KR101104610B1 - Method for production of spacer for optical fiber cable - Google Patents

Abstract

Polyethylene (1) having a density in the range of 940 to 980 kg / m 3 (density gradient pipe method of JIS K7112), MI in the range of 0.01 to 0.3 g / 10 minutes (JIS K7210), and density of 890 to It is in the range of 980 kg / m 3 (density gradient pipe method of JIS K7112), the number average molecular weight (Mn) of polyethylene conversion measured by GPC is in the range of 500 to 4,000, and satisfies the relationship represented by the following formula (I): A spacer for an optical fiber cable obtained by melting and extruding a mixture containing polyethylene wax (2) and a method for producing the same.

Equation I

B≤0.0075 × K

(In said Formula (I), B is the content rate (mass%) of the component by which the molecular weight of polyethylene conversion in the said polyethylene wax becomes 20,000 or more when it measures by GPC, and K is the 140 degreeC of the said polyethylene wax. Melt viscosity (mPa · s).)

Description

Manufacturing method of spacer for optical fiber cable {METHOD FOR PRODUCTION OF SPACER FOR OPTICAL FIBER CABLE}

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

Optical fiber cables are widely used as communication cables because they have less attenuation of signals and enable data communication at very long distances, and communication speeds are significantly faster than metal cables, compared to metal cables that communicate with electrical signals. Doing.

In particular, the spacer-type optical fiber cable, in which the optical fiber core wire is accommodated in the groove portion of the spacer, is widely used because of its excellent pressure from outside, impact characteristics, and the like. The groove of this spacer is generally formed in a spiral along the optical transmission direction of the optical fiber.

In addition, so-called tape slot type cables, which have a tape core wire made of a plurality of optical fiber core wires in one groove of a spacer, have been widely used for the purpose of easily diverging in the middle of an optical fiber cable. . In this tape slot type cable, the spiral direction of the groove is periodically reversed to the SZ phase.

And in order to reduce the optical loss of this optical fiber, for example, microbending loss, it is necessary to control the shape and dimension of the groove | channel formed in this spacer with high precision. In addition, when transmitting using light in a long wavelength region for long distance transmission, in order to reduce light loss, it is necessary to make the surface roughness of the groove of the spacer as small as possible.

In particular, in recent years, optical fiber cables have been required to have higher optical density, thinner, and lighter weight from the viewpoint of cost reduction, and thus the shape, dimensions, and surface roughness of the grooves formed in the spacer are more highly. You need to control it.

For example, the method of manufacturing the spacer for optical fiber cables which has such a characteristic using specific polyethylene is examined (for example, refer patent document 1).

Moreover, on the outer periphery of the tension tension line in which the preliminary coating layer was formed, the method which uses a crystalline thermoplastic resin which consists of specific high density polyethylene as a raw material, and forms a spacer on specific molding conditions is examined (for example, refer patent document 2). However, in these methods, the molding speed may not always be sufficient, and there existed a problem in terms of productivity, cost reduction, etc.

Patent Document 1: Japanese Patent No. 3725617

Patent Document 2: Japanese Patent No. 3579092

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

It is an object of the present invention to precisely control the shape, dimensions, and surface roughness of a spacer for an optical fiber cable, and furthermore, an optical fiber cable capable of improving the molding speed without impairing the mechanical properties required for the optical fiber cable spacer. It is providing the spacer for optical fiber cables obtained by the manufacturing method of the spacer for this, and the manufacturing method.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM The present inventors considered the said subject, and by melt-extruding the mixture containing a specific polyethylene and a specific polyethylene wax, the shape, dimension, and surface roughness of a spacer can be precisely controlled, and also the mechanical properties required as a spacer are needed. The present invention has been completed by finding out that the molding speed of the spacer can be improved without being damaged.

That is, the method for manufacturing the spacer for the optical fiber cable of the present invention,

The density measured according to the density gradient pipe method of JIS K7112 is in the range of 940-980 (kg / m <3>), and MI measured on the conditions of 190 degreeC and test load 21.18N according to JIS K7210 is 0.01-0.3 g / 10min. Polyethylene (1) which is a range of,

The density measured according to the density gradient pipe method of JIS K7112 is in the range of 890-980 (kg / m <3>), and the number average molecular weight (Mn) of polyethylene conversion measured by gel permeation chromatography (GPC) is 500-4,000. It is also characterized by melting and extruding a mixture comprising polyethylene wax (2) which satisfies the relationship represented by the following formula (I).

B≤0.0075 × K

(In Formula (I), B is a content ratio (mass%) of the component whose molecular weight in terms of polyethylene in the polyethylene wax is 20,000 or more when measured by gel permeation chromatography, and K is 140 ° C of the polyethylene wax. Melt viscosity in mPa · s.)

The polyethylene wax (2) preferably further satisfies the relationship represented by the following formula (II).

A≤230 × K ^(-0.537)

(In Formula (II), A is the content ratio (mass%) of the component whose molecular weight of polyethylene conversion in the polyethylene wax is 1,000 or less when measured by gel permeation chromatography, and K is 140 ° C of the polyethylene wax. Melt viscosity in mPa · s.)

Moreover, as a method of manufacturing the spacer for optical fiber cables of this invention,

A method of producing a wax masterbatch (3) comprising the polyethylene wax (2) and polyethylene (1) described above, and melting and extruding the mixture comprising the wax masterbatch (3) and polyethylene (1) desirable.

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

Effects of the Invention

According to the present invention, the molding speed at the time of manufacturing the spacer for the optical fiber cable can be improved, and in addition, the shape, dimensions, and surface roughness of the optical fiber cable spacer obtained can be precisely controlled, and the spacer for the optical fiber cable As a result, the required mechanical properties are not impaired.

Carrying out the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated 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 is a homopolymer of ethylene or a copolymer of ethylene and α-olefin having a MI measured in the range of 0.01 to 0.3 g / 10 min, measured at 190 ° C. under a test load of 21.18 N according to JIS K7210. , Or their blends.

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). Specifically, high density polyethylene or its blend is mentioned.

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

(MI)

According to JIS K7210, it measured on 190 degreeC and the conditions of 21.18N of test load.

(density)

It measured according to the density gradient pipe method of JISK7112.

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

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

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 exists in the said range, the balance of the moldability and the mechanical strength of the spacer obtained is excellent.

Although the shape of the said polyethylene is not specifically limited, Usually, it is a pellet form or a tablet form particle | grains.

[Polyethylene Wax]

In the present invention, the polyethylene wax is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having a number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography (GPC) in the range of 500 to 4,000, or their Say blends. The number average molecular weight (Mn) of polyethylene conversion of the said polyethylene wax is calculated | required from the gel permeation chromatography (GPC) measurement on condition of the following.

(Number average molecular weight (Mn))

The number average molecular weight was determined from the GPC measurement. The measurement was performed on condition of the following. In addition, the number average molecular weight created the analytical curve using commercially available monodisperse standard polystyrene, and calculated | required it based on the following conversion method.

Apparatus: Gel Permeation Chromatograph Alliance GPC2000 Type (manufactured by Waters)

Solvent: o-dichlorobenzene

Column: TSKgel column (manufactured by Tosoh Corporation) × 4

Flow rate: 1.0ml / min

Sample: 0.15 mg / mL o-dichlorobenzene solution

Temperature: 140 ℃

Molecular weight conversion: PE conversion / universal calibration

In addition, the coefficient of the Mark-Houwink viscosity formula shown below was used for calculation of general-purpose calibration.

Modulus of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70

Modulus of polyethylene (PE): KPE = 5.06 × 10 ^-4 , aPE = 0.70

Since polyethylene wax exists in the composition and molecular weight as mentioned above, there exists a tendency for the productivity at the time of shaping | molding to improve.

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 said polyethylene wax is the value measured by the density gradient pipe method of JISK7112. When the density of a polyethylene wax exists in the said range, there exists a tendency for the productivity at the time of shaping | molding to improve.

The polyethylene wax used in the present invention is characterized in that there is a specific relationship represented by the following formula (I) between the molecular weight and the melt viscosity.

Equation I

B≤0.0075 × K

Here, in said Formula (I), B is content ratio (mass%) in the mass reference | standard of the component whose molecular weight of polyethylene conversion in the said polyethylene wax becomes 20,000 or more when it measures by gel permeation chromatography. In addition, K is melt viscosity (mPa * s) at 140 degreeC of the said polyethylene wax measured with the Brookfield (B type) viscometer.

In the case of using the polyethylene wax that satisfies the condition of the above formula (I), the molding speed at the time of manufacturing the spacer can be improved, and the shape, dimensions, and surface roughness of the spacer obtained can be precisely controlled, In addition, the mechanical properties required as spacers are not impaired.

Usually, when the mixture of polyethylene and polyethylene wax with a low melt viscosity is melted, since the viscosity of the whole melt obtained will fall, there exists a tendency for the productivity at the time of shaping | molding to improve. However, even if productivity was improved in this way, the mechanical properties of the resulting optical fiber cable spacer were sometimes damaged. In addition, the surface roughness of the spacer obtained may not be small enough. Furthermore, there existed a problem in the precision of the shape and dimension of the spacer obtained.

As a result of examination by the present inventors, it turned out that the ratio of the component whose molecular weight is 20,000 or more in the polyethylene wax used is very important in relationship with melt viscosity to the precision of the mechanical properties, surface roughness, shape, and dimension of the spacer obtained. Although the detailed mechanism is not clear, when melt-kneading polyethylene wax and polyethylene, the component of molecular weight 20,000 or more among the whole polyethylene wax, the melt behavior is specific also in the whole wax, from the viewpoint of melt viscosity of the whole polyethylene wax, If a component having a molecular weight of 20,000 or more is not set below a certain ratio, the polyethylene wax cannot be dispersed well with polyethylene, and it is estimated that it also affects the mechanical properties, the surface roughness, the shape and the precision of the spacer obtained.

Polyethylene wax whose B value is the said range can be prepared using a metallocene catalyst. Among the metallocene catalysts, metallocene catalysts in which the ligand is uncrosslinked are preferable. As such a metallocene catalyst, the metallocene compound represented by General formula (1) mentioned later can be illustrated.

Furthermore, the said B value can also be controlled by superposition | polymerization temperature. For example, when producing a polyethylene wax with the metallocene catalyst mentioned later, superposition | polymerization temperature is the range of 100-200 degreeC normally, From a viewpoint of manufacturing the polyethylene wax which has the above-mentioned B value, superposition | polymerization temperature becomes like this. It is the range of 100-180 degreeC, More preferably, it is the range of 100-170 degreeC.

It is preferable that the polyethylene wax of this invention has further the specific relationship represented by following formula (II) between the molecular weight and melt viscosity.

Equation II

A≤230 × K ^(-0.537)

Here, in said Formula (II), A is content ratio (mass%) in the mass reference | standard of the component whose molecular weight of polyethylene conversion in the said polyethylene wax becomes 1,000 or less when it measures by gel permeation chromatography. K is the melt viscosity (mPa · s) at 140 ° C. of the polyethylene wax.

In the case of using the polyethylene wax that satisfies the condition of the above formula (II), the molding speed at the time of manufacturing the spacer can be improved, and the shape, dimensions, and surface roughness of the spacer obtained can be precisely controlled, In addition, the mechanical properties required as spacers are not impaired.

As mentioned above, when melt | melting the mixture of polyethylene and polyethylene wax with low melt viscosity normally, since the viscosity of the whole melt obtained will fall, it exists in the tendency to improve regarding productivity at the time of shaping | molding. However, even if productivity could be improved, the mechanical properties of the resulting optical fiber cable spacer were sometimes damaged. In addition, the surface roughness of the spacer obtained may not be small enough. Furthermore, there existed a problem in the precision of the shape and dimension of the spacer obtained.

As a result of examination by the present inventors, it turned out that the ratio of the component whose molecular weight is 1,000 or less in the polyethylene wax to be used for the mechanical properties of the spacer obtained etc. is very important in relationship with melt viscosity. Although the detailed mechanism is not clear, in the case of melt kneading polyethylene wax and polyethylene, the component of molecular weight 1,000 or more is easy to melt among the whole polyethylene wax, and its melting behavior is specific among the whole wax, and the melt viscosity of the whole polyethylene wax In view of the above, it is estimated that the component having a molecular weight of 1,000 or less does not bleed out to the surface, soaks to the surface, and in some cases, deteriorates and the like, and also affects the surface smoothness and the mechanical properties of the spacer obtained.

Polyethylene wax whose A value is the said range can be prepared using a metallocene catalyst. Among the metallocene catalysts, metallocene catalysts in which the ligand is uncrosslinked are preferable. As such a metallocene catalyst, the metallocene compound represented by General formula (1) mentioned later can be illustrated.

Furthermore, the said A value can also be controlled by superposition | polymerization temperature. For example, when producing a polyethylene wax with the metallocene catalyst mentioned later, superposition | polymerization temperature is the range of 100-200 degreeC normally, From a viewpoint of manufacturing the polyethylene wax which has the above-mentioned A value, superposition | polymerization temperature becomes like this. It is the range of 100-180 degreeC, More preferably, it is the range of 100-170 degreeC.

The number average molecular weight (Mn) of the said polyethylene wax is the range of 500-4,000, the range of 700-3,500 is preferable, and the range of 800-3,000 is especially preferable.

When the number average molecular weight (Mn) of polyethylene wax exists in the said range, it exists in the tendency for dispersion of the polyethylene wax with respect to polyethylene to become favorable when shape | molding. Moreover, since the tendency which the extrusion amount improves and the tendency which the load at the time of extrusion reduce becomes more remarkable, there exists a tendency which productivity improves more. Furthermore, compared with the molded object obtained without adding polyethylene wax, it exists in the tendency which can make surface roughness smaller, without compromising the mechanical characteristic of the spacer obtained.

Mn of polyethylene wax can be controlled by polymerization temperature or the like. For example, when manufacturing a polyethylene wax with the metallocene catalyst mentioned later, superposition | polymerization temperature is the range of 100-200 degreeC normally, but from a viewpoint of manufacturing the polyethylene wax which has Mn of the above-mentioned family register range, superposition | polymerization is carried out. The temperature is preferably in the range of 100 to 180 ° C, more preferably in the range of 100 to 170 ° C.

In addition, the density (D (kg / m 3)) of polyethylene wax is in the range of 890 to 980 (kg / m 3), preferably in the range of 910 to 980 (kg / m 3), and of 940 to 980 (kg / m 3) Range is particularly preferred. When the density (D) of polyethylene wax exists in the said range, it exists in the tendency for dispersion of the polyethylene wax with respect to polyethylene to become favorable at the time of shaping | molding. Moreover, since the tendency which the extrusion amount improves and the tendency which the load at the time of extrusion reduces is more remarkable at the time of spacer shaping | molding, productivity tends to improve more. Furthermore, even when compared 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, when the molecular weight of polyethylene wax is made low, the density of the polymer obtained can be controlled low. In the case where the polyethylene wax is a copolymer of ethylene and an α-olefin, the density of the polyethylene wax depends on the size of the number average molecular weight (Mn), and also depending on the amount of α-olefin to ethylene during polymerization and its type. Can be controlled. For example, by increasing the amount of α-olefin to ethylene, 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.

As an alpha olefin used for manufacture of the copolymer of the said ethylene and the C3-C20 alpha olefin, a C-C10 alpha olefin is preferable 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 alpha olefin used for manufacture of the copolymer of the said ethylene and alpha olefin exists in the range of 0-20 mol% with respect to the all monomers used.

In addition, the density of polyethylene wax can be controlled also by superposition | polymerization temperature. For example, when producing a polyethylene wax with the metallocene catalyst mentioned later, superposition | polymerization temperature is the range of 100-200 degreeC normally, but from a viewpoint of manufacturing the polyethylene wax which has the density of the above-mentioned family range, polymerization temperature is preferable. Preferably it is the range of 100-180 degreeC, More preferably, it is the range of 100-170 degreeC.

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

Further, the polyethylene wax 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.

0.501 × D-366≥Tc

More preferably, the following formula IIIa

0.501 × D-366.5≥Tc

More preferably, the following formula IIIb

0.501 × D-367≥Tc

Satisfies the relationship.

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

Polyethylene wax that satisfies the relationship of the above formula can be prepared using a metallocene catalyst. Among the metallocene catalysts, metallocene catalysts in which the ligand is uncrosslinked are preferable. As such a metallocene catalyst, the metallocene compound represented by General formula (1) mentioned later can be illustrated.

Furthermore, polyethylene wax that satisfies the relationship of the above formula can also be produced by controlling the polymerization temperature. For example, when producing a polyethylene wax with the metallocene catalyst mentioned later, superposition | polymerization temperature is the range of 100-200 degreeC normally, but from a viewpoint of manufacturing the polyethylene wax which satisfy | fills the relationship of the said Formula, superposition | polymerization temperature is preferable. Preferably it is the range of 100-180 degreeC, More preferably, it is the range of 100-170 degreeC.

Suitable metallocene catalysts in the present invention are, for example,

(A) a metallocene compound of transition metal selected from Group 4 of the periodic table, and

(B) (b-1) an organoaluminumoxy compound,

    (b-2) a compound which forms an ion pair by reacting with the crosslinked metallocene compound (A) and

    (b-3) organoaluminum compound

A catalyst for olefin polymerization consisting of at least one compound selected from

Can be mentioned.

These are demonstrated in detail below.

<Metallocene compound>

(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 a transition metal selected from Group 4 of the periodic table, and specific examples thereof include a compound represented by the following formula (1).

M ¹ Lx

Here, M ¹ is a transition metal selected from Group 4 of the periodic table, x is the 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 for coordinating to the transition metal M ¹ , at least one of the ligands L is a ligand having a cyclopentadienyl skeleton, and the ligand having a cyclopentadienyl skeleton may have a substituent. As the ligand L having a cyclopentadienyl skeleton, for example, a cyclopentadienyl group, a methyl cyclopentadienyl group, an ethyl cyclopentadienyl group, n- or i-propyl cyclopentadienyl group, n-, i- alkyl or cycloalkyl such as a sec- or t-butyl cyclopentadienyl group, a dimethyl cyclopentadienyl group, a methylpropyl cyclopentadienyl group, a methylbutyl cyclopentadienyl group, and a methylbenzyl cyclopentadienyl group Substituted cyclopentadienyl group; Furthermore, indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, etc. are mentioned. Hydrogen of the ligand having this cyclopentadienyl skeleton may be substituted with a halogen atom, a trialkylsilyl group, or the like.

In the case where the metallocene compound described above has two or more ligands having a cyclopentadienyl skeleton as the ligand L, the ligands having two cyclopentadienyl skeletons are each alkyl such as ethylene or propylene. Ren group; Substituted alkylene groups, such as isopropylidene and diphenylmethylene; It may be couple | bonded via substituted silylene groups, such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group.

As ligands other than a ligand having a cyclopentadienyl skeleton (a ligand without a cyclopentadienyl skeleton) L, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, and a sulfonic acid-containing group (-SO ₃ R ¹ ), a halogen atom or a hydrogen atom, wherein 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 aryl group substituted with an alkyl group. have.

<Example 1 of Metallocene Compound>

When the metallocene compound represented by the formula (1) is, for example, the valence of the transition metal is 4, more specifically, it is represented by the formula (2).

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ¹

Here, M ¹ is a transition metal selected from Group 4 of the periodic table, R ² is a group having a cyclopentadienyl skeleton (ligand), and R ³ , R ⁴ and R ⁵ are each independently a cyclopentadienyl skeleton A group (ligand) with or without. k is an integer of 1 or more, and k + l + m + n = 4.

Examples of the metallocene compound containing at least two ligands in which M ¹ is zirconium and also has a cyclopentadienyl skeleton are given below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethe Insulfonate), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride and the like.

Among the above compounds, compounds in which a 1,3-position substituted cyclopentadienyl group is substituted with a 1,2-position substituted cyclopentadienyl group can also be used.

In addition, as another example of the metallocene compound, in Formula 2, at least two of R ² , R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ have a cyclopentadienyl skeleton (relationship) Or 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.

As such a bridge type metallocene compound, ethylenebis (indenyl) dimethyl zirconium, ethylene bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl- fluorenyl) zirconium dichloride, diphenyl Silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride, etc. are mentioned.

<Example-2 of the metallocene compound>

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

Here, M ¹ is a periodic table group 4 transition metal, and specifically, titanium, zirconium, and hafnium are mentioned.

R ¹¹ and R ¹² may be the same as or different from each other, and are a hydrogen atom; Alkyl groups having 1 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Aryl groups having 6 to 10 carbon atoms; Aryloxy groups having 6 to 10 carbon atoms; Alkenyl groups having 2 to 10 carbon atoms; Arylalkyl groups having 7 to 40 carbon atoms; Alkylaryl groups having 7 to 40 carbon atoms; Arylalkenyl groups 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 as or different from each other, and are a hydrogen atom; Halogen atom; An alkyl group having 1 to 10 carbon atoms which may be halogenated; Aryl groups having 6 to 10 carbon atoms; -N (R ²⁰ ) ₂ , -SR ²⁰ , -OSi (R ²⁰ ) ₃ , -Si (R ²⁰ ) ₃ or -P (R ²⁰ ) ₂ groups. Wherein, R ²⁰ is a halogen atom, preferably 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> is the same as R <^13> and R <^14> except that a hydrogen atom is not contained, and may mutually be same or different, Preferably it is the same. R ¹⁵ and R ¹⁶ are preferably an alkyl group having 1 to 4 carbon atoms which may be halogenated, specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. In particular, methyl is preferred.

In 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 mutually be same or different, and may be a hydrogen atom; Halogen atom; Alkyl groups having 1 to 10 carbon atoms; Fluoroalkyl groups having 1 to 10 carbon atoms; Aryl groups having 6 to 10 carbon atoms; Fluoroaryl groups having 6 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Alkenyl groups having 2 to 10 carbon atoms; Arylalkyl groups having 7 to 40 carbon atoms; Arylalkenyl groups 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 be integrated with the atoms to which they are bonded, respectively, to form a ring. In addition, R ¹⁷ is preferably = CR ²¹ R ²² , = SiR ²¹ R ²² , = GeR ²¹ R ²² , -O-, -S-, = SO, = PR ²¹ or = P (O) R ²¹ . R <^18> and R <^19> may mutually be same or different, and the same thing as R <^{21> is} mentioned. m and n may mutually be same or different, respectively, 0, 1 or 2, Preferably it is 0 or 1, and m + n is 0, 1 or 2, Preferably it is 0 or 1.

As an example of the metallocene compound represented by the said Formula (3), the following compound is mentioned. 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 manufactured by the method of Unexamined-Japanese-Patent No. 4-268307, for example.

<Example-3 of Metallocene Compound>

In addition, as a metallocene compound, the metallocene compound represented by following 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, or the like. R ²⁴ and R ²⁵ may be the same as or different from each other, and a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group , Sulfur-containing group, nitrogen-containing group or phosphorus-containing group. R ²⁴ is preferably a hydrocarbon group, and particularly preferably an alkyl group having 1 to 3 carbon atoms of methyl, ethyl or propyl. R ²⁵ is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms of methyl, ethyl or propyl. R <^26> , R <^27> , R <^28> and R <^29> may mutually be same or different, and represent a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, and a C1-C20 halogenated hydrocarbon group. In these, it is preferable that they are a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group. R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ At least 1 group of these may be integral with the carbon atom to which they couple | bond, and may form the monocyclic aromatic ring. Moreover, when two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group which forms an aromatic ring, they may combine with each other and may be cyclic. Moreover, when R ²⁹ is substituents other than an aromatic group, it is preferable that it is a hydrogen atom. X ¹ and X ² may be the same as or different from each other, and a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen atom-containing group, or a sulfur atom Y representing a 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, a divalent germanium-containing group, and a divalent tin-containing group. Group, -O-, -CO-, -S-, -SO-, -SO _2- , -NR ^30- , -P (R ³⁰ )-, -P (O) (R ³⁰ )-, -BR ³⁰ Or -AlR ^30- (wherein R ³⁰ represents a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms).

In Chemical Formula 4, R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ Among them, at least one group includes a monocyclic aromatic ring formed by bonding to each other, and the ligands coordinated to M ³ include those represented by the following formulas.

(Y is the same as shown in the previous formula.)

<Example-4 of Metallocene Compound>

As a metallocene compound, the metallocene compound represented by following formula (5) can also be used.

In formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same as in formula (4). R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ It is preferable that two groups containing R <^26> are alkyl groups among them, and it is preferable that R <^26> and R <^28> or R <^28> and R <^29> are alkyl groups. It is preferable that this alkyl group is a secondary or tertiary alkyl group. In addition, this alkyl group may be substituted by the halogen atom and the silicon containing group, and examples of the halogen atom and the silicon-containing group include the substituents exemplified in R ²⁴ and R ²⁵ . It is preferable that group other than an alkyl group is a hydrogen atom among R <^26> , R <^27> , R <^28> and R <^29> . In addition, R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be bonded to each other by two kinds of groups selected from these to form a monocyclic or polycyclic ring other than an aromatic ring. As a halogen atom, the thing similar to the said R <^24> and R <^{25> is} mentioned. The same thing as the above is mentioned as X <^1> , X <^2> and Y.

Specific examples of the metallocene compound represented by Chemical 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 di Chloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride and the like.

In these compounds, a transition metal compound obtained by substituting a zirconium metal with a titanium metal or a hafnium metal may be used. The transition metal compound is usually used as a racemate, but R type or S type can also be used.

<Example-5 of Metallocene Compound>

As a metallocene compound, the metallocene compound represented by following formula (6) can also be used.

In formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are the same as in formula (4). R ²⁴ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms of 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. As X <^1> and X <^2> , it is preferable that they are a halogen atom and a hydrocarbon group of 1-20 carbon atoms.

Specific examples of the metallocene compound represented by the formula (6) are as follows. 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. Moreover, in these compounds, the transition metal compound which substituted the zirconium metal with the titanium metal or the hafnium metal can also be used.

<Example 6 of Metallocene Compound>

As the metallocene compound, a metallocene compound represented by the following formula (7) may also be used.

LaM ⁴ X ³ ₂

Here, M ⁴ is a metal of Group 4 or lanthanide series of the periodic table. La is a derivative of the delocalized π bond group, metal M ⁴ It is a group giving a constrained geometry to the active site. X ³ may be the same as 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 low density group containing 20 or less germanium.

In this compound, the compound represented by following formula (8) is preferable.

In formula (8), M ⁴ is titanium, zirconium or hafnium. X ³ is the same as described in the general formula (7). Cp is a π bond to M ⁴ , and is a substituted cyclopentadienyl group having a substituent Z. Z is oxygen, sulfur, boron or an element of Group 4 of the periodic table (eg silicon, germanium or tin). Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and may form a condensed ring with Z and Y. Specific examples of the metallocene compound represented by the formula (8) are as follows. (Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl)- 1,2-ethanedinyl) titanium dichloride and the like. Moreover, in this metallocene compound, the compound which substituted titanium with zirconium or hafnium is also mentioned.

<Example 7 of Metallocene Compound>

Moreover, as a metallocene compound, the metallocene compound represented by following 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, at least one of which 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, or 12 carbon atoms At least two adjacent groups of the alkylaryl group or the silicon-containing group or the group represented by R ³¹ together with the carbon atom to which they are bonded form a single or a plurality of aromatic rings or aliphatic rings. In this case, including the carbon atom to which the coupling ring, R ³¹ is formed by R ³¹ is a carbon number of 4 to 20 as a whole. Aryl group, arylalkyl group, aryl alkenyl group, alkylaryl group and R ³¹ other than the aromatic ring, R ³¹ that forms an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms or a silicon-containing group . R ³² may be the same as or different from each other, and 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, and 7 carbon atoms An arylalkyl group having from 40 to 40 carbon atoms, an aryl alkenyl group having from 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. In addition, at least two adjacent groups among the groups represented by R ³² may form a single or plural aromatic rings or aliphatic rings together with the carbon atoms to which they are bonded. In this case, the ring formed by R ^32, R ³² and the carbon number of 4 to 20 as a whole, including the carbon atom to which they bind, R ^32, which forms an aromatic ring, an aliphatic ring Other R ³² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a silicon-containing group. Moreover, the aspect by which two groups represented by R <^{32> form} single or multiple aromatic ring or aliphatic ring by which a fluoreneyl group becomes a structure as follows is also included.

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 of methyl, ethyl or propyl. As a fluorenyl group which has R <^32> as such a substituent, a 2,7-dialkyl- fluorenyl group is mentioned as a suitable example, As an alkyl group of 2,7-dialkyl in this case, it is C1-C5 An alkyl group. In addition, R <^31> and R <^32> may mutually be same or different. R ³³ and R ³⁴ may be the same as or different from each other, and the same hydrogen atom, halogen atom, alkyl group of 1 to 10 carbon atoms, aryl group of 6 to 20 carbon atoms, and 2 to 10 carbon atoms Alkenyl group, arylalkyl group having 7 to 40 carbon atoms, aryl alkenyl group having 8 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group Or a phosphorus containing group. Among 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 as or different from each other, and a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, or a sulfur-containing group Or a conjugated diene residue formed from a nitrogen containing group or X ¹ and X ² . As the conjugated diene residue formed from X ¹ and X ² , 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-diphenylbutadiene Residues are preferable, and these residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms. As X <^1> and X <^2> , it is preferable that they are a halogen atom, a C1-C20 hydrocarbon group, 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 - represents a (where, R ³⁵ is a hydrogen atom, a halogen atom, a halogenated hydrocarbon to the number of carbon atoms from 1 to 20 hydrocarbon group, of 1 to 20 carbon atoms in the group). Among these divalent groups, it is preferable that the shortest connection part of -Y- is comprised by one or two atoms. In addition, R ³⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 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, and more preferably alkylsilylene, alkylarylsilylene or aryl Particularly preferred is silylene.

<Example-8 of Metallocene Compound>

Moreover, as a metallocene compound, the metallocene compound represented by following 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, and preferably zirconium. R ³⁶ may be the same as or different from each other, 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, a silicon-containing group, It is an oxygen containing group, a sulfur containing group, a nitrogen containing group, or a phosphorus containing group. Moreover, the said alkyl group and alkenyl group may be substituted by the halogen atom. It is preferable that R <^36> is an alkyl group, an aryl group, or a hydrogen atom among these, Especially methyl, ethyl, n-propyl, i-propyl hydrocarbon group of 1-3 carbon atoms, phenyl, (alpha)-naphthyl, (beta)- It is preferable that they are aryl groups, such as naphthyl, or a hydrogen atom. R ³⁷ may be the same as or different from each other, and 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, and 7 carbon atoms An arylalkyl group having from 40 to 40 carbon atoms, an aryl alkenyl group having from 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. In addition, halogen may be substituted for the alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group, and alkylaryl group. Of these, R ³⁷ is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms of methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl. Do. In addition, said R ³⁶ and R ³⁷ may mutually be same or different. One of R ³⁸ and R ³⁹ is an alkyl group having 1 to 5 carbon atoms, the other is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and silicon Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group. Among these, R ³⁸ and R ³⁹ each preferably represent an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, or propyl, and the other is a hydrogen atom. X ¹ and X ² may be the same as or different from each other, and a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, or a sulfur-containing group Or a conjugated diene residue formed from a nitrogen containing group or X ¹ and X ² . Among them, 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 represents a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms). Of 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, more preferably a divalent silicon-containing group, and more preferably alkylsilylene and alkylarylsilylene. Or arylsilylene is particularly preferred.

<Example 9 of Metallocene Compounds>

Moreover, as a metallocene compound, the metallocene compound represented by following formula (11) can also be used.

In 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, respectively, and adjacent substituents from R ⁵ to R ¹² are bonded to each other to form a ring; may be formed, R ^13, R ¹⁴ may be the same or different it may be selected from a hydrocarbon group and a silicon-containing group, respectively, R ¹³ And R ¹⁴ may be bonded to each other to form a ring. Q may be selected in the same or different combinations from halogen, a hydrocarbon group, an anion ligand, or a neutral ligand coordinated with a lone pair, and j is an integer from 1 to 4.)

Hereinafter, after describing the cyclopentadienyl group, fluorenyl group, crosslinking part, and other characteristics which are the characteristics on the chemical structure of the crosslinked metallocene compound which concerns on this invention sequentially, the preferable crosslinked metallocene compound which has these characteristics together Explain.

Cyclopentadiene diary

The cyclopentadienyl group may or may not be substituted. The cyclopentadienyl group which may or may not be substituted means that all of R ¹ , R ² , R ³ and R ⁴ possessed by the cyclopentadienyl group moiety in the formula (11) are hydrogen atoms or R ¹ , R ² , At least one of R ³ and R ⁴ is a hydrocarbon group (f1), preferably a hydrocarbon group (f1 ') having 1 to 20 carbon atoms, or a silicon-containing group (f2), preferably having 1 to 20 carbon atoms It means the cyclopentadienyl group substituted by the silicon containing group (f2 '). When two or more of R <^1> , R <^2> , R <^3> and R <^4> are substituted, these substituents may mutually be same or different. 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. This includes those in which any two adjacent hydrogen atoms are substituted at the same time to form an alicyclic or aromatic ring. As the hydrocarbon group (f1 ') having 1 to 20 carbon atoms in total, in addition to the alkyl, alkenyl, alkynyl, and aryl groups composed of only carbon and hydrogen, some of the hydrogen atoms directly connected to these carbon atoms are halogen atoms and oxygen-containing groups. And a hetero atom-containing hydrocarbon group substituted with a nitrogen-containing group and a silicon-containing group, or those in which any two adjacent hydrogen atoms form an alicyclic group. As such a group (f '), a methyl group, an ethyl group, n-propyl group, an allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Linear hydrocarbon groups such as nonyl and n-decanyl groups; Isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1- Branched hydrocarbon groups such as propylbutyl group, 1,1-dimethyl-2-methylpropyl group and 1-methyl-1-isopropyl-2-methylpropyl group; Cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, and adamantyl group; Cyclic unsaturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group and their nuclear alkyl substituents; Saturated hydrocarbon groups in which aryl groups such as benzyl and cumyl groups are substituted; And hetero atom-containing hydrocarbon groups such as methoxy group, ethoxy group, phenoxy group, N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group and pentafluorophenyl group.

The silicon-containing group (f2) is a group in which the ring carbon of the cyclopentadienyl group is directly covalently bonded to the silicon atom, and specifically, is an alkylsilyl group or an arylsilyl group. Examples of the silicon-containing group (f2 ') having 1 to 20 carbon atoms in total include a trimethylsilyl group, a triphenylsilyl group, and the like.

Fluorenyl group

The fluorenyl group may not be substituted. The fluorenyl group which may or may not be substituted is a hydrogen atom in which all of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² possessed by the fluorenyl group moiety in Formula 11 Or any one or more of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is a hydrocarbon group (f1), preferably a hydrocarbon group having a total of 1 to 20 carbon atoms (f1) ') Or a silicon-containing group (f2), preferably a fluorenyl group substituted with a silicon-containing group (f2') having 1 to 20 carbon atoms in total. When two or more of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are substituted, these substituents may be the same as or different from each other. In addition, R <^5> , R <^6> , R <^7> , R <^8> , R <^9> , R <^10> , R <^11> and R <^12> may combine with each other, and may form the ring. From the ease of preparation of the catalyst, those in which R ⁶ and R ¹¹ and R ⁷ and R ¹⁰ are identical to each other are preferably used.

Preferred group of the hydrocarbon group (f1) is the hydrocarbon group (f1 ') having 1 to 20 carbon atoms as described above, and a preferable example of the silicon-containing group (f2) is the silicon-containing group (f2') having 1 to 20 carbon atoms as described above. )to be.

Covalent crosslinking

The main chain portion of the bond connecting the cyclopentadienyl group and the fluorenyl group is a divalent covalent crosslink containing one carbon, silicon, germanium and tin atom. For example, in the case of performing high temperature solution polymerization, an important point is that the crosslinking atoms Y of the covalent crosslinking portion have the same or different R ¹³ and R ¹⁴ . Preferred group of the hydrocarbon group (f1) is the hydrocarbon group (f1 ') having 1 to 20 carbon atoms as described above, and a preferable example of the silicon-containing group (f2) is the silicon-containing group (f2') having 1 to 20 carbon atoms as described above. )to be.

Bridge Metallocene  Other features of the compound

In Formula 11, Q is the same or different combination from halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral ligand capable of coordinating with a neutral, conjugated or nonconjugated diene, anionic ligand, or a lone pair having 10 or less carbon atoms. Is selected. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, and 2,2-di Methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, 1,3-trimethyl butyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1- cyclohexyl, etc. are mentioned. Specific examples of neutral, conjugated or nonconjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1, 4-phenyl-1, 3-butadiene, s- cis-or trans-s- -η ⁴ -3- methyl-1,3-penta diene, s- cis-or trans-s- -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 (tri Methyl silyl) -1, 3- butadiene etc. are mentioned. Specific examples of the anion 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 capable of coordinating with lone electron pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, And ethers such as 1,2-dimethoxyethane. j is an integer of 1-4, and when j is 2 or more, Q may mutually be same or different.

<Example-10 of Metallocene Compound>

Moreover, as a metallocene compound, the metallocene compound represented by following formula (12) can also be used.

Wherein 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, a hydrocarbon group, Selected from silicon-containing groups, each may be the same or different, adjacent substituents from R ¹ to R ¹⁴ may combine with each other to form a ring, M is Ti, Zr or Hf, Y is a Group 14 atom, Q is selected from the same or different combinations from the group consisting of halogens, hydrocarbon groups, neutral or conjugated or non-conjugated dienes having 10 or less carbon atoms, anion ligands, and neutral ligands capable of coordinating with lone pairs of electrons, n being 2-4 Integer, j is an integer of 1-4.

In the 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 an alkylaryl group having 7 to 20 carbon atoms, and at least one ring. It may contain a structure.

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

In the above formula (12), the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms or 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, and triphenyl. Silyl and the like.

In the present invention, R ¹ to R ¹⁴ in Chemical Formula 12 are selected from hydrogen, a hydrocarbon group and a silicon-containing hydrocarbon group, and may be the same or different. As a specific example of a preferable hydrocarbon group and a silicon containing hydrocarbon group, the thing similar to the above is mentioned.

Adjacent substituents from R ¹ to R ¹⁴ on the cyclopentadienyl ring of Formula 12 may combine with each other to form a ring.

M in Formula 12 is an element of Group 4 of the periodic table, i.e. 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 2-4, Preferably it is 2 or 3, Especially preferably, it is 2.

Q is selected from the same or different combinations from the group consisting of halogens, hydrocarbon groups, neutral or conjugated or non-conjugated dienes having 10 or less carbon atoms, anion ligands and neutral ligands capable of coordinating with lone electron pairs. When Q is a hydrocarbon group, More preferably, it is a C1-C10 hydrocarbon group.

Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, and 2,2-di Methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, 1,3-trimethyl butyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1- cyclohexyl, etc. are mentioned. Specific examples of neutral, conjugated or nonconjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1, 4-phenyl-1, 3-butadiene, s- cis-or trans-s- -η ⁴ -3- methyl-1,3-penta diene, s- cis-or trans-s- -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 (tri Methyl silyl) -1, 3- butadiene etc. are mentioned. Specific examples of the anion ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, sulfonate groups such as mesylate and tosylate and the like. Specific examples of neutral ligands capable of coordinating with lone electron pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, And ethers such as 1,2-dimethoxyethane. When j is an integer of 2 or more, some Q may be same or different.

In the formula (12), Y is present in plural numbers of 2 to 4, and plural Y's may be the same or different from each other. The plurality of R ^{13 's} and the plurality of R ¹⁴ ' s bonded to Y may be the same as or different from each other. For example, some R <^13> couple | bonded with the same Y may mutually differ, and some R <^13> couple | bonded with different Y may mutually be the same. R ¹³ Or R ¹⁴ You may form a ring.

As a preferable example of the Group 4 transition metal compound represented by General formula (12), the compound represented by following General formula (13) is mentioned.

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 selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group May be the same or different, and each of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a hydrogen atom or a hydrocarbon group, n is an integer of 1 to 3, and when n = 1, the R ¹ to R ¹⁶ are It may not be a hydrogen atom at the same time, and may be same or different, respectively. Adjacent substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, R ¹³ and R ¹⁵ may be bonded to each other to form a ring, and R ¹³ and R ¹⁵ may be bonded to each other to form a ring; R ¹⁴ and R ¹⁶ may combine with each other to form a ring, and Y ¹ And Y ² is a Group 14 atom and may be the same or different from each other, M is Ti, Zr or Hf, and Q is selected from the same or different combinations from halogen, a hydrocarbon group, an anion ligand or a neutral ligand that can be coordinated with a lone pair May be sufficient, and j is an integer of 1-4.

Compounds such as Examples 9 and 10 of such metallocene compounds are exemplified in Japanese Patent Application Laid-Open No. 2004-175707, WO2001 / 027124, WO2004 / 029062, WO2004 / 083265, and the like.

The metallocene compound demonstrated above is used individually or in combination of 2 or more types. The metallocene compound may also be diluted with a hydrocarbon or a halogenated hydrocarbon or the like.

The catalyst component reacts with (A) the crosslinked metallocene compound represented above, (B) (b-1) organoaluminumoxy compound, and (b-2) the crosslinked metallocene compound (A) to ion pairs. And at least one compound selected from (b-3) an organoaluminum compound.

Hereinafter, (B) component is demonstrated concretely.

<(b-1) organoaluminumoxy compound>

The organoaluminumoxy compound (b-1) used by this invention can use a conventionally well-known aluminoxane as it is. Specifically, Chemical Formula 14

And / or Formula 15

(Herein, R is a hydrocarbon group of 1 to 10 carbon atoms, n represents an integer of 2 or more.), In particular, methyl aluminoxane, wherein R is a methyl group, n is 3 or more, preferably 10 The above is used. Even if some organoaluminum compound is mixed in these aluminoxanes, it does not interfere. For example, when performing high temperature solution polymerization, the characteristic property is also applicable to the benzene-insoluble organoaluminumoxy compound as illustrated by Unexamined-Japanese-Patent No. 2-78687. Moreover, it has an organoaluminumoxy compound described in Unexamined-Japanese-Patent No. 2-167305, 2 or more types of alkyl groups described in Unexamined-Japanese-Patent No. 2-24701, and Unexamined-Japanese-Patent No. 3-103407. Aluminoxane etc. can also be used suitably. Moreover, the "benzene insoluble" organoaluminumoxy compound used in the said high temperature solution polymerization is the Al component which melt | dissolves in benzene of 60 degreeC is 10% or less normally in conversion of Al atom, Preferably it is 5% or less, Especially preferably, It is 2% or less and means insoluble or poorly soluble with respect to benzene.

In addition, examples of the organoaluminumoxy compound used in the present invention include a modified methyl aluminoxane such as the following formula (16).

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n represent an integer of 2 or more).

This modified methyl aluminoxane is prepared using alkyl aluminum other than trimethyl aluminum and trimethyl aluminum. Such compounds are generally called MMAO. Such MMAOs can be prepared by the methods illustrated in US4960878 and US5041584. Moreover, it is commercially produced by the name of MMAO and TMAO that R prepared by using trimethyl aluminum and triisobutyl aluminum is isobutyl group also from Doso Finechem Co., Ltd. etc. The MMAO is an aluminoxane with improved solubility and storage stability in various solvents. Specifically, MMAO is dissolved in aliphatic hydrocarbons or alicyclic hydrocarbons, unlike insoluble or poorly soluble in benzene such as Chemical Formulas 14 and 15.

Furthermore, as an organoaluminumoxy compound used by this invention, the organoaluminumoxy compound containing the boron represented by following formula (17) is also mentioned.

(Wherein, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different from each other and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

<(b-2) Compound which reacts with the crosslinked metallocene compound (A) to form an ion pair>

As compound (b-2) (hereinafter sometimes abbreviated as "ionic compound") which reacts with a crosslinked metallocene compound (A) to form an ion pair, Japanese Patent Application Laid-open No. Hei 1-501950, Japanese Patent Laid-Open No. 1-502036, Japanese Patent Laid-Open No. 3-179005, Japanese Patent Laid-Open No. 3-179006, Japanese Patent Laid-Open No. 3-207703, Japanese Patent Laid-Open No. 3-207704, Lewis acids, ionic compounds, borane compounds, carborane compounds and the like described in USP5321106 and the like. Moreover, a heteropoly compound and an isopoly compound can also be mentioned.

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

Examples of the formula, R ^{e +,} there may be mentioned H ^+, such as carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptane tilt Lai yen one ferrocenium cation having a cation, and a transition metal. R ^f to R ⁱ may be the same as or different from each other, and are an organic group, preferably an aryl group.

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 trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation and triisobutylammonium cation. N, N-dialkylanilinium cations such as alkylammonium cations, N, N-dimethylanilinium cations, N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations And dialkyl ammonium cations such as diisopropyl ammonium cation and dicyclohexyl ammonium cation.

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 +} , carbenium cations, ammonium cations and the like are preferable, and triphenyl carbenium cation, N, N-dimethylanilinium cation and N, N-diethylanilinium cation are particularly preferable.

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

Examples of the ammonium salts include trialkyl substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.

Specific examples of the trialkyl substituted ammonium salts include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium Tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) Borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-tri Fluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) Ammonium Tetrakis (o-tolyl) borate, Dioctadecylmethylammonium tetraphenylborate, Dioctadecylmethylammonium tetrakis (p-tolyl) borate, Dioctadecylmethylammonium tetrakis (o-tolyl) borate, Dioctadecyl Methylammonium Tetrakis (pentafluorophenyl) borate, Dioctadecylmethylammonium Tetrakis (2,4-dimethylphenyl) borate, Dioctadecylmethylammonium Tetrakis (3,5-dimethylphenyl) borate, Dioctadecylmethyl Ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, dioctadecylmethylammonium, and the like.

Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-di Methylanilinium 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-penta Methylanilinium tetrakis (pentafluorophenyl) borate etc. are mentioned.

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

In addition, the ionic compound disclosed by the present applicant (JP-A-2004-51676) can also be used without a restriction | limiting.

Moreover, 2 or more types of above-mentioned ionic compounds (b-2) can be mixed and used.

<(b-3) organoaluminum compound>

As an organoaluminum compound (b-3) which forms an olefin polymerization catalyst, the organoaluminum compound represented by following formula (19), the complex alkylate of group 1 metal and aluminum represented by following formula (20), etc. are mentioned, for example. have.

R ^a _m Al (OR ^b ) _n H _p X _q

(In formula, R ^<a> and R <^b> may mutually be same or different, represent a hydrocarbon group of 1-15, preferably 1-4 carbon atoms, X represents a halogen atom, m is 0 <m <= 3 and n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3 and m + n + p + q = 3.). Specific examples of such compounds include trin-alkyl aluminum such as trimethyl aluminum, triethyl aluminum, trin-butyl aluminum, trihexyl aluminum, trioctyl aluminum, and the like; Tri-branched alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, trisec-butyl aluminum, tritert-butyl aluminum, tri2-methylbutyl aluminum, tri3-methylhexyl aluminum and tri2-ethylhexyl aluminum; Tricycloalkyl aluminum, such as tricyclohexyl aluminum and tricyclooctyl aluminum; Triaryl aluminum, such as triphenyl aluminum and tritolyl aluminum; Dialkyl aluminum hydrides such as diisopropyl aluminum hydride and diisobutyl aluminum hydride; Alkenyl such as isoprenyl aluminum represented by the formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z ≦ 2x) or the like. aluminum; Alkyl aluminum alkoxides such as isobutyl aluminum methoxide and isobutyl aluminum ethoxide; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide; Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; Partially alkoxylated alkyl aluminum having an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _0.5 and the like; Alkyl aluminum aryl oxides such as diethyl aluminum phenoxide and diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide); Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; Other partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Partially alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide and the like.

M ² AlR ^a ₄

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. freight. Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) ₄ , and the like.

In addition, a compound similar to the compound represented by Formula 20 may be used, for example, an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. As such a compound there may be mentioned _{specifically, (C 2 H 5) 2} AlN (C 2 H 5) Al (C 2 H 5) 2 and the like. In terms of availability, trimethyl aluminum and triisobutyl aluminum are preferably used as the organoaluminum compound (b-3).

<Polymerization>

The polyethylene wax used in the present invention is obtained by homopolymerizing ethylene usually in the liquid phase or copolymerizing ethylene and α-olefin in the presence of the metallocene catalyst. In the polymerization, the usage and the order of addition of each component are arbitrarily selected, but the following methods are exemplified.

[q1] A method of adding component (A) alone to a polymerizer.

[q2] A method of adding the component (A) and the component (B) to the polymerizer in any order.

In the method of said q2, at least 2 or more of each catalyst component may be previously contacted. Although a hydrocarbon solvent is generally used at this time, (alpha) -olefin may be used as a solvent. In addition, each monomer used here is as above-mentioned.

The polymerization method includes suspension polymerization that polymerizes in a state where polyethylene wax is present as a particle in a solvent such as hexane, gas phase polymerization that does not use a solvent, and polyethylene wax melts together with a solvent or alone at a polymerization temperature of 140 ° C. or higher. Solution polymerization which superposes | polymerizes in the state which has been made is possible, and solution polymerization is especially preferable from both surfaces of economy and quality.

The polymerization reaction may be performed by either a batch method or a continuous method. When performing polymerization by a batch method, the above catalyst component is used under the concentration described below.

In the course of conducting the polymerization of an olefin using the catalyst for olefin polymerization as described above, component (A) per liter of the reaction volume, typically ^10-9 to ^10-1 mol, preferably ^10-8 to ^10-amount of ² moles Used as

Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) and total transition metal atoms (M) in component (A), usually 0.01 to 5,000, preferably 0.05 to 2,000 It is used in the amount of. Component (b-2) has a molar ratio [(b-2) / M] of the ionic compound in component (b-2) and the total transition metal (M) in component (A), usually from 0.01 to 5,000, preferably It is used in quantities ranging from 1 to 2,000. Component (b-3) has a molar ratio [(b-3) / M] of component (b-3) and transition metal atom (M) in component (A), usually 1 to 10,000, preferably 1 to 5,000. It is used in the amount that it becomes.

The polymerization reaction usually has a temperature of −20 to + 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 180 ° C., and the pressure usually exceeds 0 and is 7.8 MPa (80 kgf / cm 2, gauge pressure) or less, Preferably it is carried out under conditions exceeding 0 and below 4.9 MPa (50 kgf / cm <2>, gauge pressure).

At the time of polymerization, ethylene and the α-olefin used as necessary are supplied to the polymerization system in a proportion of the amount by which the polyethylene wax of the above-described specific composition is obtained. In addition, at the time of superposition | polymerization, molecular weight regulators, such as hydrogen, can also be added.

When the polymerization is carried out in this manner, the produced polymer is usually obtained as a polymerization liquid containing this. Thus, polyethylene wax is obtained by treatment by a conventional method.

In this invention, use of the catalyst containing the metallocene compound especially shown in <Example-1 of a metallocene compound is preferable.

By using such a catalyst, polyethylene wax having the above-mentioned characteristics is easily obtained.

Although the shape of the polyethylene wax of this invention does not have a restriction | limiting in particular, Usually, it is a pellet form or a tablet form particle | grains.

[Other Ingredients]

In this invention, in addition to the said polyethylene and polyethylene wax, you may add and use additives, such as stabilizers, such as antioxidant, a ultraviolet absorber, a light stabilizer, a metal soap, a filler, a flame retardant, and a pigment, as needed.

As said stabilizer, Antioxidants, such as a hindered phenol type compound, a phosphite type compound, a thioether type compound;

Ultraviolet absorbers such as benzotriazole compounds and benzophenone compounds;

Light stabilizers, such as a hindered amine compound, are mentioned.

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, carbon black, and the like.

As said flame retardant, Halogen compounds, such as halogenated diphenyl ether, such as decabrom diphenyl ether and octabrodiphenyl ether, and halogenated polycarbonate; Inorganic compounds such as antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyro antimonate, and aluminum hydroxide; A phosphorus compound etc. are mentioned.

Moreover, in order to prevent drip, as a flame retardant adjuvant, compounds, such as tetrafluoroethylene, can be added.

As said antibacterial agent and antifungal agent, Organic compounds, such as an imidazole type compound, a thiazole type compound, a nitrile type compound, a haloalkyl type compound, a pyridine type compound;

Silver, an inorganic substance, such as a silver compound, a zinc compound, a copper compound, and a titanium compound, an inorganic compound, etc. are mentioned.

Among these compounds, silver and silver compounds having high thermal stability and high performance are preferable. Examples of the silver compound include silver complexes and silver salts such as fatty acids and phosphoric acid. When silver and a silver compound are used as an antimicrobial agent and an antifungal agent, these substances may be used by supporting them on porous structures such as zeolite, silica gel, zirconium phosphate, calcium phosphate, hydrotalcite, hydroxyapatite and calcium silicate. .

As said pigment, the pigment conventionally used for coloring of synthetic resin 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 ; Hydroxides such as Al ₂ O ₃ nH ₂ O and Fe ₂ O ₃ nH ₂ O; Sulfates such as CaSO ₄ and BaSO ₄ ; Nitrates such as Bi (OH) ₂ NO ₃ ; PbCl ₂ Chlorides and the like; Chromium salts such as CaCrO ₄ and BaCrO ₄ ; Chromite, manganate and permanganate such as CoCrO ₄ ; Borate salts such as Cu (BO) ₂ ; Ureate salts such as Na ₂ U ₂ O ₇ .6H ₂ O; Nitrites such as K ₃ Co (NO ₂ ) ₆ .3H ₂ O; Silicates such as SiO ₂ ; Arsenates and arsenites such as CuAsO ₃ Cu (OH) ₂ ; Acetates such as Cu (C ₂ H ₃ O ₂ ) ₂ .Cu (OH) ₂ ; Phosphates such as (NH ₄ ) ₂ MnO ₂ (P ₂ O ₇ ) ₂ ; Inorganic pigments such as aluminates, molybdates, zincates, antimonates, tungsten selenides, titanates, iron cyanide salts, phthalates, CaS, ZnS, CdS, graphite and carbon black,

Natural organic pigments such as cochineal lake and mother lake, nitroso pigments such as naphthol green Y and naphthol green B; Nitro pigments such as naphthol yellow S and pigment chlorine 2G; Permanent red 4R; Azo pigments such as Hansa Yellow, Brilliant Carmine 68 and Scarlet 2R; Basic dye lakes such as maracaine green and rhodamine B, acid dye lakes such as acid, green lake, and eosin lake, and mordant dye lakes such as alizarin lake and perpurin lake, pio indigo red B and intansrene And organic pigments such as phthalocyanine pigments such as vat salt dye pigments such as orange, phthalocyanine blue, and phthalocyanine green.

Other additives include plasticizers, anti-aging agents, oils, and the like.

[Raw material furtherance costs]

Although the composition ratio of polyethylene and polyethylene wax used as a raw material of this invention does not have a restriction | limiting in particular unless the physical property of the spacer for optical fiber cables obtained is impaired, Usually, it is the range of 0.01-10 mass parts with respect to 100 mass parts of polyethylene, Preferably It is the range of 0.1-5 mass parts, More preferably, it is the range of 0.3-3 mass parts, Especially preferably, it is the range of 0.5-2 mass parts.

When polyethylene and polyethylene wax are used in the composition ratio of the said range, the effect of improving fluidity | liquidity at the time of shape | molding a spacer is large, and also there exists a tendency for the forming speed to improve further and productivity improve. Furthermore, there is a tendency not to impair the mechanical properties inherent in polyethylene. Moreover, compared with the case where it was shape | molded without adding polyethylene wax, there exists a tendency which can be shape | molded at lower shaping | molding temperature, and cooling time may be shortened. Further, by lowering the molding temperature, not only the thermal degradation of the resin can be suppressed, the fall of the resin strength can be suppressed, but the sticking and the black spot of the resin can be suppressed in some cases.

[Wax Masterbatch]

In the present invention, a method for producing a spacer for an optical fiber cable by first producing the polyethylene wax and a wax masterbatch containing the polyethylene, followed by melt extrusion of the wax masterbatch and the mixture containing the polyethylene, is particularly preferred. to be. In this way, when the spacer is manufactured using the wax masterbatch, the shape, dimensions, and surface roughness of the spacer obtained can be precisely controlled, and the mechanical properties required as the spacer are not impaired, and the molding is further performed. Can improve speed.

Although the manufacturing method of the wax masterbatch used by this invention does not have a restriction | limiting in particular, For example, the said polyolefin wax, the said polyethylene, and the additive mentioned above can be manufactured by melt-kneading as needed. Melt kneading can be performed with an extruder, a flask mill, a blower, a kneader, a roll mixer, a Banbury mixer, etc., for example.

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

Moreover, the wax masterbatch used by this invention can also be obtained by mixing the solution containing polyethylene wax, and the solution containing polyethylene, and desolventing from this mixed solution.

Although the compounding quantity of the said polyethylene wax in the wax masterbatch used by this invention does not have a restriction | limiting in particular, It is the range of 5-95 mass parts normally with respect to 100 mass parts of polyethylene contained in a wax masterbatch, Preferably it is the range of 10-90 mass parts More preferably, it is the range of 20-80 mass parts.

When the masterbatch which mix | blended polyethylene wax in the said range is used, the effect of improving the fluidity | liquidity at the time of shaping | molding of a spacer is large, and also there exists a tendency for the forming speed to improve further.

Moreover, the composition ratio of the whole polyethylene and polyethylene wax and its preferable aspect at the time of using a wax masterbatch are the same as the case demonstrated in the term of the "raw material composition ratio" mentioned above.

In the present invention, additives such as stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, metal soaps, fillers, flame retardants, plasticizers, antioxidants, pigments, colorants, oils, etc. may be further added to the wax masterbatch as necessary.

[Method for Manufacturing Spacer]

The spacer of the present invention can be prepared by melt extruding a mixture comprising polyethylene and polyethylene wax, or a mixture comprising polyethylene and wax masterbatches, to a desired shape on a tension member.

Examples of the tensile tension line used for the optical fiber cable spacer include forged steel wires, stranded wires, FRP wire-shaped articles reinforced with various reinforcing fibers, and coated tensile tension lines provided with a preliminary coating layer made of resin and the like.

More specifically, an example of the manufacturing method will be described as follows. A crosshead and an extruder equipped with a rotary die at the outlet of the crosshead are prepared. This rotary die has an opening corresponding to the cross-sectional shape of the spacer. The shape of the opening is usually a concave-convex gear shape, and the shape of the spacer groove portion is determined by this shape. The shape of the spacer groove portion is determined depending on the number of optical fiber core wires or the tape core wires, the purpose of use of the optical fiber, and the like, but the shape includes an angle groove, a U groove, a V groove, and the like. The number of grooves in the spacer is also determined by the number of openings in this rotary die.

In this extruder, the mixture containing the said polyethylene and a polyethylene wax, or the mixture containing the said polyethylene and a wax masterbatch is melt-kneaded, and the obtained melt is extruded from the rotating die on the tension line | wire introduced into the crosshead. At the time of extrusion, the rotating die is rotating, and the spiral pitch of the spacer is determined by the rotational speed. Moreover, when manufacturing the spacer for tape slot type cables by which the direction of a spiral was periodically reversed to SZ shape, a rotating die is reversed according to a desired shape.

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

Thus, although the spacer for optical fiber cables of this invention can be manufactured, when manufacturing a spacer, you may combine the technique for manufacturing other well-known spacer with the said method. Furthermore, you may manufacture by the other well-known manufacturing method of the spacer for optical fiber cables using polyethylene as a spacer.

By applying such a manufacturing method, the molding speed at the time of manufacturing the spacer for an optical fiber cable can be improved, and the shape, dimensions, and surface roughness are precisely controlled, and the required mechanical properties are impaired. A spacer for an optical fiber cable is obtained.

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))

Number average molecular weight (Mn) is calculated | required from GPC measurement. The measurement was performed on condition of the following. In addition, the number average molecular weight (Mn) created the analytical curve using commercially available monodisperse standard polystyrene, and calculated | required molecular weight based on the following conversion method.

Apparatus: Gel Permeation Chromatograph Alliance GPC2000 Type (manufactured by Waters)

Solvent: o-dichlorobenzene

Column: TSKgel column (manufactured by Tosoh Corporation) × 4

Flow rate: 1.0ml / min

Sample: 0.15 mg / mL o-dichlorobenzene solution

Temperature: 140 ℃

Molecular weight conversion: PE conversion / universal calibration

In addition, the coefficient of the Mark-Houwink viscosity formula shown below was used for calculation of general-purpose calibration.

Modulus of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70

Modulus of polyethylene (PE): KPE = 5.06 × 10 ^-4 , aPE = 0.70

(A value, B value)

From the measurement result of GPC mentioned above, the ratio of the component of molecular weight 1,000 or less was calculated | required by mass%, and it was set as A value. In addition, from the measurement result of GPC, the ratio of the component of molecular weight 20,000 or more was calculated | required by mass%, and it was set as B value.

(Melt viscosity)

It measured at 140 degreeC using the Brookfield viscometer.

(density)

It measured according to the density gradient method of JISK7112.

(Melting point)

It measured using the differential scanning calorimeter (DSC) [DSC-20 (made by Seiko Denshi Kogyo KK)]. 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 DSC measured on the conditions of the temperature increase rate of 10 degree-C / min in the temperature range of -20 degreeC to 200 degreeC. Melting | fusing point was made into the value of the endothermic peak of the curve obtained from the measurement result.

(Crystallization temperature)

Crystallization temperature (Tc, ° C) was measured under the condition of a temperature-fall rate of 2 ° C / min in accordance with ASTM D3417-75.

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

(Mechanical characteristics)

The test piece No. 4 prescribed | regulated to ASTM D638 was produced, the tensile test was done on condition of 23 degreeC and the speed of 50 mm / min, and the tensile yield stress was measured.

(productivity)

The take-out speed | rate (m / min) at the time of melt-extruding resin by a tension line was evaluated.

(Surface roughness of the side of the spacer)

According to JIS B0601, the average roughness Ra (unit: micrometer) of the groove side surface of the produced spacer was measured.

○ Ra≤1.0

Δ 1.0 <Ra≤1.5

× Ra> 1.5

(Lip shape retention of spacer)

Lip shape retention of the produced spacer was evaluated.

○ No lip wave or fall

× Ribbed or collapsed

 [Creation of Masterbatch]

Metallocene-based polyethylene wax (Eccelex 40800T; Mitsui) prepared using 30 parts by mass of a pellet and a metallocene catalyst of a high density polyethylene resin (Hyex 5100B; manufactured by Prime Polymer Co., Ltd., MI = 0.27 (g / 10 minutes)) 70 parts by mass of pellets manufactured by Kagaku Co., Ltd., density = 980 (kg / m 3), Mn = 2,400, A value = 7.3, B value = 4.2, melt viscosity = 600 (mPas)) using a mixer Then, the mixture was melt-extruded using a twin screw extruder set at a die temperature of 180 ° C, and the extrudate was pelletized to prepare a masterbatch (1).

Example 1

Metallocene-based polyethylene wax (Eckselex 40800T; Mitsui Kaga) in 100 parts by mass of high density polyethylene resin (Hyex 6300M; manufactured by Prime Polymer Co., Ltd., MI = 0.11 (g / 10 minutes), density = 951 (kg / m 3)) 2 mass parts of density | concentration = 980 (kg / m <3>), Mn = 2,400, A value = 7.3, B value = 4.2 and melt viscosity = 600 (mPa * s) manufactured by KK. Next, on the outer circumference of the coated tensile tension line whose outer diameter is 3.8 mm which provided the preliminary coating layer of modified polyethylene in the outer periphery of the forged steel wire of outer diameter 2.0 mm using the extruder of φ 45 mm equipped with the crosshead which has a rotating die at the exit, The resultant mixture was melt-extruded while the die was rotated under a pulling speed of 18 m / min and a die temperature of 180 ° C., and the outer diameter of 10.00 mm having five spiral grooves having a groove width of 1.45 mm and a groove depth of 3.20 mm, The spacer of 500 mm spiral pitch of the groove was obtained. The discharge was stable, and the obtained spacer had no uneven surface roughness on the groove side, and a good shape was obtained. The results are shown in Table 2.

[Example 2]

A spacer was obtained by melt extrusion at a pulling speed of 12 m / min in the same manner as in Example 1 except that the amount of the metallocene-based polyethylene wax (Eckselex 40800T; manufactured by Mitsui Chemicals, Inc.) was changed to 1 part by mass. . The results are shown in Table 2.

Example 3

The polyethylene wax is a metallocene-based polyethylene wax (Eckselex 30200BT; manufactured by Mitsui Chemicals, Inc., density: 913 (kg / m 3), Mn = 2,000, A value = 9.3, B value = 2.2, melt viscosity = 300 (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.

Example 4

The polyethylene wax is a metallocene-based polyethylene wax (Eckselex 10500; manufactured by Mitsui Chemicals, Inc., density = 960 (kg / m 3), Mn = 700, A value = 47.8, B value = 0, melt viscosity = 18 (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.

Example 5

2.9 parts by mass of the masterbatch (1) was mixed with 99.1 parts by mass of high density polyethylene resin (Hyex 6300M; manufactured by Prime Polymer Co., Ltd., MI = 0.11 (g / 10 min), density = 951 (kg / m 3)). Next, on the outer circumference of the coated tensile tension line whose outer diameter is 3.8 mm which provided the preliminary coating layer of modified polyethylene in the outer periphery of the forged steel wire of outer diameter 2.0 mm using the extruder of φ 45 mm equipped with the crosshead which has a rotating die at the exit, The resultant mixture was melt-extruded while the die was rotated under a pulling speed of 18 m / min and a die temperature of 180 ° C., and the outer diameter of 10.00 mm having five spiral grooves having a groove width of 1.45 mm and a groove depth of 3.20 mm, The spacer of 500 mm spiral pitch of the groove was obtained. The discharge was stable, and the obtained spacer had no uneven surface roughness on the groove side, and a good shape was obtained. The results are shown in Table 2.

Example 6

High density polyethylene resin (Hyex 6300M; manufactured by Prime Polymer Co., Ltd., MI = 0.11 (g / 10 minutes), density = 951 (kg / m 3)) except 99.6 parts by mass and masterbatch (1) 1.4 parts by mass Was melt-extruded at a pulling speed of 12 m / min in the same manner as in Example 5 to obtain a spacer. The results are shown in Table 2.

Comparative Example 1

At the outer periphery of the coated tensile tension line having an outer diameter of 3.8 mm, a preliminary coating layer of modified polyethylene was provided on the outer periphery of a forged steel wire having an outer diameter of 2.0 mm using a φ 45 mm extruder equipped with a crosshead having a rotary die at its exit. High density polyethylene resin (HIJEX 6300M; product made from Prime Polymer Co., Ltd., MI = 0.11 (g / 10min), density = 951 (kg /) while rotating die | dye on condition of die temperature of 180 degreeC of 18 m / min. M 3)) 100 parts by mass was melt-extruded to obtain a spacer having an outer diameter of 10.00 mm and a spiral pitch of 500 mm with five spiral grooves having a groove width of 1.45 mm and a groove depth of 3.20 mm. The surface of the obtained spacer groove side surface was rough, and the favorable shape was not obtained. The results are shown in Table 2.

Comparative Example 2

The spacer was obtained by melt-extruding by the method similar to the comparative example 1 except having changed the take-out speed into 12 m / min. The results are shown in Table 2.

Comparative Example 3

The spacer was obtained by melt-extruding by the method similar to the comparative example 1 except having changed the take-out speed into 6 m / min. The results are shown in Table 2.

[Comparative Example 4]

Change polyethylene wax into polyethylene wax (Highwax 420P; manufactured by Mitsui Chemicals, Density = 930 (kg / m 3), Mn = 2,000, A value = 8.3, B value = 6.2, melt viscosity = 700 (mPas)) A spacer was obtained by melt-extrusion in the same manner as in Example 1 except for the one. The results are shown in Table 2.

[Comparative Example 5]

The polyethylene wax was changed into polyethylene wax (A-C6; manufactured by Hanwellwell, density = 913 (kg / m 3), Mn = 1,800, A value = 6.5, B value = 3.3, melt viscosity = 420 (mPa · s)). A spacer was obtained by melt extruding in the same manner as in Example 1 except for the above. The results are shown in Table 2.

Claims (5)

The density measured according to the density gradient pipe method of JIS K7112 is in the range of 940-980 (kg / m <3>), and MI measured on the conditions of 190 degreeC and test load 21.18N according to JIS K7210 is 0.01-0.3 g / 10min. Polyethylene (1) which is a range of, The density measured according to the density gradient pipe method of JIS K7112 is in the range of 890-980 (kg / m <3>), and the number average molecular weight (Mn) of polyethylene conversion measured by gel permeation chromatography (GPC) is 500-4,000. A method for producing a spacer for an optical fiber cable by melting and extruding a mixture comprising polyethylene wax (2), which also satisfies the relationship represented by the following formula (I). Equation I B≤0.0075 × K (In Formula (I), B is a content ratio (mass%) of the component whose molecular weight in terms of polyethylene in the polyethylene wax is 20,000 or more when measured by gel permeation chromatography, and K is 140 ° C of the polyethylene wax. Melt viscosity in mPa · s.) The method of claim 1, A method for producing a spacer for an optical fiber cable, wherein the polyethylene wax (2) further satisfies the relationship represented by the following formula (II). Equation II A≤230 × K ^(-0.537) (In Formula (II), A is the content ratio (mass%) of the component whose molecular weight of polyethylene conversion in the polyethylene wax is 1,000 or less when measured by gel permeation chromatography, and K is 140 ° C of the polyethylene wax. Melt viscosity in mPa · s.) The wax masterbatch (3) containing the polyethylene wax (2) of Claim 1 or 2 and the polyethylene (1) of Claim 1 is produced, and the wax masterbatch (3) and Claim 1 are described, A method of melting and extruding a mixture comprising polyethylene (1) to produce a spacer for an optical fiber cable. The optical fiber cable spacer obtained by the manufacturing method of Claim 1 or 2. The optical fiber cable spacer obtained by the manufacturing method of Claim 3.