacer having 5 spiral grooves of 20 mm and an outer diameter of 10.00 mm and a spiral pitch of 500 mm was obtained. The discharge was stable, and the obtained spacer had no uneven surface roughness on the groove side surface, and a good shape was obtained. The results are shown in Table 2.

Example 6
High density polyethylene resin (Hi-Zex 6300M; manufactured by Prime Polymer Co., Ltd., MI = 0.11 (g / 10 min), density = 951 (kg / m ³ )) 99.6 parts by mass and masterbatch (1) 1 A spacer was obtained by melt extrusion at a take-up speed of 12 m / min in the same manner as in Example 5 except that the amount was changed to 4 parts by mass. The results are shown in Table 2.

[Comparative Example 1]
Using a 45 mm extruder equipped with a crosshead having a rotary die at its outlet, a precoated layer of modified polyethylene is provided on the outer periphery of a single steel wire having an outer diameter of 2.0 mm, and the outer diameter is 3.8 mm. A high-density polyethylene resin (Hi-Zex 6300M; manufactured by Prime Polymer Co., Ltd., MI = 0.11) while rotating the die on the outer periphery of the tensile strength wire under the conditions of a take-up speed of 18 m / min and a die temperature of the rotary die of 180 ° C. (G / 10 min), density = 951 (kg / m ³ )) 100 parts by mass are melt-extruded to have five spiral grooves having a groove width of 1.45 mm and a groove depth of 3.20 mm. A spacer having a groove pitch of 10.00 mm and a spiral pitch of 500 mm was obtained. The surface of the obtained spacer groove side surface was rough, and a good shape could not be obtained. The results are shown in Table 2.

[Comparative Example 2]
A spacer was obtained by melt extrusion in the same manner as in Comparative Example 1 except that the take-up speed was changed to 12 m / min. The results are shown in Table 2.

[Comparative Example 3]
A spacer was obtained by melt extrusion in the same manner as in Comparative Example 1 except that the take-up speed was changed to 6 m / min. The results are shown in Table 2.

[Comparative Example 4]
Polyethylene wax is made of polyethylene wax (high wax 420P; manufactured by Mitsui Chemicals, density = 930 (kg / m ³ ), Mn = 2,000, A value = 8.3, B value = 6.2, melt viscosity = 700 ( Except for the change to mPa · s)), melt extrusion was performed in the same manner as in Example 1 to obtain a spacer. The results are shown in Table 2.

[Comparative Example 5]
Polyethylene wax is made of polyethylene wax (A-C6; manufactured by Honeywell, density = 913 (kg / m ³ ), Mn = 1,800, A value = 6.5, B value = 3.3, melt viscosity = 420 (mPa -Except having changed into s)), it melt-extruded by the method similar to Example 1 and obtained the spacer. The results are shown in Table 2.

Claims (4)

The density measured according to the density gradient tube method of JIS K7112 is in the range of 940-980 (kg / m ³ ), and the MI measured under the conditions of 190 ° C. and test load 21.18 N according to JIS K7210 is 0.01-0. Polyethylene (1) in the range of 3 g / 10 min;
The density measured according to the density gradient tube method of JIS K7112 is in the range of 890 to 980 (kg / m ³ ), and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) is 500 to 4 A method for producing a spacer for an optical fiber cable by melting and extruding a mixture containing polyethylene wax (2) that is in the range of 1,000 and satisfying the relationship represented by the following formula (I).
B ≦ 0.0075 × K (I)
(In the above formula (I), B is a content ratio (mass%) of a component having a polyethylene conversion molecular weight of 20,000 or more in the polyethylene wax when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.) The method for producing a spacer for an optical fiber cable according to claim 1, wherein the polyethylene wax (2) further satisfies a relationship represented by the following formula (II).
A ≦ 230 × K ^(-0.537) (II)
(In the above formula (II), A is the content (mass%) of the component having a molecular weight in terms of polyethylene in the polyethylene wax of 1,000 or less when measured by gel permeation chromatography, and K Is the melt viscosity (mPa · s) of the polyethylene wax at 140 ° C.)   A wax masterbatch (3) comprising the polyethylene wax (2) according to claim 1 or 2 and the polyethylene (1) according to claim 1 is prepared, and the wax masterbatch (3) and A method for producing a spacer for an optical fiber cable by melting and extruding a mixture containing polyethylene (1).   The spacer for optical fiber cables obtained from the manufacturing method of any one of Claims 1-3.