JP5790172B2 - Ethylene-based resin composition, molded product, electric wire and cable - Google Patents

Description

  The present invention relates to an ethylene-based resin composition molded article, an electric wire, and a cable.

  Ethylene-based resins are used as materials for various molded products such as films, sheets and pipes. Particularly in applications where heat resistance and solvent resistance are required, silane cross-linking obtained by melting and kneading a resin composition containing an ethylene resin, an alkoxysilane compound and an organic peroxide into a desired shape is performed. Ethylene resin molded products are widely used. For example, Patent Document 1 describes a composition containing an ethylene-α-olefin copolymer, an alkoxysilane compound, and an organic peroxide as an ethylene-based resin composition that gives a molded article having a high degree of crosslinking with silane. ing.

JP 2009-227764 A

Among silane-crosslinked ethylene-based resin molded products, for example, those used for some wire coating applications, etc., are less deformed when a load is applied to the molded product at a high temperature, and the load is applied at a high temperature. After the addition, it has been demanded that the amount of deformation after removing the load and cooling is small, and improvement of such characteristics has been demanded.
Under such circumstances, the problem to be solved by the present invention is that the amount of deformation is small when a load is applied at a high temperature, and the amount of deformation after removing the load and cooling after applying the load at a high temperature. An object of the present invention is to provide an ethylene-based resin composition that provides a small number of molded articles, and a molded article comprising such a resin composition.

That is, the first of the present invention is 99 to 60 parts by weight of an ethylene-α-olefin copolymer (I) satisfying all of the following requirements (a1), (a2) and (a3):
1 to 40 parts by weight of ethylene-α-olefin copolymer (II) satisfying all of the following requirements (b1), (b2) and (b3) (however, ethylene-α-olefin copolymer (I) and ethylene) -The total weight of the α-olefin copolymer (II) is 100 parts by weight),
For a total weight of 100 parts by weight of the ethylene-α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II),
0.1 to 4 parts by weight of an alkoxysilane compound having a double bond;
An ethylene-based resin composition containing 0.01 to 4 parts by weight of an organic peroxide.
Ethylene-α-olefin copolymer (I)
(A1) The melt flow rate (MFR) is 0.05 to 20 g / 10 min.
(A2) The density is 905 to 935 kg / m ³ .
(A3) Flow activation energy (Ea) is 40 kJ / mol or more.
Ethylene-α-olefin copolymer (II)
( B1 ) The number average molecular weight is 30000 g / mol or more and 45000 g / mol or less .
(B2) The density is 905 to 940 kg / m ³ .
(B3) Flow activation energy (Ea) is less than 35 kJ / mol.

The second of the present invention is a molded article obtained by molding the ethylene resin composition.
A third aspect of the present invention is an electric wire in which a conductor is coated with the resin composition.
The fourth of the present invention is a cable having a wire bundle and a sheath formed by covering the wire bundle,
The wire bundle is a wire bundle formed by bundling a plurality of wires whose conductors are coated with a resin or a resin composition,
The cable is a cable in which the sheath is a sheath made of the ethylene resin composition.

  According to the present invention, an ethylene-based resin composition that gives a molded product that has a small deformation amount when a load is applied at a high temperature and that has a small deformation amount after the load is removed and then cooled after removing the load. , And a molded article comprising such a resin composition can be provided.

The present invention includes 99 to 60 parts by weight of an ethylene-α-olefin copolymer (I) satisfying all of the following requirements (a1), (a2) and (a3):
1 to 40 parts by weight of ethylene-α-olefin copolymer (II) satisfying all of the following requirements (b1), (b2) and (b3) (however, ethylene-α-olefin copolymer (I) and ethylene) -The total weight of the α-olefin copolymer (II) is 100 parts by weight),
For a total weight of 100 parts by weight of the ethylene-α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II),
0.1 to 4 parts by weight of an alkoxysilane compound having a double bond;
An ethylene-based resin composition containing 0.01 to 4 parts by weight of an organic peroxide.
Ethylene-α-olefin copolymer (I)
(A1) The melt flow rate (MFR) is 0.05 to 20 g / 10 min.
(A2) The density is 905 to 935 kg / m ³ .
(A3) Flow activation energy (Ea) is 40 kJ / mol or more.
Ethylene-α-olefin copolymer (II)
(B1) The number average molecular weight is 30000 g / mol or more.
(B2) The density is 905 to 940 kg / m ³ .
(B3) Flow activation energy (Ea) is less than 35 kJ / mol.

The ethylene-α-olefin copolymer (I) in the present invention is an ethylene-α-olefin copolymer comprising a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. It is a coalescence.
Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned, and 1-butene, 1-hexene and 1-octene are preferable.
The ethylene-α-olefin copolymer (I) of the present invention may contain two or more monomer units based on the α-olefin having 3 to 20 carbon atoms.

  Examples of the ethylene-α-olefin copolymer (I) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, An ethylene-1-butene-1-hexene copolymer, an ethylene-1-butene-1-octene copolymer, and the like, preferably an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, An ethylene-1-octene copolymer, an ethylene-1-butene-1-hexene copolymer, and an ethylene-1-butene-1-octene copolymer.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer is usually 50 to 99% by weight, with the total weight of the ethylene-α-olefin copolymer being 100% by weight. The content of the monomer unit based on the α-olefin is usually 1 to 50% by weight, where the total weight of the ethylene-α-olefin copolymer is 100% by weight.

  The melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene-α-olefin copolymer (I) is 0.05 to 20 g / 10 minutes (requirement (a1)). From the viewpoint of obtaining a resin composition that gives a molded product with a smaller amount of deformation when a load is applied at a high temperature, and after a load is applied at a high temperature, and after the load is removed and cooled, the amount of deformation is less. The MFR of the α-olefin copolymer (I) is preferably 5 g / 10 minutes or less, more preferably 1 g / 10 minutes or less. The MFR is preferably 0.1 g / 10 min or more, more preferably 0.15 g / 10 min or more, from the viewpoint of reducing the load of extrusion. The MFR is measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. in the method defined in JIS K7210-1995.

The density of the ethylene-α-olefin copolymer (I) is 905 to 935 kg / m ³ (requirement (a2)). From the viewpoint of obtaining a molded article having excellent bending rigidity, the density of the ethylene-α-olefin copolymer (I) is preferably 930 kg / m ³ or less, more preferably 925 kg / m ³ or less. From the viewpoint of obtaining a resin composition excellent in more heat resistance, density of the ethylene -α- olefin copolymer (I) is preferably 910 kg / m ³ or more, more preferably 915 kg / m ³ or more.
The density is measured according to a method defined in Method A of JIS K7112-1980 using a test piece subjected to annealing described in JIS K6760-1995.

  The ethylene-α-olefin copolymer (I) in the present invention is an ethylene-α-olefin copolymer having a long chain branch, and the flow activation of such an ethylene-α-olefin copolymer is activated. The energy (hereinafter sometimes referred to as “Ea”) is 40 kJ / mol or more (requirement (a3)). From the viewpoint of obtaining a resin composition that gives a molded product with a smaller amount of deformation when a load is applied at a high temperature, and after a load is applied at a high temperature, and after the load is removed and cooled, the amount of deformation is less. The Ea of the -α-olefin copolymer (I) is preferably 45 kJ / mol or more, more preferably 50 kJ / mol or more, and further preferably 60 kJ / mol or more. Further, from the viewpoint that a molded article having higher impact strength can be obtained, Ea of the ethylene-α-olefin copolymer (I) is preferably 100 kJ / mol or less, more preferably 90 kJ / mol or less.

The activation energy (Ea) of the flow of the ethylene-α-olefin copolymer (I) is an angular frequency (unit: Pa · sec) at 190 ° C. based on the temperature-time superposition principle. (Unit: rad / sec) A numerical value calculated by an Arrhenius equation from a shift factor (aT) when creating a master curve showing dependency, and a value obtained by the following method. That is, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (the unit of melt complex viscosity is Pa · sec. , The unit of angular frequency is rad / sec). Based on the temperature-time superposition principle, the melt complex viscosity-angular frequency curve at each temperature (T) is changed to the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer (I) at 190 ° C. superimposing seek shift factor (a _T) at each temperature (T) obtained when allowed, the respective temperature (T), from a shift factor (a _T) at each temperature (T), the least square method To calculate a first-order approximation formula (the following formula (I)) of [ln (a _T )] and [1 / (T + 273.16)]. Next, Ea is obtained from the slope m of the linear expression and the following expression (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. Moreover, the correlation coefficient when calculating | requiring (I) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

  The above-mentioned melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics). Usually, geometry: parallel plate, plate diameter: 25 mm, plate interval: It is performed under the conditions of 1.2 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. Note that the measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.

  The molecular weight distribution (hereinafter sometimes referred to as “Mw / Mn”) of the ethylene-α-olefin copolymer (I) is preferably 6-25. From the viewpoint of obtaining a resin composition that gives a molded product with a smaller amount of deformation when a load is applied at a high temperature, and after a load is applied at a high temperature, and after the load is removed and cooled, the amount of deformation is less. The Mw / Mn of the α-olefin copolymer is preferably 7 or more, more preferably 8 or more, and further preferably 9 or more. Further, from the viewpoint that a molded article having higher impact strength can be obtained, Mw / Mn of the ethylene-α-olefin copolymer (I) is preferably 20 or less, more preferably 17 or less. The value of the molecular weight distribution (Mw / Mn) is determined from the molecular weight distribution curve obtained by gel permeation chromatography method and the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene. , Mw is divided by Mn.

  Examples of the method for producing the ethylene-α-olefin copolymer (I) include solid particles obtained by supporting a promoter compound such as an organoaluminum compound, an organoaluminum oxy compound, a boron compound, and an organozinc compound on a particulate compound. And a ligand having a structure in which two cyclopentadienyl type anion skeletons are bonded to each other by a cross-linking group such as an alkylene group or a silylene group. Examples thereof include a method in which ethylene and an α-olefin are copolymerized in the presence of a polymerization catalyst using a transition metal compound (hereinafter referred to as component (b)) as a catalyst component.

  Examples of the component (a) include a component in which methylalumoxane is mixed with porous silica, a component in which diethyl zinc, water, and fluorinated phenol are mixed with porous silica.

More specific examples of component (a) include component (a) diethylzinc, component (b) fluorinated phenol, component (c) water, component (d) porous silica and component (e) 1,1,1, Examples include a promoter component (hereinafter referred to as component (I) -2) obtained by contacting 3,3,3-hexamethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH).

  Examples of the fluorinated phenol of component (b) include pentafluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol, 2,4,6-trifluorophenol and the like. From the viewpoint of increasing the flow activation energy (Ea) and molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer, it is preferable to use two types of fluorinated phenols having different fluorine numbers. The molar ratio of phenol having a large number of fluorines and phenol having a small number of fluorines is usually 20/80 to 80/20, and a higher molar ratio of phenol having a small number of fluorines is preferable.

  The amount of component (a), component (b) and component (c) used is the molar ratio of the amount of each component used: component (a): component (b): component (c) = 1: y: z Then, it is preferable that y and z satisfy the following formula. | 2-y-2z | ≦ 1 In the above formula, y is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably 0.00. The number is 20 to 1.50, and most preferably 0.30 to 1.00.

  The amount of the component (d) used relative to the component (a) is such that the number of moles of zinc atoms contained in the particles obtained by contacting the component (a) and the component (d) is 0.00 per gram of the particles. The amount is preferably 1 mmol or more, and more preferably 0.5 to 20 mmol. The amount of the component (e) to be used with respect to the component (d) is preferably an amount that makes the component (e) 0.1 mmol or more per 1 g of the component (d), and an amount that becomes 0.5 to 20 mmol. More preferably.

  The component (b) includes a zirconocene complex in which two indenyl groups are bonded by a crosslinking group such as an ethylene group, a dimethylmethylene group, and a dimethylsilylene group; Zirconocene complex in which a methylindenyl group is bonded (bridged bisindenylzirconium complex); Zirconocene complex in which two methylcyclopentadienyl groups are bonded through a crosslinking group such as an ethylene group, a dimethylmethylene group, or a dimethylsilylene group; an ethylene group And a zirconocene complex in which two dimethylcyclopentadienyl groups are bonded by a bridging group such as a dimethylmethylene group and a dimethylsilylene group. Moreover, as a metal atom of a component (b), a zirconium and hafnium are preferable, and also as a remaining substituent which a metal atom has, a diphenoxy group and a dialkoxy group are preferable. From the viewpoint of increasing the flow activation energy (Ea) and vinyl bond degree (A908 / A720) of the ethylene-α-olefin copolymer (I), a cross-linked bisindenyl zirconium complex is used as the component (b). It is preferable to use ethylenebis (1-indenyl) zirconium diphenoxide.

  In the polymerization catalyst comprising the above component (a) and component (b), an organoaluminum compound may be used as a co-catalyst component as appropriate. Examples of the organoaluminum compound include triisobutylaluminum, trinormal Examples include octyl aluminum.

The amount of the component (b) used is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol per 1 g of the component (b). The amount of the organoaluminum compound used is preferably such that the aluminum atom of the organoaluminum compound is 1 to 2000 mol per mol of the metal atom of the metallocene complex.

  In addition, in the polymerization catalyst comprising the above component (a) and component (b), an electron donating compound may be used as a catalyst component as appropriate. Examples of the electron donating compound include triethylamine, Examples thereof include normal octylamine.

  When two types of fluorinated phenols having different numbers of fluorine are used as the component (b) fluorinated phenol, it is preferable to use an electron donating compound in combination.

  The amount of the electron-donating compound used is usually 0.1 to 10 mol% with respect to the number of moles of aluminum atoms in the organoaluminum compound used as the promoter component, and the molecular weight distribution (Mw / Mn) is increased. From this viewpoint, the amount used is preferably higher.

  More specifically, the method for producing the ethylene-α-olefin copolymer (I) of the present invention comprises contacting the component (I) -2, a crosslinked bisindenylzirconium complex and an organoaluminum compound. Examples thereof include a method of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst.

  The polymerization method is preferably a continuous polymerization method involving formation of particles of the ethylene-α-olefin copolymer (I), for example, continuous gas phase polymerization, continuous slurry polymerization, continuous bulk polymerization, preferably Continuous gas phase polymerization. The gas phase polymerization reaction apparatus is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method for supplying each component of the polymerization catalyst used in the production of the ethylene-α-olefin copolymer (I) of the present invention to the reaction vessel, usually inert gas such as nitrogen and argon, hydrogen, ethylene, etc. And a method in which the components are supplied without moisture, and a method in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state. Each component of the polymerization catalyst may be supplied individually, or arbitrary components may be supplied in contact in advance in any order.

  Moreover, it is preferable to carry out prepolymerization before carrying out the main polymerization and to use the prepolymerized prepolymerized catalyst component as a catalyst component or catalyst for the main polymerization. In the main polymerization and the prepolymerization, the same α-olefin may be used or different α-olefins may be used. The α-olefin used for the prepolymerization is preferably an α-olefin having 4 to 12 carbon atoms, and more preferably an α-olefin having 6 to 8 carbon atoms.

  The polymerization temperature in gas phase polymerization or slurry polymerization is usually lower than the temperature at which the ethylene-α-olefin copolymer (I) melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C. Yes, more preferably 50-90 ° C. From the viewpoint of increasing the molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer (I), a higher polymerization temperature is preferable.

  The polymerization temperature in bulk polymerization is usually 150 to 300 ° C.

  The polymerization temperature in the solution polymerization is usually 150 to 300 ° C.

  The polymerization time is usually 1 to 20 hours (as an average residence time in the case of a continuous polymerization reaction). From the viewpoint of increasing the molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer (I), a longer polymerization time (average residence time) is preferable.

  Further, for the purpose of adjusting the melt fluidity of the copolymer, hydrogen may be added to the polymerization reaction gas as a molecular weight regulator, and an inert gas may be allowed to coexist in the polymerization reaction gas. The molar concentration of hydrogen in the polymerization reaction gas with respect to the molar concentration of ethylene in the polymerization reaction gas is usually 0.1 to 3 mol% as the molar concentration of ethylene in the polymerization reaction gas is 100 mol%.

  When the α-olefin concentration in the polymerization reaction gas is increased, an ethylene-α-olefin copolymer (I) having a low density can be obtained.

The ethylene-α-olefin copolymer (II) in the present invention is an ethylene-α-olefin copolymer comprising a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. It is a coalescence.
Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned, and 1-butene, 1-hexene and 1-octene are preferable.
The ethylene-α-olefin copolymer (II) of the present invention may contain two or more monomer units based on the α-olefin having 3 to 20 carbon atoms.

  Examples of the ethylene-α-olefin copolymer (II) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, An ethylene-1-butene-1-hexene copolymer, an ethylene-1-butene-1-octene copolymer, and the like, preferably an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, An ethylene-1-octene copolymer, an ethylene-1-butene-1-hexene copolymer, and an ethylene-1-butene-1-octene copolymer.

  The number average molecular weight (hereinafter sometimes referred to as “Mn”) of the ethylene-α-olefin copolymer (II) in the present invention is preferably 30000 g / mol or more. From the viewpoint of obtaining a resin composition that gives a molded product with a smaller amount of deformation when a load is applied at a high temperature, and after a load is applied at a high temperature, and after the load is removed and cooled, the amount of deformation is less. The Mn of the α-olefin copolymer is preferably 32000 g / mol or more (requirement (b1)). Further, from the viewpoint of obtaining a resin composition having a low extrusion load, the Mn of the ethylene-α-olefin copolymer (II) is preferably 50000 g / mol or less, more preferably 45000 g / mol or less, and still more preferably. 42000 g / mol or less. The number average molecular weight (Mn) is a polystyrene-converted number average molecular weight (Mn) determined from a molecular weight distribution curve obtained by gel permeation chromatography.

The density of the ethylene-α-olefin copolymer (II) is 905 to 940 kg / m ³ (requirement (b2)). From the viewpoint of obtaining a resin composition that gives a molded product with a smaller amount of deformation when a load is applied at a high temperature, and after a load is applied at a high temperature, and after the load is removed and cooled, the amount of deformation is less. The density of the -α-olefin copolymer (II) is preferably 930 kg / m ³ or less, more preferably 925 kg / m ³ or less. From the viewpoint of obtaining a resin composition excellent in more heat resistance, density of the ethylene -α- olefin copolymer (II) is preferably 910 kg / m ³ or more, more preferably 915 kg / m ³ or more.
The density is measured according to a method defined in Method A of JIS K7112-1980 using a test piece subjected to annealing described in JIS K6760-1995.

The flow activation energy (Ea) of the ethylene-α-olefin copolymer (II) is less than 35 kJ / mol (requirement (b3)). From the viewpoint of obtaining a molded article having higher strength, the Ea of the ethylene-α-olefin copolymer is preferably less than 33 kJ / mol, more preferably less than 30 kJ / mol.
The flow activation energy (Ea) of the ethylene-α-olefin copolymer (II) is the same as the method for obtaining the flow activation energy (Ea) of the ethylene-α-olefin copolymer (I). This is the value obtained by.

  The contents of the ethylene-α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II) contained in the resin composition of the present invention are: ethylene-α-olefin copolymer (I) and ethylene. When the total weight of the -α-olefin copolymer (II) is 100 parts by weight, the content of the ethylene-α-olefin copolymer (I) is 99 to 60 parts by weight, and the ethylene-α-olefin copolymer The content of the polymer (II) is 1 to 40 parts by weight. From the viewpoint of obtaining a resin composition that gives a molded product with a smaller amount of deformation when a load is applied at a high temperature, and after a load is applied at a high temperature, and after the load is removed and cooled, the amount of deformation is less. When the total weight of the α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II) is 100 parts by weight, the content of the ethylene-α-olefin copolymer (I) is preferably The content of the ethylene-α-olefin copolymer (II) is preferably 5 parts by weight or more, and more preferably the content of the ethylene-α-olefin copolymer (I) is 90 parts by weight or less. The content of the ethylene-α-olefin copolymer (II) is 10 parts by weight or more. From the viewpoint of obtaining a molded article having higher impact strength, when the total weight of the ethylene-α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II) is 100 parts by weight, ethylene- The content of the α-olefin copolymer (I) is preferably 70 parts by weight or more, and the content of the ethylene-α-olefin copolymer (II) is preferably 30 parts by weight or less, more preferably ethylene. The content of the -α-olefin copolymer (I) is 80 parts by weight or more, and the content of the ethylene-α-olefin copolymer (II) is 20 parts by weight or less.

  Examples of the alkoxysilane compound having a double bond in the present invention include vinyl alkoxysilane compounds and acrylic alkoxysilane compounds.

  Examples of vinyl-based alkoxysilane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, and vinylmethyldimethoxysilane. can give.

  Examples of the acrylic alkoxysilane compound include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-acryloxypropyltrimethoxysilane.

  From the viewpoint that a condensation reaction between the alkoxysilane compounds described later is likely to occur, methoxysilane such as vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-acryloxypropyltrimethoxysilane is preferable. More preferred is vinyltrimethoxylane.

  These alkoxysilane compounds may be used alone or in combination of two or more.

  When the ethylene-based resin composition of the present invention is melt-kneaded, the ethylene-α-olefin copolymer (I) and the alkoxysilane compound having a double bond are combined, and the ethylene-α-olefin copolymer (II) and Bonds with an alkoxysilane compound having a double bond. Thereafter, when moisture is present, the alkoxysilane compound bonded to the ethylene-α-olefin copolymer (I) or the ethylene-α-olefin copolymer (II) undergoes a condensation reaction, and a silane-crosslinked molded product is obtained. can get. The water necessary for the condensation reaction between the alkoxysilane compounds is water or water contained in the air.

  A compound for accelerating the condensation reaction between alkoxysilane compounds may be added to the ethylene resin composition of the present invention. Examples of the compound for promoting the condensation reaction between alkoxysilane compounds include organotin compounds.

  Examples of organotin compounds include tin tetraacetate, butyltin triacetate, butyltin tributylate, butyltin trihexylate, butyltin trioctate, butyltin trilaurate, butyltin trimethylmaleate, octyltin tria Cetate, octyltin tributylate, octyltin trihexylate, octyltin trioctate, octyltin trilaurate, octyltin trimethyl maleate, phenyltin tributyrate, phenyltin Trilaurate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin dihexylate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diethyl maleate, dioctyltin diacetate, Dioctyltin dibutyrate, Dioctylus Dihexylate, Dioctyltin dioctate, Dioctyltin dilaurate, Dioctyltin diethyl maleate, Tributyltin acetate, Tributyltin butyrate, Tributyltin hexylate, Tributyltin octate, Tributyltin laurate -Tributyltin methyl maleate, trioctyltin acetate, trioctyltin butyrate, trioctyltin hexylate, trioctyltin octate, trioctyltin laurate, trioctyltin Examples thereof include methyl maleate.

  As the organic peroxide in the present invention, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl-peroxy-2-ethylhexanate, dicumyl peroxide, t-butyl peroxyisopropyl carbonate, Examples thereof include t-butyl peroxybenzoate, di-t-amyl peroxide, cumyl hydroperoxide, t-butyl peroxybivalate and the like.

  The content of the alkoxysilane compound having a double bond contained in the ethylene-based resin composition of the present invention is the sum of the ethylene-α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II). The amount is 0.1 to 4 parts by weight with respect to 100 parts by weight. From the viewpoint of obtaining a resin composition that gives a molded product that has a smaller deformation amount when a load is applied at a high temperature, and a load that is applied at a high temperature, and then the load is removed and the deformation amount after the cooling is less. The silane content is preferably 0.5 parts by weight or more, more preferably 0.8 parts by weight or more. Further, from the viewpoint of reducing bleeding of the unreacted alkoxysilane compound, the content of alkoxysilane is preferably 3 parts by weight or less, more preferably 2 parts by weight or less.

  The content of the organic peroxide contained in the ethylene resin composition is 100 parts by weight based on the total weight of the ethylene-α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II). 0.01 to 4 parts by weight. From the viewpoint of obtaining a resin composition that gives a molded product that has a smaller amount of deformation when a load is applied at a high temperature, and after the load is applied at a high temperature and then the load is removed and the amount of deformation is less after cooling. The content of the peroxide is preferably 0.05 parts by weight or more, more preferably 0.08 parts by weight or more. Further, from the viewpoint of suppressing molding defects due to gel generation caused by organic peroxide, the content of organic peroxide is preferably 1 part by weight or less, more preferably 0.5 part by weight or less.

  The number of moles of the organic peroxide is preferably 1 to 100 when the number of moles of the alkoxysilane compound having a double bond is 100. From the viewpoint of obtaining a resin composition that gives a molded product with a smaller amount of deformation when a load is applied at a high temperature, and after a load is applied at a high temperature, and after the load is removed and cooled, the amount of deformation is less. The amount of the organic peroxide in the system resin composition is preferably 2 or more, more preferably 4 or more, when the number of moles of the alkoxysilane compound is 100. Moreover, from a viewpoint of suppressing the shaping | molding defect by the gel production | generation caused by an organic peroxide, Preferably it is 20 or less, More preferably, it is 10 or less.

  When the ethylene resin composition of the present invention contains a compound for promoting the condensation reaction between alkoxysilane compounds, the amount is 0.1 to 50 mol when the number of moles of the alkoxysilane compound is 100. It is preferable that From the viewpoint of obtaining a resin composition that gives a molded product that has a smaller deformation amount when a load is applied at a high temperature, and a load that is applied at a high temperature, and then the load is removed and the deformation amount after the cooling is less. The amount of the compound for promoting the condensation reaction between the silane compounds is preferably 0.3 mol or more, more preferably 0.7 mol or more, when the number of moles of the alkoxysilane compound is 100. Moreover, from a viewpoint of suppressing the elution of the compound for accelerating the condensation reaction of alkoxysilane compounds, it is preferably 20 mol or less, more preferably 10 mol or less.

  The ethylene-based resin composition of the present invention includes an antioxidant, an anti-blocking agent, a filler, a lubricant, an antistatic agent, a weathering stabilizer, a pigment, a workability improver, a flame retardant, a metal soap, etc., if necessary. An additive may be blended, and two or more of these additives may be used in combination.

  As the antioxidant, generally used are a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like.

  Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol (BHT) and n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate (trade name Irganox 1076, manufactured by Ciba Specialty Chemicals), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name Irganox 1010, manufactured by Ciba Specialty Chemicals) 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name Irganox 3114, manufactured by Ciba Specialty Chemicals), 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-tert-butyl-4-hydroxybenzine ) Benzene, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10- And tetraoxaspiro [5,5] undecane (trade name Sumilizer GA80, manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite (trade name ADK STAB PEP8), tris (2,4-di-tert-butylphenyl) phosphite (trade name Irgafos 168, manufactured by Ciba Specialty Chemicals). Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphonite (trade name Sandostab P-EPQ , Manufactured by Clariant Shapin Co., Ltd.), bis (2-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and the like.

  As an antioxidant having both a phenol structure and a phosphate structure, for example, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10 tetra-tert- And butyl dibenz [d, f] [1,3,2] -dioxaphosphabin (trade name Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of the sulfur-based antioxidant include 4,4′-thiobis (3-methyl-6-tert-butylphenol) (trade name Sumilizer WXR, manufactured by Sumitomo Chemical Co., Ltd.), 2,2-thiobis- (4-methyl- 6-tert-butylphenol) (trade name IRGANOX 1081, manufactured by Ciba Specialty Chemical Co., Ltd.).

  Examples of other antioxidants include vitamin E and vitamin A.

  Examples of the flame retardant include metal hydroxides, metal oxides, inorganic salts / inorganic hydrated compounds, silane compounds, phosphorus compounds, bromine compounds, and chlorine compounds.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, zirconium hydroxide, hydrotalcite and the like.

  Examples of the metal oxide include antimony pentoxide, antimony trioxide, zinc oxide, ferrocene, copper oxide, calcium oxide, nickel oxide, bismuth oxide, zinc stannate, and calcium aluminate.

  Examples of the inorganic salt / inorganic hydrated compound include calcium carbonate, barium metaborate, kaolin clay, wax stone clay, dosonite, calcium aluminate silicate, and the like.

  Examples of the silane compound include silicon oil, silicon gum, and those in which a functional group is introduced.

  Examples of phosphorus compounds include non-halogen phosphates such as triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate; trichloroethyl phosphate, trisdichloropropyl phosphate, tris β-chloropropyl phosphate, and the like. Examples thereof include halogenated phosphoric acid ester; polyphosphoric acid ammonium; polyphosphoric acid amide; polychlorophosphate; condensed phosphonic acid ester; aromatic condensed phosphoric acid ester;

  Examples of the bromine-based compound include decabromodiphenyl oxide, hexabromochlorodecane, ethylenebistetrabromophthalimide, hexapromobenzene, and the like.

  Examples of the chlorinated compound include perchlorocyclopentadecane, chlorinated paraffin, chlorinated polyolefin, and chlorinated polyethylene.

  The flame retardant may be used alone or in combination of two or more.

  The molded article of the present invention contains an ethylene-α-olefin copolymer (I), an ethylene-α-olefin copolymer (II), an alkoxysilane compound having a double bond, and an organic peroxide. The obtained ethylene-based resin composition is melt-kneaded with a kneading apparatus such as an extruder, a roll molding machine, or a kneader, and then molded into a desired shape.

  An alkoxysilane compound having a double bond and an organic peroxide are each used alone or a masterbatch containing both an alkoxysilane compound and an organic peroxide is produced, and the masterbatch and an ethylene-α-olefin copolymer are produced. You may melt knead | mix (I) and ethylene-alpha-olefin copolymer (II). When producing a masterbatch, the base resin is an ethylene-based copolymer such as ethylene-α-olefin copolymer, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methacrylate copolymer. A polymer is used. When using an alkoxysilane compound or an organic peroxide as a master batch, the alkoxysilane compound and the organic peroxide are preferably different master batches. As a specific example in the case of using a masterbatch, the alkoxysilane compound and the organic peroxide are different masterbatches, and these 32 types of masterbatch, ethylene-α-olefin copolymer (I) and ethylene-α are used. -Method of melt-kneading olefin copolymer (II), masterbatch containing both alkoxysilane compound and organic peroxide, ethylene-α-olefin copolymer (I) and ethylene-α-olefin copolymer And a method of melt-kneading (II).

  As a method for forming a shape as a molded product after melt-kneading the ethylene-based resin composition, it can be formed into a desired shape by a method such as extrusion molding, injection molding, or press molding.

  Further, the molded product of the present invention is obtained by melt-kneading and molding an ethylene-based resin composition, and then holding it in water or in a high-humidity gas phase so that the ethylene-α-olefin copolymer (I) or ethylene- It is preferable that the alkoxysilane compound bonded to the α-olefin copolymer (II) undergoes a condensation reaction, and is a molded product obtained by performing a water-crosslinking accelerating treatment for silane crosslinking. By performing the water crosslinking promotion treatment, the alkoxysilane compounds are subjected to a condensation reaction, and a molded product having a high degree of crosslinking by the silane can be obtained. The water temperature at the time of performing the water crosslinking promotion treatment in water is usually 40 ° C. or higher, and preferably 60 ° C. or higher, more preferably 80 ° C. or higher from the viewpoint of increasing the degree of silane crosslinking. The relative humidity at the time of water crosslinking promotion treatment in a high-humidity gas phase is usually 30% or more, and preferably 50% or more, more preferably 70% or more from the viewpoint of increasing the degree of silane crosslinking. It is. The temperature at which water crosslinking promotion treatment is performed in a high-humidity gas phase is usually 40 ° C. or higher, and preferably 60 ° C. or higher, more preferably 80 ° C. or higher from the viewpoint of increasing the degree of silane crosslinking. is there. The time for performing the water crosslinking treatment is usually 1 hour or longer, and preferably 6 hours or longer, more preferably 12 hours or longer from the viewpoint of increasing the degree of silane crosslinking.

  Further, the molded article of the present invention was bonded to the ethylene-α-olefin copolymer (I) or the ethylene-α-olefin copolymer (II) by moisture in the air without being brought into direct contact with water. Alkoxysilane compounds undergo a condensation reaction, and silane crosslinking proceeds. Therefore, the degree of crosslinking with silane increases with time.

  A molded product obtained by molding the ethylene-based resin composition of the present invention can be obtained in a short time without being immersed in high-temperature water due to moisture contained in the air during storage of the molded product. -The alkoxysilane compound couple | bonded with olefin copolymer (I) or ethylene-alpha-olefin copolymer (II) produces condensation reaction, and silane bridge | crosslinking tends to advance. The method of cross-linking silane with moisture contained in the air during storage of the molded product is preferable because a treatment step for silane cross-linking is unnecessary as compared with a case of silane cross-linking by immersing in high-temperature water.

  Since the molded article of the present invention is highly silane-crosslinked, it is excellent in dimensional stability, heat resistance, long-term creep characteristics, and solvent resistance.

  Examples of the molded article of the present invention include wire coverings, sheaths, cross-linked pipes, heat resistant hoses, heat resistant tubes, chemical resistant tubes, hot water tubes, high strength tubes, sleeves, containers / containers, industrial parts such as gears, and the like. .

  The resin composition of the present invention has a small amount of deformation when a load is applied at a high temperature when formed into a molded product, and a small amount of deformation after cooling after removing the load after applying a load at a high temperature. It is preferably used as a wire coating material or a sheath material.

The conductor of the present invention can be obtained by coating the conductor with a molten resin composition obtained by melt-kneading the ethylene-based resin composition of the present invention.
Moreover, the cable of this invention can be obtained by coat | covering the electric wire bundle formed by bundling a plurality of electric wires with the sheath which consists of an ethylene-type resin composition of this invention. In this case, the electric wire bundle is an electric wire bundle formed by bundling a plurality of electric wires whose conductors are coated with a resin or a resin composition. Examples of the resin or resin composition covering the conductor include polyethylene resins, ethylene- Acrylic acid ester resin, ethylene-methacrylic acid ester resin, ethylene-vinyl acetate resin, olefin rubber such as polyvinyl chloride, ethylene propylene rubber, chloroprene rubber, butyl rubber, nitrile rubber, silicon rubber, Rubbers such as styrene-butadiene rubber, natural rubber and ebonite, phenolic resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins and other insulating resins or resin compositions, insulating paper, mineral oil, alkylbenzene, polybutene, Insulating oil such as alkyl naphthalene or silicone oil It can be used and impregnated, ethylene resin composition of the present invention is preferably used.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

(1) Melt flow rate (MFR, unit: g / 10 minutes)
In the method defined in JIS K7210-1995, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(2) Density (Unit: kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The measurement sample piece was annealed according to JIS K6760-1995 and used for measurement.

(3) Flow activation energy (Ea, unit: kJ / mol)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software Rhios V. The activation energy (Ea) was determined using 4.4.4.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.2-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Under nitrogen

(4) Number average molecular weight (Mn)
Using a gel permeation chromatograph (GPC) method, molecular weight distribution curves were measured under the following conditions (1) to (8). Next, the number average molecular weight (Mn) in terms of polystyrene was determined.
(1) Apparatus: Waters 150C manufactured by Water
(2) Separation column: TOSOH TSKgelGMH-HT
(3) Measurement temperature: 145 ° C
(4) Carrier: Orthodichlorobenzene (5) Flow rate: 1.0 mL / min (6) Injection volume: 500 μL
(7) Detector: Differential refraction (8) Molecular weight standard material: Standard polystyrene (TSK STANDARD POLYSTYRNE manufactured by Tosoh Corporation)

(5) Hot set test As a test piece, a molded product produced by pressing was punched into the dumbbell shape of FIG. 12 described in JIS C3660-1-1. In the method specified in JIS C3660-2-1, measurement is performed under the conditions of the crosslinked polyethylene described in 16.9 of JIS C3667 (load 20 N / cm ² , temperature 200 ° C., load application time 15 minutes). It was. Before measurement, mark the center of the sample punched into a dumbbell shape, put a mark, put the sample in an oven at 200 ° C, apply the load, and stretch the line between the marks 15 minutes after hot set elongation, take it out of the oven The elongation between marked lines after cooling was defined as permanent elongation after cooling. Hot set elongation and permanent elongation after cooling were determined by the following (Formula 1) and (Formula 2).
In the hot set test, those in which the test piece broke within 15 minutes are described as “break” in Table 3.

Hot set elongation (%) = 100 x Distance between marked lines (mm) 15 minutes after applying load / Distance between marked lines before test (mm) Formula (1)

Permanent elongation after cooling (%) = 100 x Distance between marked lines after cooling at room temperature (mm) / Distance between marked lines before test (mm) Formula (2)

[Polymerization of PE-1]
(1) Synthesis of solid catalyst component (I) After replacing a 200 L internal volume SUS reaction vessel equipped with a stirrer with nitrogen, 80 L of hexane, 20.6 kg of tetraethoxysilane, and 2.2 kg of tetrabutoxy titanium were added. And 5 ° C. Next, 50 L of butyl magnesium chloride (dibutyl ether solvent 2.1 mol / L) was added dropwise with stirring over 4 hours while maintaining the temperature at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and further at 20 ° C. for 1 hour. After filtration and washing with 70 L of toluene three times, 63 L of toluene, 14.4 kg of phenyltrichlorosilane, and 9.5 kg of diisobutyl phthalate were added. The reaction was carried out at 105 ° C. for 2 hours. Then, after filtration and washing with 90 L of toluene three times, 63 L of toluene was added, the temperature was raised to 70 ° C., 13.0 kg of TiCl 4 was added, and the reaction was carried out at 105 ° C. for 2 hours. Thereafter, solid-liquid separation was performed, and washing with 90 L of toluene at 95 ° C. and washing with 90 L of hexane at room temperature twice were performed, followed by drying. 15.2 kg of solid catalyst component (I) having excellent powder properties Got. The resulting solid product contained Ti: 1.17 wt%.

(2) Prepolymerization of solid catalyst component After replacing an autoclave with an internal volume of 210 L with a stirrer with nitrogen, 1.515 kg of the solid catalyst component obtained in (1) above, 98.4 L of butane, and 3.2337 mol of triethylaluminum were added. I put it in. Next, the temperature was set to 40 ° C., hydrogen was added until the total pressure became 0.928 MPa, and 28 kg of ethylene was further added at a rate of 2.44 g / g solid catalyst component · hr per 1 g of the solid catalyst component. After completion of the reaction, butane was flushed to obtain 28.55 kg of a prepolymerized catalyst.

(3) Polymerization Random copolymerization of ethylene and 1-butene was carried out using the above prepolymerization catalyst and using a continuous fluidized bed gas phase polymerization facility. After heating the polymerization tank to 90 ° C., 80 kg of polyethylene powder dried under reduced pressure in advance was added as a dispersant, and then a mixed gas adjusted so that the molar ratio of ethylene / 1-butene / hydrogen was 63/27/10 It was circulated under a pressure of 2 MPa so as to obtain a flow rate of 0.34 m / sec in the polymerization tank. When the molar ratio of ethylene / 1-butene / hydrogen deviated from the set value, the molar ratio was adjusted by adding. Next, the reactor was charged into the tank at a flow rate of 46.7 mmol / hr of triethylaluminum and 0.73 g / hr of the prepolymerized catalyst, and fluidized bed gas phase copolymerization of ethylene / 1-butene was continuously performed for 24 hours. The obtained polymer had good particle properties, and hardly adhered to the polymerization wall. The amount of polymer produced per catalyst (polymerization activity) was 28100 g polymer / g solid catalyst component. Table 2 shows the physical properties of the obtained ethylene-1-butene copolymer (hereinafter sometimes referred to as “PE-1”).

[Polymerization of PE-2]
Using a prepolymerized catalyst obtained by using the same solid catalyst component (I) as that of PE-1, except for the conditions shown in Table 1, ethylene-1-butene was copolymerized by the same gas phase polymerization method as that of PE-1. A polymer (hereinafter sometimes referred to as “PE-2”) was produced. Table 2 shows the physical properties.

[Polymerization of PE-3]
(1) Synthesis of solid catalyst component (a) Silica heated by a reactor equipped with a nitrogen-replaced stirrer at 300 ° C. under a flow of nitrogen (Sypolol 948 manufactured by Devison; 50% volume average particle size = 55 μm; fine (Pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 1.73 kg of diethylzinc in hexane (diethylzinc concentration: 50 mass%) and 1.02 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of 3,4,5-trifluorophenol and 1.44 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then cooled to 22 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.11kg the temperature of the reactor 22 ° C.. After completion of dropping, the mixture was stirred at 22 ° C. for 1.5 hours, then heated to 40 ° C., stirred at 40 ° C. for 2 hours, further heated to 80 ° C., and stirred at 80 ° C. for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the solid catalyst component (a) was obtained by drying.

(2) Prepolymerization of solid catalyst component In an autoclave with a stirrer having an internal volume of 210 liters previously purged with nitrogen, 0.7 kg of the solid catalyst component (a) described above, 80 liters of butane, and 0 as hydrogen at normal temperature and pressure After charging 1 liter, the autoclave was raised to 35 ° C. Further, ethylene was charged for 0.03 MPa at the gas phase pressure in the autoclave, and after the system was stabilized, 263 mmol of triisobutylaluminum and 88 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. . While raising the temperature to 50 ° C. and continuously supplying ethylene and hydrogen, preliminary polymerization was carried out at 50 ° C. for a total of 6.5 hours. After the polymerization was completed, ethylene, butane, hydrogen gas and the like were purged and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst in which 28 g of ethylene polymer was prepolymerized per 1 g of the solid component (a). .

(3) Polymerization Using the above prepolymerization catalyst, ternary copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 87 ° C., a total pressure of 2 MPa, a gas linear velocity of 0.3 m / s, a hydrogen molar ratio to ethylene of 1.2%, a 1-butene molar ratio to ethylene of 2.2%, and a 1-hexene mole to ethylene. The ratio was 0.8%, and ethylene, 1-butene, 1-hexene and hydrogen were continuously fed during the polymerization in order to keep the gas composition constant. Further, the pre-polymerization catalyst and triisobutylaluminum were continuously supplied at a constant ratio so that the total powder mass of the fluidized bed was maintained at 80 kg and the average polymerization time was 4 hours. By polymerization, a powder of an ethylene-1-butene-1-hexene copolymer (hereinafter sometimes referred to as “PE-3”) was obtained with a production efficiency of 22 kg / hr.

(4) Granulation of ethylene-1-butene-1-hexene copolymer (PE-3) powder The PE-3 powder obtained above was fed at a feed rate of 50 kg using an LCM50 extruder manufactured by Kobe Steel. / Hr, screw rotation speed 450 rpm, gate opening degree 4.2 mm, suction pressure 0.2 MPa, resin temperature 200-230 ° C., granulation was performed to obtain PE-3 pellets. Table 2 shows the physical property measurement results of PE-3 pellets.

In addition, the polyethylene used in this example is shown below.
Sumitomo Chemical Co., Ltd., ethylene-1-butene copolymer Sumikacene-L FS150 (hereinafter referred to as PE-4)).
Sumitomo Chemical Co., Ltd., ethylene-1-butene copolymer Sumikacene-L CL1079 (hereinafter referred to as PE-5)).
Sumitomo Chemical Co., Ltd., ethylene-1-hexene copolymer Sumikacene α CS1009 (hereinafter referred to as PE-6)).
Sumitomo Chemical Co., Ltd., ethylene-1-hexene copolymer Sumikacene E FV205 (hereinafter referred to as PE-7)).
Sumitomo Chemical Co., Ltd., high pressure radical polymerization low density polyethylene Sumikacene G201 (hereinafter referred to as PE-8)).
Table 2 shows the physical property measurement results of these polyethylenes.

[Example 1]
(1) Preparation of ethylene-based resin composition 85 parts by weight of PE-3, 15 parts by weight of PE-1 and vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter “VTMOS”) as an alkoxysilane compound having a double bond ”And 1.7 parts by weight of dicumyl peroxide (trade name: Perkadox BC-FF, manufactured by Kayaku Akzo Co., Ltd., hereinafter referred to as“ DCP ”). ) 0.17 parts by weight and 0.068 parts by weight of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as “DBTDL”) as a compound for promoting the condensation reaction between alkoxysilane compounds Were mixed and extruded at 210 ° C. using a single screw extruder to obtain a resin composition.

(2) Production of molded product The obtained ethylene-based resin composition was pressed at 210 ° C. and 4 MPa to obtain a flat molded product having a thickness of 1 mm and a side of 150 mm.

(3) Silane cross-linking The obtained molded product was allowed to elapse for 7 days in a temperature-controlled room at 23 ° C. and a relative humidity of 50% to cross-link the molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

[Example 2]
The same procedure as in Example 1 except that the amounts of vinyltrimethoxysilane (VTMOS), dicumyl peroxide (DCP), and dibutyltin dilaurate (DBTDL) were changed as shown in Table 3 in the preparation of the ethylene-based resin composition. To obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

Example 3
The same procedure as in Example 1 except that the amounts of vinyltrimethoxysilane (VTMOS), dicumyl peroxide (DCP), and dibutyltin dilaurate (DBTDL) were changed as shown in Table 3 in the preparation of the ethylene-based resin composition. To obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

Example 4
The same procedure as in Example 1 except that the amounts of vinyltrimethoxysilane (VTMOS), dicumyl peroxide (DCP), and dibutyltin dilaurate (DBTDL) were changed as shown in Table 3 in the preparation of the ethylene-based resin composition. To obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

Example 5
Preparation of the ethylene-based resin composition was performed in the same manner as in Example 1 except that the amounts of PE-3 and PE-1 were changed as shown in Table 3 to obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

Example 6
In the preparation of the ethylene-based resin composition, the same as Example 5 except that the amounts of vinyltrimethoxysilane (VTMOS), dicumyl peroxide (DCP), and dibutyltin dilaurate (DBTDL) were changed as shown in Table 3. To obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

Example 7
In the preparation of the ethylene-based resin composition, the same as Example 5 except that the amounts of vinyltrimethoxysilane (VTMOS), dicumyl peroxide (DCP), and dibutyltin dilaurate (DBTDL) were changed as shown in Table 3. To obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

Example 8
Preparation of the ethylene-based resin composition was performed in the same manner as in Example 1 except that PE-1 was changed to PE-2 to obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

Example 9
Preparation of the ethylene-based resin composition was performed in the same manner as in Example 2 except that PE-1 was changed to PE-4, and a silane-crosslinked molded product was obtained. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

[Comparative Example 1]
Preparation of the ethylene-based resin composition was performed in the same manner as in Example 6 except that PE-1 was changed to PE-8, and a silane-crosslinked molded product was obtained. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

[Comparative Example 2]
Preparation of the ethylene-based resin composition was performed in the same manner as in Example 2 except that PE-1 was changed to PE-6 to obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

[Comparative Example 3]
Preparation of the ethylene-based resin composition was performed in the same manner as in Example 1 except that PE-1 was changed to PE-5 to obtain a silane-crosslinked molded product. A hot set test was performed on the molded product after silane crosslinking, and the results are shown in Table 3.

[Comparative Example 4]
In the preparation of the ethylene-based resin composition, PE-3 was not used and the amount of PE-1 was changed as shown in Table 3 and the same procedure as in Example 2 was performed. The resin composition could not be obtained.

[Comparative Example 5]
In the preparation of the ethylene-based resin composition, an attempt was made in the same manner as in Example 2 except that PE-3 was changed to PE-7. As a result, stable extrusion could not be performed, and a resin composition could not be obtained.

Claims (4)

99 to 60 parts by weight of ethylene-α-olefin copolymer (I) satisfying all of the following requirements (a1), (a2) and (a3);
1 to 40 parts by weight of ethylene-α-olefin copolymer (II) satisfying all of the following requirements (b1), (b2) and (b3) (however, ethylene-α-olefin copolymer (I) and ethylene) -The total weight of the α-olefin copolymer (II) is 100 parts by weight),
For a total weight of 100 parts by weight of the ethylene-α-olefin copolymer (I) and the ethylene-α-olefin copolymer (II),
0.1 to 4 parts by weight of an alkoxysilane compound having a double bond;
An ethylene-based resin composition containing 0.01 to 4 parts by weight of an organic peroxide.
Ethylene-α-olefin copolymer (I)
(A1) The melt flow rate (MFR) is 0.05 to 20 g / 10 min.
(A2) The density is 905 to 935 kg / m ³ .
(A3) Flow activation energy (Ea) is 40 kJ / mol or more.
Ethylene-α-olefin copolymer (II)
( B1 ) The number average molecular weight is 30000 g / mol or more and 45000 g / mol or less .
(B2) The density is 905 to 940 kg / m ³ .
(B3) Flow activation energy (Ea) is less than 35 kJ / mol.   A molded product obtained by molding the ethylene-based resin composition according to claim 1.   An electric wire in which a conductor is coated with the ethylene-based resin composition according to claim 1. A cable having a wire bundle and a sheath covering the wire bundle,
The wire bundle is a wire bundle formed by bundling a plurality of wires whose conductors are coated with a resin or a resin composition,
A cable in which the sheath is a sheath made of the ethylene-based resin composition according to claim 1.