JP6520599B2 - Flame retardant resin composition for electric wire and cable coating - Google Patents

Description

  The present invention relates to a flame retardant resin composition using an ethylene / α-olefin copolymer and a wire / cable using the same, and more particularly, a flame retardant resin composition excellent in mechanical strength and moldability. And a wire / cable coated with the composition.

  In the past, polyvinyl chloride resin compositions have been used as flame retardant materials such as wire and cable covering materials, but polyvinyl chloride resin compositions are toxic halogens when burned during fires or waste incineration Improvements have been sought to produce contained gases. In order to overcome such a defect of polyvinyl chloride, a resin composition (non-halogen flame retardant material) in which a metal hydroxide such as magnesium hydroxide is mixed with a polyolefin resin has been proposed.

In order to impart sufficient flame retardancy to such non-halogen flame retardant materials, it is necessary to blend metal hydroxides of the same weight to the base polyolefin material, and therefore the mechanical properties of the materials There is a problem that In order to solve this problem, polyethylene (metallocene-based polyethylene) manufactured using a single site catalyst is used as a base material of the flame retardant resin composition, and mechanical properties are impaired even if a large amount of metal hydroxide is blended. Such high strength flame retardant resin compositions have been proposed (Patent Document 1).
However, while metallocene-based polyethylene has good mechanical properties, the narrowness of its molecular weight distribution tends to cause appearance defects such as melt fracture during wire and cable production, and has problems in molding processability. In recent years, as a means to solve this problem, the report of the flame retardant resin composition which made mechanical characteristics and moldability process compatible by using metallocene type polyethylene which introduced long-chain branching, and a wire / cable using it However, it can not always be said that sufficient effects can be exhibited.

  Under these circumstances, there is a need for a non-halogen flame retardant material that overcomes the problems of conventional flame retardant resin compositions for wire and cable coating and is excellent in moldability and mechanical properties.

JP 2005-226053 A JP 2007-177186 A Unexamined-Japanese-Patent No. 2007-023229

  An object of the present invention is to provide a flame retardant resin composition for electric wire and cable which is excellent in molding process characteristics and at the same time excellent in mechanical characteristics in view of the problems of the prior art described above.

  As a result of intensive studies to solve the above problems, the present inventors have a specific long chain branching index and a relatively narrow inverse comonomer composition distribution index, and have a specific melt flow rate and density. A flame retardant resin composition using an ethylene / α-olefin copolymer has been found to have excellent effects on moldability and mechanical properties as a wire / cable coating material, based on these findings. The present invention has been completed.

That is, according to the first aspect of the present invention, 50 to 5% by mass of ethylene / α-olefin copolymer (A) and ethylene / vinyl acetate copolymer satisfying the following conditions (1) to (5) And / or flame retardant resin composition for electric wire / cable coating containing 30 to 300 parts by mass of magnesium hydroxide (D) with respect to 100 parts by mass of resin component containing 50 to 95% by mass of ethylene / ethyl acrylate copolymer Is provided.
(1) The melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg exceeds 0.1 g / 10 min and is 10 g / 10 min or less.
(2) The density is 0.895 to 0.940 g / cm ³ .
(3) The lowest molecular weight of the branching index (g ') between 100,000 and 1,000,000 as measured by a gel permeation chromatography (GPC) measuring device combining a differential refractometer, a viscosity detector and a light scattering detector The value (gc) is 0.40 to 0.85.
(4) The weight of the ethylene / α-olefin copolymer among the components eluted below the temperature at which the elution amount determined from the integral elution curve measured by cross fractionation chromatography (CFC) is 50% by mass or less Among the components eluted at a temperature higher than the temperature at which the proportion of components above the average molecular weight (W ₂ ) and the elution amount determined from the integral elution curve becomes 50 mass%, the molecular weight is the weight of the ethylene / α-olefin copolymer The sum (W ₂ + W ₃ ) of the proportion (W ₃ ) of the components below the average molecular weight is 40 to 80% by mass.
(5) the ratio of the W ₂ and component molecular weight is more than the weight average molecular weight of the component elution amount obtained is eluted at a temperature higher than the temperature at which 50 mass% from the integrated elution curve measured by CFC (W ₄₎ The difference (W ₂ -W ₄ ) is more than 0% by mass and less than 20% by mass.

Further, according to the second invention of the present invention, in the first invention, the ethylene / α-olefin copolymer has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by GPC ( A flame retardant resin composition for electric wire / cable coating having Mw / Mn) of 3.0 to 7.0 is provided.
Further, according to the third invention of the present invention, in the first or second invention, the ethylene / α-olefin copolymer (A) is a wire / cable having a carbon number of α-olefin of 3 to 10 A flame retardant resin composition for coating is provided.

Further, according to the fourth invention of the present invention, in any of the first to third inventions, the ethylene / α-olefin copolymer (A) and the ethylene / vinyl acetate copolymer and / or ethylene / acrylic The flame-retardant resin composition for electric wire and cable coating which further contains 1-30 mass parts of modified polyolefin resin (E) with respect to 100 mass parts of ethyl acid copolymers is provided.

According to the fifth invention of the present invention, in any of the first to fourth inventions, a flame retardant resin composition for electric wire / cable coating, which has a tensile elongation at break of 540% or more, is provided.
According to the sixth invention of the present invention, in any of the first to fifth inventions, a flame retardant resin composition for electric wire / cable coating, having a tensile elongation at break of 540 to 740% is provided.
Moreover, according to the 7th invention of this invention, the electric wire and cable formed by coat | covering the flame-retardant resin composition for electric wire and cable coating | cover of the invention in any one of 1st-6th are provided.

  The flame retardant resin composition of the present invention is excellent in molding process characteristics and at the same time excellent in flame retardancy, and also has an effect of being excellent in mechanical properties such as tensile breaking strength and tensile breaking elongation. A molded product obtained by extrusion molding the flame retardant resin composition has excellent strength and durability as a wire / cable coating material, so it is toxic when it is burned at the time of fire or waste incineration. It is possible to economically and advantageously provide excellent molded products which do not generate halogen-containing gases.

It is a graph which shows a baseline and a section of a chromatogram used by gel permeation chromatography (GPC) method. It is a graph which shows the relationship between branching index (g ') and molecular weight (M).

  The present invention has a particular long chain branching index and a relatively narrow inverse comonomer composition distribution index, and has a particular MFR, an ethylene / α-olefin copolymer having a density, or a novel ethylene / α-olefin co-polymer. A flame retardant resin composition comprising 100 parts by mass of a resin component based on a polymer and another polyolefin resin and 30 to 300 parts by mass of a metal hydroxide and the flame retardant resin composition coated thereon It relates to electric wires and cables. Since the present invention has been outlined with respect to the constituent requirements and features, the respective requirements of the present invention will be specifically described in detail below as a mode for carrying out the present invention.

1. Ethylene / α-olefin copolymer (A)
The ethylene / α-olefin copolymer (A) of the present invention is characterized by satisfying all the conditions (1) to (5) described below. In particular, a relatively narrow inverse comonomer composition distribution (conditions 4 and 5) having a suitable range of long chain branching (condition 3) and low density high molecular weight components in appropriate proportions at a particular MFR and density (conditions 1 and 2) Has a novel feature of having the

1-1. Condition (1) MFR
The ethylene / α-olefin copolymer (A) used in the present invention has a melt flow rate (MFR) of more than 0.1 g / 10 min and 10 g / 10 min or less, preferably 0.1 g / 10 min. More than 5.0 g / 10 minutes or less, more preferably more than 0.1 g / 10 minutes, or less than 2.0 g / 10 minutes.
When MFR is in this range, it is excellent in the processing characteristics at the time of covering an electric wire and a cable. On the other hand, when the MFR is 0.1 g / 10 min or less, the fluidity is insufficient at the time of high-speed extrusion molding, and problems such as appearance defects occur when coating on a wire / cable. When the MFR is more than 10 g / 10 min, the effect of improving mechanical strength such as tear strength and tensile strength is not sufficient, and melt tension at the time of molding is insufficient to cause resin breakage and appearance defects.
In the present invention, MFR of ethylene / α-olefin copolymer is based on JIS K 7210 “Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic”. 190 ° C, 21.18 N (2.16 kg) load value when measured under the conditions.
Adjustment of MFR can be adjusted by changing the amount of chain transfer agent (such as hydrogen) coexisting in ethylene polymerization, or changing the polymerization temperature to increase the amount of hydrogen or increase the polymerization temperature. By doing this, you can make it bigger.

1-2. Conditions (2) Density The ethylene / α-olefin copolymer of the present invention has a density of 0.895 to 0.940 g / cm ³ , preferably 0.898 g / cm ^{3 to} 0.934 g / cm ³ , more preferably 0.900~0.930g / cm ^3, more preferably 0.910~0.930g / cm ^3, particularly preferably 0.915~0.925g / cm ^3.
It is desirable that the density be in this range, because of the balance of rigidity and flexibility when the wire / cable is coated. If the density is less than 0.895 g / cm ³ , the rigidity of the polyolefin resin is reduced, and the product is too soft and deformed, so that a thicker design is required. In addition, handling may be difficult due to stickiness, and the product itself of the polyolefin resin may stick. In addition, if the density is more than 0.940 g / cm ³ , the flexibility of the coated electric wire / cable decreases, and when a large amount of metal hydroxide is compounded, the mechanical properties of the material may be significantly reduced. .
The density can be adjusted by the amount of α-olefin at the time of polymerization of ethylene · α-olefin.
In the present invention, the density of the ethylene / α-olefin copolymer can be measured by JIS K 7112 (1999 edition): Method A (substitution method in water). That is, the density of the ethylene / α-olefin copolymer can be measured by the following method.

  The pellets are hot pressed to make a 2 mm thick pressed sheet, which is placed in a 1,000 ml beaker filled with distilled water, covered with a watch glass and heated with a mantle heater. After boiling for 60 minutes after boiling of distilled water, place the beaker on a wooden table and allow it to cool. At this time, the boiling distilled water after boiling for 60 minutes is made into 500 ml, and the time until it reaches room temperature is adjusted not to be less than 60 minutes. In addition, the test sheet is immersed in approximately the center of the water so as not to be in contact with the beaker and the water surface. After annealing the sheet at 23 ° C and 50% humidity for 16 hours or more and 24 hours or less, the sheet is punched so as to be 2 mm in height and width, and tested at a test temperature of 23 ° C. And measurement according to “Specific gravity measurement method”.

1-3. Condition (3) gc
In addition to the above conditions (1) and (2), the ethylene / α-olefin copolymer (A) used in the present invention is further gel-perm combined with a differential refractometer, a viscosity detector and a light scattering detector. The lowest value (gc) of the molecular weight between 100,000 and 1,000,000 of the branching index (g ') measured by a color chromatography (GPC) measurement device is 0.40-0.85. It is preferably 0.50 to 0.80, more preferably 0.50 to 0.77, and particularly preferably 0.51 to 0.75. If the g _C value is greater than 0.85, the effect of improving moldability tends not to be sufficiently exhibited. When the g _C value is less than 0.40, the moldability of the flame retardant resin composition is improved, but the impact strength tends to decrease.
In the present invention, the g _C value of the ethylene / α-olefin copolymer is an index for evaluating the amount of long chain branching using a molecular weight distribution curve or branching index (g ′) calculated from the following GPC-VIS measurement. is there.
The long-chain branched structure (that is, g _C ) of the ethylene / α-olefin copolymer (A) of the present invention can be roughly defined by the types of catalyst component (A) and catalyst component (B) described later Also, it can be adjusted by changing the polymerization conditions such as the molar ratio of the catalyst, the polymerization temperature and pressure, and the time and the polymerization process.

[Branch structure analysis by GPC-VIS]
As GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer), Alliance GPCV2000 manufactured by Waters can be used. As a light scattering detector, DAWN-E manufactured by Multiangle Laser Light Scattering Detector (MALLS) Wyatt Technology can be used. Detectors are connected in the order of MALLS, RI, Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (addition of the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As the column, two Tohoh GMHHR-H (S) HTs can be used in combination.
The temperature of the column, sample injection unit and each detector is 140.degree. The sample concentration is 1 mg / mL. The injection volume (sample loop volume) is 0.2175 mL. In order to determine the absolute molecular weight (M) obtained from MALLS, the radius of inertia square (Rg) and the limiting viscosity ([η]) obtained from Viscometer, use the data processing software ASTRA (version 4.73.04) attached to MALLS. The calculation can be performed with reference to the following documents.

References:
1. Developments in polymer characterization, vol. 4. Essex: Applied Science; 1984. Chapter 1.
2. Polymer, 45, 4695-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

[Calculation of branching index (g _C ), etc.]
The branching index (g ') is calculated as the ratio (ηbranch / ηlin) between the limiting viscosity (ηbranch) obtained by measuring the sample with the above Viscometer and the limiting viscosity (ηlin) separately obtained by measuring the linear polymer. Do.
When long chain branching is introduced into the polymer molecule, the radius of inertia is smaller compared to linear polymer molecules of the same molecular weight. Since the smaller the radius of inertia, the smaller the limiting viscosity, the ratio (極限 branch / bralin) of the limiting viscosity (分岐 branch) of the branched polymer to the limiting viscosity (ηlin) of the linear polymer of the same molecular weight decreases as the long chain branching is introduced. It will be. Therefore, if the branching index (g '= bra branch /) lin) becomes smaller than 1, it means that branching is introduced, and as the value becomes smaller, the introduced long chain branching increases It means that. In the present invention, in particular, the lowest value of the above g 'at a molecular weight of 100,000 to 1,000,000 is calculated as g _C as an absolute molecular weight obtained from MALLS. An example of the analysis result by said GPC-VIS is shown in FIG. 2, and the branch index (g ') in molecular weight (M) is represented. Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used as a linear polymer.

1-4. Condition (4) W ₂ + W ₃
In addition to the above conditions (1) to (3), the ethylene / α-olefin copolymer (A) used in the present invention is further determined from the integral elution curve measured by cross fractionation chromatography (CFC) The ratio (W ₂ ) of the component having a molecular weight of not less than the weight average molecular weight among the components eluted below the temperature at which the elution amount becomes 50% by mass and the temperature at which the elution amount determined from the integral elution curve is 50% by mass Among the components eluted at high temperature, the sum (W ₂ + W ₃ ) of the proportion (W ₃ ) of components having a molecular weight less than the weight average molecular weight is more than 40% by mass and less than 56% by mass. Preferably, it is more than 41% by mass, less than 56% by mass, more preferably more than 43% by mass, less than 56% by mass, particularly preferably more than 45% by mass and less than 56% by mass.

When the W ₂ + W ₃ value is 40% by mass or less, the proportion of the low density high molecular weight component that effectively acts to improve the impact strength of the polyolefin resin decreases, or the rigidity of the polyolefin resin is effectively improved. The action of high density and low molecular weight components is reduced, and it is uneconomical to require a blend of a large amount of ethylene / α-olefin copolymer in order to exhibit the physical property improving effect. On the other hand, when the W ₂ + W ₃ value is 56% by mass or more, the balance between the high density low molecular weight component and the low density high molecular weight component contained in the ethylene / α-olefin copolymer collapses, The physical property modification effect of the flame retardant resin composition may not be exhibited as expected.
The W ₂ + W ₃ value of the ethylene / α-olefin copolymer (A) of the present invention can be roughly determined by the types of catalyst component (A) and catalyst component (B) described later, and the catalyst It can be adjusted by changing the polymerization conditions such as the molar ratio of, the polymerization temperature, the pressure, and the time, and the polymerization process.

[CFC measurement conditions]
The cross fractionation chromatograph (CFC) is composed of a temperature rising elution fractionation (TREF) portion for performing crystalline fractionation and a gel permeation chromatography (GPC) portion for performing molecular weight fractionation.
The analysis using this CFC is performed as follows.
First, after completely dissolving the polymer sample in orthodichlorobenzene (ODCB) containing 0.5 mg / mL BHT at 140 ° C., this solution is passed through the sample loop of the device and held at 140 ° C. TREF column (inert The solution is injected into a column packed with a glass bead carrier, and gradually cooled to a predetermined first elution temperature to crystallize the polymer sample. After holding at a predetermined temperature for 30 minutes, ODCB is passed through a TREF column, whereby the eluted components are injected into the GPC part and molecular weight fractionation is performed, and an infrared detector (MIRAN 1A IR detector manufactured by FOXBORO, A chromatogram is obtained with a measurement wavelength of 3.42 μm). Meanwhile, in the TREF section, the temperature is raised to the next elution temperature, and after the chromatogram of the first elution temperature is obtained, the elution component at the second elution temperature is injected into the GPC section. Hereinafter, by repeating the same operation, chromatograms of the eluted components at each elution temperature can be obtained.

In addition, the measurement conditions of CFC are as follows.
Device: Diamond Instruments CFC-T102L
GPC column: Showa Denko AD-806 MS (three connected in series)
Solvent: ODCB
Sample concentration: 3 mg / mL
Injection volume: 0.4 mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stability time after GPC measurement: 5 minutes Elution temperature: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 , 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, 140

[Data analysis]
From the chromatogram of the eluted components at each elution temperature obtained by the measurement, the elution amount (proportional to the area of the chromatogram) standardized so that the total sum becomes 100% is determined.
Furthermore, an integrated elution curve is calculated with respect to the elution temperature, and this integrated elution curve is differentiated by temperature to obtain a differential elution curve.
Also, from each chromatogram, the molecular weight distribution can be determined by the following procedure. The conversion from the retention volume to the molecular weight is performed using a calibration curve with standard polystyrene prepared in advance. The standard polystyrenes used are all of the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is generated by injecting 0.4 mL of a solution of ODCB (containing 0.5 mg / mL BHT) so that each standard polystyrene is 0.5 mg / mL.
The calibration curve uses a cubic equation obtained by approximation using the least squares method.
For conversion to molecular weight, a general-purpose calibration curve is used with reference to "Side Exclusion Chromatography" by Kyori Mori (Kyoritsu Publishing). The following numerical values are used for the viscosity formula [ ^α ] = K × M ^α used at that time.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
In the chromatogram at the first elution temperature, the peak due to BHT added to the solvent may overlap with the low molecular weight side of the eluted component, but in that case, the baseline is drawn as shown in FIG. Determine the section to be sought.

Furthermore, as shown in Table 1 below, the weight average molecular weight of whole (whole) is determined from the elution ratio (mass% in the table) and weight average molecular weight (Mw in the table) at each elution temperature.

In addition, from the molecular weight distribution and elution amount at each elution temperature, the document (S. Nakano, Y. Goto, "Development of automatic Cross Fractionation: Combination of Crystallability Fractionation and Molecular Weight Fractionation", J. Appl. Polym. Sci., Vol. 26, pp. 4217-4231 (1981), to obtain a graph (contour map) showing the elution amount related to the elution temperature and the molecular weight as contour lines.
The following component amounts are determined using the above contour map.
W ₁ : Proportion of components having molecular weight less than the weight average molecular weight among the components eluted below the temperature at which the elution amount determined from the integral elution curve is 50% by mass W ₂ : The elution amount determined from the integral elution curve is 50% by mass The ratio of components with molecular weight higher than the weight average molecular weight among components eluted below the temperature where W ₃ : Molecular weight among the components eluted at a temperature higher than the temperature at which the elution amount determined from the integral elution curve becomes 50 mass% Proportion of component less than average molecular weight W ₄ : Proportion of component having molecular weight of weight average molecular weight or more among components eluted at a temperature higher than the temperature at which the elution amount determined from the integral elution curve becomes 50% by mass W ₁ + W ₂ + W ₃ + W ₄ = 100% by mass.
The value of W ₂ + W ₃ can be in a predetermined range mainly by selecting the polymerization catalyst and the polymerization conditions, preferably in a predetermined range by using a specific metallocene catalyst. Can.

1-5. Condition (5) W ₂ -W ₄
In addition to the above conditions (1) to (4), the ethylene / α-olefin copolymer (A) in the present invention further has an elution amount determined from the integrated elution curve measured by the above W ₂ and CFC. the percent difference between the molecular weight is weight average molecular weight or more components of the components eluted at a temperature higher than the temperature at which 50 _{wt% (W 4) (W 2} -W 4) is greater than 0 wt%, less than 20 wt% is there. Preferably, it is more than 0 mass%, less than 15 mass%, more preferably more than 1 mass%, less than 15 mass%, still more preferably more than 2 mass%, less than 14 mass%, particularly preferably more than 2 mass%, It is less than 13% by mass.
When W ₂ -W ₄ is 0% by mass or less, the low-density high-molecular-weight components which particularly effectively affect the impact strength improvement of the polyolefin resin contained in the ethylene / α-olefin copolymer tend to decrease . On the other hand, when the W ₂ -W ₄ value is 20% by mass or more, the balance between the content of the high density high molecular weight component and the low density high molecular weight component contained in the ethylene / α-olefin copolymer is broken, and the flame retardant Property modification effect of the water-soluble resin composition tends not to be exhibited as expected.
The W ₂ -W ₄ value of the ethylene / α-olefin copolymer (A) of the present invention can be roughly determined by the types of catalyst component (A) and catalyst component (B) described later, and It can be adjusted by changing the polymerization conditions such as the molar ratio of the catalyst, polymerization temperature, pressure, time and the like and the polymerization process.

  The ethylene / α-olefin copolymer (A) in the present invention essentially satisfies the above conditions (1) to (5), but as a preferred embodiment, ethylene / α-olefin copolymer (A) further satisfies the following condition (6). An alpha-olefin copolymer is mentioned.

1-6. Condition (6) Mw / Mn
The ethylene / α-olefin copolymer in the present invention preferably has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of preferably 3.0 to 7.0, more preferably 3. 0 to 5.9, more preferably 3.0 to 5.1, still more preferably 3.2 to 5.1, particularly preferably 3.3 to less than 5.0. If the Mw / Mn is less than 3.0, the processability at the time of extrusion molding tends to be reduced, which tends to cause appearance defects such as melt fracture.
Moreover, when Mw / Mn is larger than 7.0, it will lead to the fall of the rigidity and impact strength of a flame retardant resin composition.
In addition, in this invention, Mw and Mn of an ethylene * alpha-olefin copolymer mean what was measured by the gel permeation chromatography (GPC) method.
The Mw / Mn of the ethylene / α-olefin copolymer (A) of the present invention can be roughly determined by the types of catalyst component (A) and catalyst component (B) described later, and the molar ratio of the catalyst It can be adjusted by changing the polymerization conditions such as the ratio, polymerization temperature, pressure, time and the like and the polymerization process. The Mw / Mn can also be adjusted by combining a plurality of ethylene / α-olefin copolymers having different molecular weights.

In the measurement of GPC, conversion from the retention volume to the molecular weight is performed using a calibration curve with standard polystyrene prepared in advance. The standard polystyrenes used are all of the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each standard polystyrene is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation using the least squares method. For conversion to molecular weight, a general-purpose calibration curve is used with reference to "Side Exclusion Chromatography" by Kyori Mori (Kyoritsu Publishing). The following numerical values are used for the viscosity formula [ ^α ] = K × M ^α used at that time.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733

In addition, the measurement conditions of GPC are as follows.
Device: GPC (ALC / GPC 150C) manufactured by Waters
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD 806 M / S (3)
Mobile phase solvent: ODCB
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Preparation of sample: The sample is prepared using a solution of 1 mg / mL with ODCB (containing 0.5 mg / mL BHT) and dissolved for about 1 hour at 140 ° C.
In addition, the baseline and the section of the obtained chromatogram are performed as illustrated in FIG.

1-7. Constitution of the ethylene / α-olefin copolymer (A) of the present invention The ethylene / α-olefin copolymer (A) used in the present invention is a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms It is. As the α-olefin which is a copolymerization component used here, propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, pentene-1, hexene-1, heptene -1, octene-1, nonene-1, decene-1 and the like. Moreover, only 1 type of these alpha-olefins may be sufficient, and 2 or more types may be used together. Among these, more preferable α-olefins are those having 3 to 8 carbon atoms, and specifically, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, pentene-1, hexene-1 , Heptene-1, octene-1 and the like. More preferable α-olefins are those having 4 or 6 carbon atoms, and specific examples thereof include butene-1, 4-methylpentene-1, and hexene-1. An especially preferred α-olefin is hexene-1.

  The proportions of ethylene and α-olefin in the ethylene / α-olefin copolymer (A) used in the present invention are 75 to 99.8% by mass of ethylene and 0.2 to 25% by mass of α-olefin, preferably Is 80 to 99.6% by mass of ethylene, 0.4 to 20% by mass of α-olefin, more preferably 82 to 99.2% by mass of ethylene, 0.8 to 18% by mass of α-olefin, still more preferably Is 85 to 99% by mass of ethylene and 1 to 15% by mass of an α-olefin, and particularly preferably 88 to 98% by mass of ethylene and 2 to 12% by mass of an α-olefin. If the ethylene content is within this range, the effect of reforming the polyethylene resin is high.

  The copolymerization of ethylene and α-olefin may be any of alternating copolymerization, random copolymerization and block copolymerization. Of course, it is also possible to use a small amount of comonomers other than ethylene and α-olefin, in which case styrene, styrenes such as 4-methylstyrene, 4-dimethylaminostyrene, etc., 1,4-butadiene, 1,5- It has a polymerizable double bond such as dienes such as hexadiene, 1,4-hexadiene, 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, and oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenoate Compounds can be mentioned. However, it goes without saying that when a diene is used, it must be used within the range in which the long chain branched structure satisfies the above condition (3).

2. Method for Producing Ethylene / α-Olefin Copolymer (A) The ethylene / α-olefin copolymer of the present invention is produced and used so as to satisfy at least the above conditions (1) to (5). The production is carried out by a method of copolymerizing ethylene and the above-mentioned α-olefin using a catalyst for olefin polymerization.

The specific catalyst components described below as an example of a suitable production method for simultaneously achieving the above-mentioned long-chain branched structure, composition distribution structure, MFR, and density related conditions of the ethylene / α-olefin copolymer of the present invention The method of using the catalyst for olefin polymerization containing (A), (B) and (C) can be mentioned.
Catalyst component (A): bridged cyclopentadienylindenyl compound containing transition metal element Catalyst component (B): compound which reacts with the compound of catalyst component (A) to form a cationic metallocene compound Catalyst component (C): Inorganic compound carrier

2-1. Catalyst component (A)
A preferred catalyst component (A) for producing the ethylene / α-olefin copolymer of the present invention is a bridged cyclopentadienylindenyl compound containing a transition metal element, more preferably the following general formula [1] And more preferably a metallocene compound represented by the following general formula [2].

[Wherein, in the formula [1], M represents a transition metal of either Ti, Zr or Hf. A ¹ crosslinks a ligand having a cyclopentadienyl ring (conjugated 5-membered ring) structure, A ² crosslinks a ligand having an indenyl ring structure, and Q ¹ crosslinks A ¹ and A ² at any position. Indicates a bonding group. X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a carbon atom having 1 to 20 carbon atoms A hydrogen group substituted amino group or a C1-C20 alkoxy group is shown. ]

[Wherein, in the formula [2], M represents a transition metal of either Ti, Zr or Hf. Q ¹ represents a linking group linking the cyclopentadienyl ring and the indenyl ring. X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a carbon atom having 1 to 20 carbon atoms A hydrogen group substituted amino group or a C1-C20 alkoxy group is shown. Each of 10 R's independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, 20 represents a halogen-containing hydrocarbon group having 20, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. ]
A particularly preferable catalyst component (A) for producing the ethylene / α-olefin copolymer of the present invention is a metallocene compound represented by the general formula (1c) described in JP-A-2013-227271.

[Wherein, in the formula (1c), M ^1c represents a transition metal of either Ti, Zr or Hf. X ^1c and X ^2c each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or 1 to 20 carbon atoms Or a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Each of Q ^1c and Q ^2c independently represents a carbon atom, a silicon atom or a germanium atom. R ^1c each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of four R ^1c are combined to form a ring together with Q ^1c and Q ^2c , It is also good. m ^c is 0 or 1, and when m ^c is 0, Q ^1c is directly bonded to a conjugated 5-membered ring containing R ^2c . R ^2c and R ^4c are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, 1 carbon atom And -20 halogen-containing hydrocarbon groups, C1-C20 hydrocarbon groups containing an oxygen atom or C1-C20 hydrocarbon group-substituted silyl groups are shown. R ^3c represents a substituted aryl group represented by the following general formula (1-ac). ]

[Wherein, in the formula (1-ac), Y ^1c represents an atom of Groups 14, 15, or 16 of the periodic table. R ^5c , R ^6c , R ^7c , R ^8c and R ^9c each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon number containing oxygen or nitrogen 1 to 20 hydrocarbon group, C 1 to C 20 hydrocarbon group-substituted amino group, C 1 to C 20 alkoxy group, C 1 to C 18 silicon-containing hydrocarbon group containing 1 to 6 silicon atoms, carbon 1 to 20 halogen-containing hydrocarbon group or hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, wherein R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are bonded to each other by adjacent groups And may form a ring together with the atoms to which they are attached. n ^c is 0 or 1, and when n ^c is 0, there is no substituent R ^{5c in} Y ^1c . ^pc is 0 or 1, and when ^pc is 0, the carbon atom to which R ^7c is bonded is directly bonded to the carbon atom to which R ^9c is bonded. When Y ^1c is a carbon atom, at least one of R ^5c , R ^6c , R ^7c , R ^8c and R ^9c is not a hydrogen atom. ]

  The most preferable catalyst component (A) for producing the ethylene / α-olefin copolymer of the present invention is a metallocene compound represented by the general formula (2c) described in JP-A-2013-227271.

In the metallocene compound represented by the above general formula (2c), M ^1c , X ^1c , X ^2c , Q ^1c , R ^1c , R ^2c and R ^4c are the descriptions of the metallocene compound represented by the above-mentioned general formula (1c) The same structure as the atom and group shown in can be selected. In addition, R ^10c can select a structure similar to the atoms and groups of R ^5c , R ^6c , R ^7c , R ^8c and R ^9c shown in the description of the metallocene compound represented by the general formula (1c) above. .

  As specific examples of the above metallocene compounds, compounds described in General Formulas (4c) and Tables 1c-1 to 5 and General Formulas (5c) and (6c) and Tables 1c-6 to 9 of JP-A-2013-227271 are described. Although compounds can be mentioned, it is not limited to these.

  The compounds of the above specific examples are preferably zirconium compounds or hafnium compounds, and more preferably zirconium compounds.

  Two or more kinds of the above-mentioned crosslinked cyclopentadienylindenyl compounds can also be used as a catalyst component (A) preferable for producing the ethylene / α-olefin copolymer of the present invention.

2-2. Catalyst component (B)
The preferred catalyst component (B) for producing the ethylene / α-olefin copolymer of the present invention is a compound which reacts with the compound of the catalyst component (A) to form a cationic metallocene compound, more preferably It is a catalyst component (B) described in opening 2013-227271 [0064]-[0083], More preferably, it is an organic aluminum oxy compound described in the same [0065]-[0069].

2-3. Catalyst component (C)
A preferred catalyst component (C) for producing the ethylene / α-olefin copolymer of the present invention is an inorganic compound carrier, more preferably it is described in JP-A 2013-227271 [0084] to [0088] Inorganic compounds. At this time, preferable as the inorganic compound is the metal oxide described in the above-mentioned publication [0085].

2-4. Process for producing a catalyst for olefin polymerization The ethylene / α-olefin copolymer of the present invention is a copolymer of ethylene and the above-mentioned α-olefin using a catalyst for olefin polymerization containing the above-mentioned catalyst components (A) to (C) It is preferably manufactured by the following method. The contact method of each catalyst component in obtaining the catalyst for olefin polymerization from the above catalyst components (A) to (C) of the present invention is not particularly limited, and, for example, the method of (I) to (III) shown below It can be adopted arbitrarily.

(I) A catalyst component (A) which is a bridged cyclopentadienylindenyl compound containing the transition metal element and a catalyst component which is a compound which reacts with the compound of the catalyst component (A) to form a cationic metallocene compound After contacting with (B), the catalyst component (C) which is an inorganic compound carrier is contacted.
(II) After contacting the catalyst component (A) with the catalyst component (C), the catalyst component (B) is contacted.
(III) After contacting the catalyst component (B) with the catalyst component (C), the catalyst component (A) is contacted.

  Of these contacting methods, (I) and (III) are preferred, and (I) is most preferred. In any contacting method, generally, in an inert atmosphere such as nitrogen or argon, generally, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene (usually having a carbon number of 6 to 12), pentane, heptane, hexane, decane A method in which each catalyst component is brought into contact with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as dodecane and cyclohexane. Ru. This contact is usually performed at a temperature of -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably It is desirable to carry out for 30 minutes to 12 hours.

  Further, when contacting the catalyst component (A), the catalyst component (B) and the catalyst component (C), as described above, an aromatic hydrocarbon solvent in which certain catalyst components are soluble or poorly soluble, and Any aliphatic or alicyclic hydrocarbon solvent in which the catalyst component is insoluble or poorly soluble can be used.

  In the case where the catalytic reaction of each catalyst component is carried out stepwise, this may be used as it is as the solvent for the subsequent catalytic reaction without removing the solvent used in the former stage. In addition, liquid inactive hydrocarbons in which some catalyst components are insoluble or sparingly soluble after catalytic reaction in the former stage using a soluble solvent (eg, pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc. fat) Group hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon) to recover the desired product as a solid, or once or partially removing the soluble solvent by means such as drying. After removal of the desired product as a solid, subsequent catalytic reaction of the desired product can also be carried out using any of the above-mentioned inert hydrocarbon solvents. In the present invention, multiple catalytic reactions of each catalyst component are not hindered.

  In the present invention, the use ratio of the catalyst component (A), the catalyst component (B) and the catalyst component (C) is not particularly limited, but the following range is preferable.

  When an organoaluminum oxy compound is used as the catalyst component (B), the atomic ratio (Al / M) of aluminum of the organoaluminum oxy compound to the transition metal (M) in the catalyst component (A) is usually 1 to 100, Preferably, it is in the range of 100, preferably 100 to 1,000, more preferably 210 to 800, particularly preferably 250 to 500, and when a borane compound or a borate compound is used, the transition metal (M) in the catalyst component (A) The atomic ratio (B / M) of boron to) is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Furthermore, in the case of using a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound as the catalyst component (B), the same use as described above for the transition metal (M) for each compound in the mixture It is desirable to select by ratio.

  The amount of the catalyst component (C) used is preferably 0.0001 to 0.5 mmol, more preferably 0.001 to 0.2 mmol, and more preferably 0.005 to 0.1 mmol per 0.0001 to 5 mmol of the transition metal in the catalyst component (A). Particularly preferably, it is 1 g per 0.01 to 0.04 mmol.

  In the present invention, the ratio of the number of moles of the metal of the catalyst component (B) to 1 g of the catalyst component (C) is preferably more than 0.006 and not more than 0.020 (mole / g), more preferably 0. More than .006 to 0.015 (mol / g) or less, more preferably more than 0.006 to 0.012 (mol / g) or less, particularly preferably 0.007 to 0.010 (mol / g) It is.

  The catalyst component (A), the catalyst component (B) and the catalyst component (C) are brought into contact with each other by selecting the above-mentioned contact methods (I) to (III) as appropriate, and then removing the solvent, The olefin polymerization catalyst can be obtained as a solid catalyst. The solvent is removed at 0 to 200 ° C., preferably 20 to 150 ° C., more preferably 20 to 100 ° C. for 1 minute to 100 hours, preferably 10 minutes to 50 hours, more preferably 30 minutes under normal pressure or reduced pressure. It is desirable to do in ~ 20 hours.

The olefin polymerization catalyst can also be obtained by the methods (IV) and (V) shown below.
(IV) The catalyst component (A) is brought into contact with the catalyst component (C) to remove the solvent, and this is used as a solid catalyst component, and under polymerization conditions, an organoaluminum oxy compound, a borane compound, a borate compound or a mixture thereof Make contact.
(V) The catalyst component (C) is brought into contact with the catalyst component (C) by contacting the catalyst component (C) with the organoaluminum oxy compound, borane compound, borate compound or a mixture thereof, which is the catalyst component (B). Contact with the catalyst component (A).
Also in the case of the contact method of said (IV) and (V), the conditions similar to the above can be used for catalyst component ratio, contact conditions, and solvent removal conditions.

  Further, as an olefin polymerization catalyst suitable for obtaining the ethylene / α-olefin copolymer of the present invention, a catalyst component (B) which reacts with the catalyst component (A) to form a cationic metallocene compound and a catalyst component ( As a catalyst component also serving as C), layered silicates well known and described in Japanese Patent Application Laid-Open Nos. 05-301917 and 08-127613 can also be used. The layered silicate is a silicate compound having a crystal structure in which planes constituted by ionic bonds and the like are stacked in parallel with each other by weak bonding force. Most layered silicates are naturally produced mainly as a main component of clay minerals, but these layered silicates are not particularly limited to naturally occurring ones, and may be artificially synthesized ones.

  Among these, smectites, vermiculites, micas such as montmorillonite, saukonite, beidellite, nontronite, saponite, hectorite, Stephenite, bentonite, and teniolite are preferable.

  The use ratio of the catalyst component (A) and the layered silicate carrier is not particularly limited, but the following range is preferable. The amount of the catalyst component (A) supported is 0.0001 to 5 millimoles, preferably 0.001 to 0.5 millimoles, more preferably 0.01 to 0.1 millimoles, per gram of the layered silicate carrier.

  The olefin polymerization catalyst thus obtained may be used after prepolymerization of monomers, if necessary.

2-5. Polymerization method of ethylene / α-olefin copolymer The ethylene / α-olefin copolymer of the present invention is preferably ethylene using a catalyst for olefin polymerization prepared by the production method described in the above 2-4. And the above-mentioned .alpha.-olefin.

  As an alpha-olefin which is a comonomer, as above-mentioned, a C3-C10 alpha-olefin can be used, It is also possible to copolymerize two or more types of alpha-olefin with ethylene, Said alpha It is also possible to use small amounts of comonomers other than olefins.

In the present invention, the above copolymerization reaction can be carried out preferably in a gas phase method or a slurry method. In the case of gas phase polymerization, ethylene and the like are polymerized in a reactor in which a gas stream of ethylene and a comonomer is introduced, circulated or circulated while oxygen and water are substantially cut off.
In the case of slurry polymerization, an inert hydrocarbon selected from aliphatic hydrocarbons such as isobutane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Ethylene and the like are polymerized in the presence or absence of a solvent. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as the solvent.
In the present invention, a further preferred polymerization is gas phase polymerization. The polymerization conditions are such that the temperature is 0 to 250 ° C., preferably 20 to 110 ° C., more preferably 60 to 100 ° C., and the pressure is normal pressure to 10 MPa, preferably normal pressure to 4 MPa, further preferably 0.5 to 2 MPa The polymerization time is usually 5 minutes to 20 hours, preferably 30 minutes to 10 hours.

In order to obtain a relatively narrow inverse comonomer composition distribution copolymer having a suitable range of long chain branching and low density high molecular weight components in an appropriate ratio, which is one of the features of the present invention, a catalyst component ( Besides the selection of the type of A) and the catalyst component (B), the molar ratio of the catalyst component (A) and the catalyst component (B), the molar ratio of the catalyst component (A) and the catalyst component (C), the catalyst component B) a molar ratio of the catalyst component (C), polymerization temperature, ethylene partial pressure, H 2 _/ C ₂ ratio, by varying the polymerization conditions such as the comonomer / ethylene ratio can be suitably adjusted.
Specifically, for example, in the case of using the complex described in Example 1, as a method of adjusting the catalyst, complex / silica = 10 to 40 μmol / g, organic aluminum oxy compound / silica = 7 to 10 mmol / g, adjustment The use of an agent is optional, polymerization conditions 60 to 90 ° C., ethylene partial pressure 0.3 to 2.0 MPa, H ₂ / C ₂ % = 0.2 to 2.0%, C ₆ / C ₂ = 0. It sets suitably in 1 to 0.8% of range.
Moreover, even if it adds the component for the purpose of water removal in the polymerization system, a so-called scavenger, it can be implemented without any problem.
Such scavengers include organic aluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the aforementioned organic aluminum oxy compounds, modified organic aluminum compounds containing branched alkyl, organic zinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutyl magnesium and ethylbutyl magnesium, and Grignard compounds such as ethyl magnesium chloride and butyl magnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.

The long chain branching structure (ie, g _C ) and the comonomer copolymerization composition distribution (ie, X and W _{1 to} W ₄ ) of the formed copolymer, which is one of the features of the present invention, are the catalyst component (A) and the catalyst component ( The range is roughly determined by the type of B), but can be adjusted by changing the molar ratio of the catalyst, the polymerization conditions such as the polymerization temperature, pressure and time, and the polymerization process. Even if a catalyst component type that easily forms a long chain branched structure is selected, it is also possible to produce, for example, a copolymer having less long chain branched structure by lowering the polymerization temperature or increasing the ethylene pressure. Also, even if a catalyst component having a wide molecular weight distribution or copolymer composition distribution is selected, a copolymer having a narrow molecular weight distribution or copolymer composition distribution can be produced by changing, for example, the catalyst component molar ratio, polymerization conditions and polymerization process. It is also possible.

  The ethylene / α-olefin copolymer of the present invention is also suitable if the polymerization conditions are appropriately set even in a two or more multistage polymerization system in which the polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, polymerization temperature are different from each other. Although it may be possible to produce the ethylene / α-olefin copolymer of the present invention when it is produced by a one-step polymerization reaction, it is more economical to set complicated polymerization operating conditions. It is preferable because it can be manufactured to

3. Other polyolefin resin (B)
The other polyolefin resin (B) in the composition of the present invention is a polyolefin other than the ethylene / α-olefin copolymer (A) satisfying the above conditions (1) to (5), and has a low density Polyethylene, medium density polyethylene, high density polyethylene, polyolefins comprising copolymers of ethylene and α, β-unsaturated carboxylic acids or derivatives thereof, eg polyethylene resins produced by ionic polymerization (b1), high pressure radicals It includes homopolymers or alternating copolymers of α-olefins having 3 or more carbon atoms such as a formal ethylene (co) polymer (b2) and a polypropylene resin (b3).
The polyethylene resin (b1) produced by the above-mentioned ionic polymerization is an ethylene homopolymer or an ethylene · α-olefin having a density of 0.94 to 0.97 g / cm ³ and MFR of 0.05 to 100 g / 10 min. A high-density polyethylene resin composed of a copolymer, an ethylene / α-olefin copolymer having a density of 0.91 to less than 0.94 g / cm ³ , and an MFR of 0.05 to 100 g / 10 min. Linear low density polyethylene resin, linear ultra low density composed of ethylene / α-olefin copolymer having density of 0.86 to less than 0.91 g / cm ³ and MFR of 0.05 to 100 g / 10 min. It includes polyethylene resin.

  The above α-olefin is preferably a linear or branched olefin having 3 to 20 carbon atoms, and examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, -Octene, 1-decene and the like can be mentioned. Also, two or more of them may be used in combination. Among these copolymers, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer are economical. It is suitable from the viewpoint.

The polyethylene resin (b1) produced by the above-mentioned ionic polymerization is not particularly limited to the production catalyst or process, and the reference book "polyethylene technical reader" (Matsuura Kazuo / Mikami ed., Ed. Year) p. 123-160, p. It is possible to manufacture by the method described in 163-196 etc. That is, it is possible to use various polymerization systems, polymerization conditions and catalysts in various polymerization modes such as slurry method, solution method and gas phase method using Ziegler type catalyst, single site type catalyst, etc. is there.
The polyethylene resin (b1) according to the present invention comprises ethylene in the presence of an olefin polymerization catalyst comprising an organoaluminum oxy compound and a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton. When it is a copolymer obtained by copolymerizing と and an α-olefin having 3 to 20 carbon atoms, it is more preferable. The polyethylene resin (b1) according to the present invention may be a mixture of two or more polyethylene resins (b1) as long as the above conditions are satisfied.

  The high-pressure radical method ethylene (co) polymer (b2) according to the present invention refers to an ethylene homopolymer (low density polyethylene resin), an ethylene-vinyl ester copolymer, ethylene and Examples thereof include copolymers with saturated carboxylic acids or derivatives thereof, and these low density polyethylene resins are produced by a known high pressure radical polymerization method, and may be produced by any of a tubular method and an autoclave method.

The low density polyethylene resin described above has a density of 0.91 to 0.935 g / cm ³ , an MFR of 0.05 to 100 g / 10 min, preferably a density of 0.915 to 0.930 g / cm ³ , and an MFR The thing of the range of 0.1-50 g / 10min is used suitably.
The ethylene / vinyl ester copolymer described above is mainly composed of ethylene and vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. And copolymers thereof.
Among these, vinyl acetate is particularly preferable. A copolymer comprising 50 to 99.5% by mass of ethylene, 0.5 to 50% by mass of vinyl ester, and 0 to 49.5% by mass of another copolymerizable unsaturated monomer is preferable. Furthermore, the vinyl ester content is selected in the range of 3 to 20% by mass, particularly preferably 5 to 15% by mass.
Moreover, a functional group containing ethylene-type copolymer is mentioned as a preferable example among other polyolefin resin (B). Specific examples of functional group-containing ethylene-based copolymers include ethylene / methyl acrylate copolymer, ethylene-based copolymer as a representative copolymer of the above-mentioned copolymer of ethylene and α, β-unsaturated carboxylic acid ester. · Ethylene (meth) acrylic acid or its alkyl ester copolymer such as ethyl acrylate copolymer, ethylene · butyl acrylate copolymer, ethylene · methyl methacrylate copolymer, ethylene · ethyl methacrylate copolymer, etc. Binary or multicomponent copolymers such as ethylene / maleic anhydride / vinyl acetate copolymer, ethylene / maleic anhydride / methyl acrylate copolymer, ethylene / maleic anhydride / ethyl acrylate copolymer Etc. The (meth) acrylic acid ester content is in the range of 3 to 30% by mass, preferably 5 to 20% by mass.

  Examples of the polypropylene-based resin (b3) include propylene homopolymers, copolymers of propylene and other α-olefins, such as block copolymers of propylene and ethylene, random copolymers, etc. is there.

4. Thermoplastic elastomer (C)
As thermoplastic elastomer (C) in the composition of the present invention, various thermoplastic elastomers such as olefin elastomer, styrene elastomer, polyester elastomer, polyamide elastomer, polyurethane elastomer, natural rubber, polyisobutylene, polyisoprene, Included are natural or synthetic rubbers such as chloroprene rubber, butyl rubber, nitrile butyl rubber and the like. Among these, olefin-based elastomers and styrene-based elastomers described in detail below are preferable.

As the olefin elastomer, the density of an ethylene / propylene copolymer (EPR), an ethylene / propylene / diene copolymer (EPDM), an ethylene / 1-butene copolymer, an ethylene / 1-octene copolymer, etc. Partially crosslinked product obtained by crosslinking amorphous or microcrystalline ethylene / α-olefin copolymer at 86 to 0.91 g / cm ³ , polybutene, chlorinated polyethylene, polypropylene and EPDM and optionally polyethylene in the presence of a crosslinking agent Or a completely crosslinked product.

  As styrene-based elastomers, block copolymers such as styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-isoprene-butadiene-styrene copolymer (SIBS), etc. Or styrene / ethylene / butene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS), styrene / butadiene / butylene / styrene copolymer (partially hydrogenated styrene / butadiene / styrene copolymer Partially or completely hydrogenated products of block copolymers such as coalesced.

5. Metal hydroxide (D)
As the metal hydroxide (D) of the present invention, for example, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, basic magnesium carbonate, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite And the like can be used alone or in combination of two or more compounds having a hydroxyl group or crystal water. Among these metal hydroxides, magnesium hydroxide and aluminum hydroxide are preferred, and magnesium hydroxide is most preferred. Moreover, those to which surface treatment was given especially are preferable.

As the above magnesium hydroxide, magnesium hydroxide generally used in a flame retardant resin composition, that is, magnesium chloride in seawater is made to react with calcium hydroxide as a raw material, and processes such as sedimentation, washing, concentration, etc. The obtained magnesium hydroxide, for example, "Kisuma 5", "Kisuma 5A", "Kisuma 5B", "Kisuma 5J" (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.), etc. may be mentioned.
In addition, known substances such as magnesium hydroxide obtained by grinding a natural mineral (brucite) containing magnesium hydroxide as a main component can also be used. Furthermore, in recent years, magnesium chloride obtained by treating a natural mineral containing magnesium (such as brucite, serpentine, dolomite, chlorite, etc.) with hydrochloric acid is used as a raw material to react, for example, with calcium hydroxide to precipitate, wash, In addition to magnesium hydroxide obtained by a process such as concentration, magnesium hydroxide obtained by hydrating magnesium oxide obtained by dissolution, purification or thermal decomposition can also be used. However, the present invention is not limited to the above.
Among these, magnesium hydroxide obtained by calcining magnesium carbonate to form magnesium oxide and hydrating it has a large specific surface area of 8 m ² / g or more of particles, and the performance of the conventional flame retardant composition is also obtained. It is preferable because it has high flame retardancy and economical cost without reducing it, and is excellent in ease of cutting of wire and cable end (peel cutting processability) at the time of installation of wire and cable, and good workability. used.

As a preferable method for producing the above metal hydroxide, as a natural mineral (magnesite) disclosed in Japanese Examined Patent Publication Nos. 3-60774, 5-208810 and 8-67515. The produced magnesium carbonate is fired and pulverized to form a fine powder of lightly burned magnesia, which is subjected to a saturating (hydration) reaction.
In addition, by using a method of obtaining magnesium hydroxide by quenching reaction of lightly burned magnesia obtained by calcining and pulverizing magnesium carbonate produced as a natural mineral (magnesite), the pulverizing time at the pulverizing step is obtained. By controlling the milling speed, the pH at the smelting step, the reaction temperature and the like, it is possible to inexpensively manufacture magnesium hydroxide in which the average particle diameter, the specific surface area and the aggregation structure are optimized.

Moreover, in order to improve the dispersion effect in a thermoplastic resin, suppression of moisture absorption, the inactivation of a metal active point, etc., it is preferable to perform the process by a surface treatment agent.
The surface treatment agent may, for example, be a fatty acid and a fatty acid metal salt or a mixture thereof, a fatty acid ester, a fatty acid amide, a wax or a modified product thereof, a curable resin, an organosilane, an organic titanate, an organoborane and the like. Furthermore, polycarboxylic acid-based dispersions have recently been disclosed as disclosed in Japanese Patent Application Laid-Open Nos. 2002-167219, 2002-173682, 2003-003167, 2004-337698, and the like. , Polyglycerin derivatives, N-acyl basic amino acids, or dibasic acid erythritol esters, phosphoric acid esters, phosphorous acid esters, alcohol phosphoric acid esters, magnesium phosphate surface-treated with phosphorus compounds etc. There is.
In the present invention, although not particularly limited thereto, fatty acids and fatty acid metal salts or mixtures thereof and combinations with fatty acid esters are particularly preferable from the viewpoint of low cost and effectiveness. These may be surface-treated in advance, or resin components and magnesium hydroxide may be mixed and used simultaneously.

As the above fatty acid, a saturated or unsaturated acid having 8 or more carbon atoms is desirable, and octanoic acid, decanoic acid, myristic acid, behenic acid, palmitic acid, stearic acid, oleic acid, arachic acid, coconut oil, beef tallow, large Bean oil, palm oil, hydrogenated oil and the like can be mentioned. Examples of the fatty acid metal salt include metal salts such as stearic acid, oleic acid, palmitic acid, linoleic acid, lauric acid, caprylic acid, behenic acid and montanic acid, and metals such as Na, K, Al, Ca, Mg, Zn, Ba, Co, Sn, Ti, Fe and the like can be mentioned. As the above fatty acid ester, methyl laurate, methyl myrysylate, methyl palmitate, methyl stearate, methyl oleate, methyl erbate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, isopropyl palmitate, And monoesters such as octyl palmitate, coconut fatty acid octyl ester, octyl stearate, special beef tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, long chain fatty acid higher alcohol ester, behenyl behenate and cetyl mycylinate. Neopentyl polyol long chain fatty acid ester, partial esterified product of neopentyl polyol long chain fatty acid ester, neopentyl polyol fatty acid ester, in neopentyl polyol Fatty acid esters, neopentyl polyol C9 chain fatty acid esters, dipentaerythritol long chain fatty acid esters, special fatty acid esters such as complex medium chain fatty acid esters.
These surface treatment agents can be used in any treatment method such as a wet method or a dry method. The amount of the surface treatment agent used is preferably in the range of 1 to 10% by mass with respect to the metal hydroxide.

6. Modified polyolefin resin (E)
In the flame retardant resin composition of the present invention, a modified polyolefin resin (E) can be blended, if necessary. The modified polyolefin resin has good compatibility with resins such as ethylene / α-olefin copolymer (A), other polyolefin resins and other polyolefin resins (B) and thermoplastic elastomers (C). , The effect of coupling with metal hydroxide (D) is remarkable, and it promotes mechanical strength of the flame retardant resin composition, promotes formation of a carbonized layer at the time of combustion, and uses it as a role to improve mechanical strength and flame retardancy Be Specifically, the modified polyolefin resin (E) is further added to 100 parts by mass of the ethylene / α-olefin copolymer (A) and the other polyolefin resin (B) and / or the thermoplastic elastomer (C). Those containing 30 to 30 parts by mass are preferred.

The modified polyolefin resin is (i) an unsaturated carboxylic acid or a derivative thereof, (ii) an epoxy group-containing compound, (iii) a hydroxyl group-containing compound, (iv) an amino group-containing compound, (v) an organosilane compound, vi) A polyolefin resin modified with a functional group-containing compound such as an organic titanate compound can be mentioned.
(I) Examples of unsaturated carboxylic acids or derivatives thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinylacetic acid, pentenoic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, etc. Or an α, β-unsaturated dicarboxylic acid or anhydride thereof, or a metal salt thereof.
(Ii) As an epoxy group-containing compound, acrylic acid glycidyl, glycidyl methacrylate, monoglycidyl itaconate, butene tricarboxylic acid monoglycidyl ester, butene tricarboxylic acid diglycidyl ester, butene tricarboxylic acid triglycidyl ester, α-chloroallyl, and maleic acid Acids, glycidyl esters such as crotonic acid and fumaric acid or vinyl glycidyl ether, allyl glycidyl ether, glycidyl oxyethyl vinyl ether, glycidyl ethers such as styrene-p-glycidyl ether, p-glycidyl styrene and the like are particularly preferable. As a thing, glycidyl methacrylate and allyl glycidyl ether can be mentioned.
(Iii) As a hydroxyl group containing compound, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate etc. are mentioned.
(Iv) Examples of amino group-containing compounds include tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate.
(V) Examples of the organic silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane and vinyltrichlorosilane.
(Vi) Examples of organic titanate compounds include tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexoxy) titanate, titanium lactate ammonium and the like.

  The content of the functional group-containing compound in the modified polyolefin resin is selected in the range of 0.05 to 10% by mass, preferably 0.1 to 8.0% by mass. When the content is less than 0.05% by mass, the effects of the invention are not sufficient, and there is a possibility that the coupling effect between the resin and the flame retardant is not exhibited. Moreover, when it exceeds 10 mass%, there exists a possibility that decomposition | disassembly and a crosslinking reaction may occur simultaneously, when denatured.

A modified polyolefin resin is obtained by modifying a polyolefin resin by heating in the presence of a functional group-containing compound and an organic peroxide. What made content of a functional group containing compound 0.05-10 mass%, or what mixed this modified substance with unmodified | non_denatured polyolefin resin, and adjusted the content to the said range is used.
As said polyolefin resin used for modification | denaturation, the said polyolefin resin and these mixtures can be used. Among these, ethylene homopolymers or ethylene / α-olefin copolymers having a density of 0.87 to 0.97 g / cm ³ are mentioned, and among these, those modified with linear low density polyethylene and the polyolefin resin Excellent compatibility with magnesium hydroxide, maintaining heat resistance without losing flexibility of the soft resin, promoting formation of a carbonized layer at the time of combustion, improving flame retardancy, and hope for improvement in mechanical strength Most preferred.

7. Other Components In the flame retardant resin composition of the present invention, in order to further improve the performance, additives such as a flame retardant auxiliary may be added to the present invention.
As a flame retardant auxiliary, red phosphorus, antimony trioxide, antimony pentoxide, calcium phosphate, zircon oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, calcium carbonate, magnesium carbonate, barium sulfate, barium borate, barium metaborate, boric acid Zinc, zinc metaborate, molybdenum disulfide, clay, diatomaceous earth, kaolinite, montmorillonite, hydrotalcite, talc, silica, white carbon, zeolite, hydromagnesite, organic bentonite and the like may be used in combination. It is desirable to add up to 50% by mass of these flame retardant aids with respect to the metal hydroxide (D).

  Furthermore, in the flame retardant resin composition of the present invention, various additives and auxiliary materials can be blended according to the purpose of use as long as the characteristics of the present invention are not impaired. As various additives and auxiliary materials, stabilizers, antioxidants, antioxidants, UV absorbers, light stabilizers, antistatic agents, processability improvers, fillers, copper inhibitors, neutralizers, A foaming agent, an anti-whitening agent, an antifoaming agent, a nucleating agent, a coloring agent, a lubricant, a process oil, a silicone oil, a carbon black and the like can be mentioned. Further, crosslinking can be performed by adding a crosslinking agent such as an organic peroxide, sulfur or a silane based crosslinking agent or a crosslinking assistant, or can be crosslinked by irradiation with ionizing radiation.

8. Flame Retardant Resin Composition The flame retardant resin composition of the present invention can be composed of an ethylene / α-olefin copolymer (A) and a metal hydroxide (D), but a large amount of metal Since a hydroxide is compounded, in order to secure the acceptance amount and to maintain flexibility, other polyolefin resin (B) and / or in addition to the ethylene / α-olefin copolymer (A) It is desirable that the thermoplastic elastomer (C) be used in combination. The composition ratio is 100 to 5% by mass, more preferably 50 to 10% by mass, and particularly preferably 40 to 20% by mass of the ethylene / α-olefin copolymer (A). B) and / or the thermoplastic elastomer (C) is 0 to 95% by mass, more preferably 50 to 90% by mass, particularly preferably 60 to 80% by mass, and the other polyolefin resin (B) and / or heat By selecting the above-mentioned soft resins (b1) to (b3) or olefinic elastomers such as EPR and EPDM as the plasticizable elastomer (C), high flame retardancy and high moldability are maintained, and mechanical strength is maintained. It can be improved.

9. Composition Ratio of Flame Retardant Resin Composition The composition ratio of each component in the flame retardant resin composition of the present invention is ethylene / α-olefin copolymer (A) and other polyolefin resin (B) and / or heat The metal hydroxide (D) is 30 to 300 parts by mass, preferably 50 to 250 parts by mass, more preferably 70 to 200 parts by mass, further 100 parts by mass of the resin component composed of the plasticizable elastomer (C). Preferably it is 70-150 mass parts. If the compounding amount of the metal hydroxide (D) is less than 30 parts by mass, the flame retardancy is insufficient, and if it exceeds 300 parts by mass, the material becomes brittle and becomes hard, and the flexibility and mechanical strength of the product Not only does it tend to lower, it can also have the negative effects of scratching and whitening.
In the above composition, the modified polyolefin resin (E) is not necessarily required when the resin component is sufficiently soft, but when the modified polyolefin resin (E) is used, 100 parts by mass of the resin component The resin composition is composed of 30 to 300 parts by mass of metal hydroxide (D) and 1 to 30 parts by mass of modified polyolefin resin (E). The modified polyolefin resin (E) is generally blended in an amount of 1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass. By the presence of the modified polyolefin resin (E), a coupling effect between the resin component and the metal hydroxide (D) is generated, and the mechanical properties of the flame retardant resin composition are improved. When the amount is less than 1 part by mass, the reforming effect is not sufficiently exhibited, and when the amount is more than 30 parts by mass, the coupling effect is excessive, the material becomes hard, and flexibility and flexibility are lost. There may be adverse effects such as a decrease in workability when winding the electric wire / cable on the drum.

10. Method for Producing Flame Retardant Resin Composition The flame retardant resin composition of the present invention comprises the ethylene / α-olefin copolymer (A), another polyolefin resin (B) and / or a thermoplastic elastomer (C). ), Metal hydroxide (D), and, if necessary, modified polyolefin resin (E) in any order according to the above-mentioned mixing ratio, a single screw extruder, a twin screw extruder, a super mixer, a Henschel mixer It can manufacture by knead | mixing and granulating using normal kneaders, such as a Banbury mixer, a roll mixer, Brabender plastograph, and a kneader. In this case, it is preferable to select a kneading and granulation method that can make the dispersion of each component good, and in particular, kneading and granulation using a twin-screw extruder is preferable from the viewpoint of economy and the like.
As a preferable production method of the flame retardant composition of the present invention, the metal hydroxide (D) may be ethylene / α-olefin copolymer (A), other polyolefin resin (B), thermoplastic elastomer (C) And a portion of any of the modified polyolefin resin (E), and the mixture and the remaining ethylene / α-olefin copolymer (A), other polyolefin resins (B), thermoplastic elastomer (C) A method of kneading more uniformly by mixing with the modified polyolefin resin (E).

11. Electric wire / cable The flame retardant resin composition of the present invention may be an electric wire, a power cable, an insulating layer and / or a sheath layer such as an optical fiber cable, an inner semiconductive layer and / or an outer semiconductive layer, or optionally copper, aluminum, It may be used as a covering layer provided in a usual electric wire / cable such as an external metal shielding layer such as lead or a water-impervious layer wound with aluminum tape. Also, the method for producing the electric wire / cable may be a general method, and it may be used after being crosslinked by organic peroxide or silane crosslinking, or in a non-crosslinked state or in a foamed state, thermoplastic resin or metal foil It may be used by laminating with other base materials such as nonwoven fabric and woven fabric, and it is not particularly limited.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples to demonstrate the superiority of the present invention and the superiority in the configuration of the present invention, but the present invention is limited by these examples. It is not a thing.
In addition, the measuring method used in the Example and the comparative example is as follows. Further, the following catalyst synthesis step and polymerization step were all performed under a purified nitrogen atmosphere, and the solvent used was one that has been dehydrated and purified using molecular sieve 4A.

[Method of measuring physical properties]
(1) MFR
Measured under the conditions of 190 ° C. and 21.18 N (2.16 kg) load according to JIS K 7210 “Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic” .
(2) Density Measured according to JIS K7112 (1999 edition): Method A (substitution method in water).

(3) Molecular weight distribution (Mw / Mn) measured by GPC
It measured by the gel permeation chromatography (GPC) method. The measurement conditions of GPC are as follows.
Device: GPC (ALC / GPC 150C) manufactured by Waters
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD 806 M / S (3)
Mobile phase solvent: ODCB
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Preparation of sample: The sample is prepared using a solution of 1 mg / mL with ODCB (containing 0.5 mg / mL BHT) and dissolved for about 1 hour at 140 ° C.
In addition, the baseline and the section of the obtained chromatogram were performed as illustrated in FIG.
The conversion from the retention volume to the molecular weight was performed using a calibration curve with standard polystyrene prepared in advance. The standard polystyrenes used are all of the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve was generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each standard polystyrene is 0.5 mg / mL. The calibration curve used the cubic equation obtained by approximating by the least squares method. For conversion to molecular weight, a general-purpose calibration curve was used with reference to "Side Exclusion Chromatography" written by Mori Sadao (Kyoritsu Publishing). The following numerical values were used for the viscosity formula [η] = K × M ^α used at that time.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733

(4) The lowest value (gc) of the branching index (g ') of a molecular weight between 100,000 and 1,000,000 as measured by a GPC measuring device combining a differential refractometer, a viscosity detector and a light scattering detector
As GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer), Alliance GPCV2000 made by Waters Co. was used. As a light scattering detector, DAWN-E manufactured by Multiangle Laser Light Scattering Detector (MALLS) Wyatt Technology was used. Detectors were connected in the order of MALLS, RI, Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (addition of the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As a column, two GMHHR-H (S) HTs manufactured by Tosoh Corporation were used in combination. The temperature of the column, sample injection unit and each detector is 140.degree. The sample concentration was 1 mg / mL. The injection volume (sample loop volume) is 0.2175 mL. In order to determine the absolute molecular weight (M) obtained from MALLS, the radius of inertia square (Rg) and the limiting viscosity ([η]) obtained from Viscometer, use the data processing software ASTRA (version 4.73.04) attached to MALLS. The calculation was performed with reference to the above-mentioned documents.
[Calculation of branching index (g _C ), etc.]
The branching index (g ') is calculated as the ratio (ηbranch / ηlin) between the limiting viscosity (ηbranch) obtained by measuring the sample with the above Viscometer and the limiting viscosity (ηlin) separately obtained by measuring the linear polymer. did.
As the absolute molecular weight obtained from the MALLS, the minimum value of the g 'in the molecular weight 100,000 from 1,000,000, was calculated as _{g C.} Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used as a linear polymer.

(5) W ₂ + W ₃ and W ₂ -W ₄
It was carried out by cross fractionation chromatography (CFC) comprising a temperature rising elution fractionation (TREF) part performing crystalline fractionation and a gel permeation chromatography (GPC) part performing molecular weight fractionation.
That is, after completely dissolving the polymer sample in orthodichlorobenzene (ODCB) containing 0.5 mg / mL BHT at 140 ° C., this solution is passed through the sample loop of the device and kept at 140 ° C. on the TREF column (inert The polymer sample was crystallized by injecting into a column packed with a glass bead carrier and gradually cooling to a predetermined first elution temperature.
After holding at a predetermined temperature for 30 minutes, ODCB is passed through a TREF column, whereby the eluted components are injected into the GPC part and molecular weight fractionation is performed, and an infrared detector (MIRAN 1A IR detector manufactured by FOXBORO, A chromatogram was obtained at a measurement wavelength of 3.42 μm. Meanwhile, the temperature was raised to the next elution temperature in the TREF section, and a chromatogram of the first elution temperature was obtained, and then the elution component at the second elution temperature was injected into the GPC section. Hereinafter, by repeating the same operation, chromatograms of the eluted components at each elution temperature were obtained.
In addition, the measurement conditions of CFC are as follows.
Device: Diamond Instruments CFC-T102L
GPC column: Showa Denko AD-806 MS (three connected in series)
Solvent: ODCB
Sample concentration: 3 mg / mL
Injection volume: 0.4 mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stability time after GPC measurement: 5 minutes Elution temperature: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 , 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, 140

[Data analysis]
From the chromatograms of the eluted components at each elution temperature obtained by the measurement, the elution amount (proportional to the area of the chromatogram) normalized so that the total sum becomes 100% was determined.
Further, from each chromatogram, the molecular weight distribution was determined by the same procedure as the above-mentioned GPC.

From the molecular weight distribution and elution amount at each elution temperature, the document (S. Nakano, Y. Goto, "Development of automatic Cross Fractionation: Combination of Crystallization Fractionation and Molecular Weight Fractionation", J. Appl. Polym. Sci., Vol. 26 , Pp. 4217-4231 (1981)), a graph (contour map) showing the elution amount related to the elution temperature and the molecular weight as contour lines was obtained.
The following component amounts were determined using the above contour map.
W ₁ : The ratio of the component whose molecular weight is less than the weight average molecular weight of the ethylene / α-olefin copolymer among the components eluted below the temperature at which the elution amount determined from the integral elution curve becomes 50% by mass.
W _2: ratio of the weight average molecular weight or more components having a molecular weight of component elution volume as determined from integral elution curve is eluted with the following temperature at which 50 wt% is the ethylene · alpha-olefin copolymer.
W ₃ : The ratio of the component whose molecular weight is less than the weight average molecular weight of the ethylene / α-olefin copolymer among the components eluted at a temperature higher than the temperature at which the elution amount determined from the integral elution curve becomes 50% by mass.
W ₄ : The ratio of the component having a molecular weight equal to or more than the weight-average molecular weight of the ethylene / α-olefin copolymer among the components eluted at a temperature higher than the temperature at which the elution amount determined from the integral elution curve becomes 50% by mass.
Note _that it is _{W 1 + W 2 + W 3} + W 4 = 100 wt%.

[Evaluation of material properties]
[Tension breaking strength and tensile breaking elongation]
A dumbbell-shaped No. 3 test piece was punched out of the obtained press sheet according to JIS C3005 (2000) “Rubber / Plastic Insulated Wire Testing Method”, and the tensile breaking strength and the elongation were determined at a tensile speed of 200 mm / min.
[Oxygen Index]
Based on the test method of JISK7201-1 (1999), it measured using the IV type test piece pierced from the press sheet with a thickness of 3 mm. A large number indicates that the flame retardancy is excellent.
[Evaluation of extrusion appearance]
Extrusion characteristics were evaluated by extruding the flame retardant resin composition under the following conditions and observing the strand appearance.
Testing machine: Capirograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd.
Orifice: L / D = 25.4 / 1.53, inlet angle 90 °, setting temperature 190 ° C., piston speed 500 mm / min.
Appearance evaluation method: The appearance of the strand was visually observed and judged by the following method.
○: Strand surface is smooth and good. X: The strand surface is not smooth.
[Comprehensive evaluation]
About the flame retardant resin composition, comprehensive judgment was performed according to the following judgment criteria.
That is, when the content of magnesium hydroxide is 70 parts by mass or less, the tensile strength at break is 10.0 MPa or more, the tensile elongation at break is 500% or more, the oxygen index is 23.0% or more, and extrusion Those with an appearance of ○ were designated as “○”, and those other than that were designated as “x”. When the content of magnesium hydroxide exceeds 70 parts by mass, the tensile strength at break is 8.8 MPa or more, the tensile elongation at break is 260% or more, the oxygen index is 25.0% or more, and the extrusion appearance is The thing which is (circle) was made into "(circle)", and the thing which is (circle) was made into "x".

( Reference Example 1 )
(1) Synthesis of Bridged Cyclopentadienyl Indenyl Compound Synthesis of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride according to the method described in JP-A-2013-227271 did.
(2) Synthesis of catalyst for olefin polymerization In a nitrogen atmosphere, 30 g of silica calcined at 400 ° C. for 5 hours was put in a 500 ml three-necked flask, and then 195 ml of dehydrated toluene was added to make a slurry. The dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride 412 milligram of the dimethylsilylene synthesized in the above (1) is charged under a nitrogen atmosphere into a separately prepared 200 ml two-necked flask and dehydrated toluene After dissolution with 80.7 ml, 78.9 ml of Albemarle's 20% methylaluminoxane / toluene solution was further added at room temperature and stirred for 30 minutes. While heating and stirring a 500 ml three-necked flask containing a toluene slurry of silica in a 40 ° C. oil bath, the entire amount of the toluene solution of the reaction product of the above zirconocene complex and methylaluminoxane was added. After stirring at 40 ° C. for 1 hour, the solution was allowed to stand still for 15 minutes while heating to 40 ° C., and 221 ml of the supernatant was removed, dehydrated hexane was added, stirring was performed with static settling and supernatant removed to obtain toluene content in the solvent. After substituting to 3% or less, it was evaporated under reduced pressure to obtain a powdery catalyst.
(3) Treatment of catalyst for olefin polymerization In a nitrogen atmosphere, 32 g of the powdery catalyst obtained in the above (2) is put in a 500 ml three-necked flask, and 195 ml of dehydrated hexane and dehydrated liquid paraffin (manufactured by MORESCO; trade name Moresco) A mixture of 180 g of White P-120) was added at room temperature and stirred for 10 minutes, and the mixture was evaporated under reduced pressure until the hexane content in the solvent became 5% or less at room temperature to obtain a slurry catalyst.
(4) Production of ethylene / α-olefin copolymer Ethylene / 1-hexene gas phase continuous copolymerization was performed using the slurry catalyst obtained in (3) above. That is, 0.027 g of the powdered catalyst was added to a gas-phase continuous polymerization apparatus prepared at a temperature of 85 ° C., a hexene / ethylene molar ratio of 0.43%, a hydrogen / ethylene molar ratio of 0.52% and an ethylene pressure of 1.5 MPa. The polymerization was carried out with constant gas composition and temperature while intermittently supplying at the speed of. In addition, triethylaluminum (TEA) was supplied to the gas circulation line at 0.04 mmol / hr to maintain the cleanliness of the system. As a result, the average formation rate of the produced polyethylene was 180 g / hour (average residence time 10 hours). The MFR and density of the ethylene / 1-hexene copolymer obtained after producing a cumulative amount of 5 kg or more of polyethylene were 0.36 g / 10 min and 0.921 g / cm ³ , respectively. The results are shown in Table 2.
1,000 ppm of antioxidant (Sumilyzer GP manufactured by Sumitomo Chemical Co., Ltd.) was added to the polymer and evaluated by extruding at an extrusion temperature of 180 ° C. using a single-screw extruder (USV type 30φ extruder manufactured by Union Plastics) It was pelletized for use.
A composition prepared by blending 70 parts by mass of magnesium hydroxide (d1) (Kyosuma Chemical Co., Ltd., Kisuma 5A) with 100 parts by mass of ethylene / α-olefin copolymer (a1) is kneaded under the following conditions, and a flame retardant Resin composition was obtained.

[Kneading conditions]
Using a Laboplast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd. as a kneading apparatus, kneading was performed at a kneading temperature of 200 ° C., a rotation number of 50 rpm, and a kneading time of 5 minutes to obtain a flame retardant resin composition. The obtained flame retardant resin composition was further kneaded for 5 minutes using a roll kneader, and then press molding was performed to obtain press sheets having a thickness of 1 mm and 3 mm.
The evaluation results of the above flame retardant resin composition are shown in Table 2.

( Reference example 2 )
An ethylene / α-olefin copolymer (a2) was produced according to the method for producing an ethylene / α-olefin copolymer of Reference Example 1 .
A resin composition prepared by blending 70 parts by mass of magnesium hydroxide (d1) with 100 parts by mass of ethylene / α-olefin copolymer (a2) is kneaded under the same conditions as in Example 1 to obtain a flame retardant resin composition. Obtained. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

( Reference Example 3 )
An ethylene / α-olefin copolymer (a3) was produced according to the method for producing an ethylene / α-olefin copolymer of Reference Example 1 .
A resin composition prepared by blending 70 parts by mass of magnesium hydroxide (d1) with 100 parts by mass of ethylene / α-olefin copolymer (a3) is kneaded under the same conditions as in Example 1 to obtain a flame retardant resin composition. Obtained. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Example 4)
70 parts by mass of magnesium hydroxide (d1) is blended with 100 parts by mass of a resin component consisting of 20% by mass of ethylene / α-olefin copolymer (a1) and 80% by mass of ethylene / ethyl acrylate copolymer (b1) The resin composition was kneaded under the same conditions as in Reference Example 1 to obtain a flame retardant resin composition. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 .
As other polyolefin resin (B), ethylene having an MFR of 0.8 g / 10 min, gc of 0.32, W ₂ + W ₃ of 43% by mass, and an ethyl acrylate unit content of 15% by mass An ethyl acrylate copolymer (b1) was used.
The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Example 5)
Water to 100 parts by mass of a resin component consisting of 20% by mass of ethylene / α-olefin copolymer (a1), 75% by mass of ethylene / ethyl acrylate copolymer (b1), 5% by mass of maleic anhydride-modified polyethylene (e1) A resin composition comprising 70 parts by mass of magnesium oxide (d1) was kneaded under the same conditions as in Reference Example 1 to obtain a flame retardant resin composition. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 .
As other polyolefin resin (B), ethylene having an MFR of 0.8 g / 10 min, gc of 0.32, W ₂ + W ₃ of 43% by mass, and an ethyl acrylate unit content of 15% by mass Using ethyl acrylate copolymer (b1), as modified polyolefin resin (E), MFR is 1.3 g / 10 min, density is 0.920 g / cm ³ , and maleic anhydride grafting amount is 0.21 mass% Maleic anhydride modified polyethylene (e1) was used.
The evaluation results of the above flame retardant resin composition are shown in Table 2.

( Reference Example 6 )
A resin composition prepared by blending 100 parts by mass of magnesium hydroxide (d1) with 100 parts by mass of ethylene / α-olefin copolymer (a1) is kneaded under the same conditions as in Example 1 to obtain a flame retardant resin composition. Obtained. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

( Reference Example 7 )
A resin composition comprising 100 parts by mass of magnesium hydroxide (d1) in 100 parts by mass of a resin component consisting of 95% by mass of ethylene / α-olefin copolymer (a1) and 5% by mass of maleic anhydride-modified polyethylene (e1) The mixture was kneaded under the same conditions as in Reference Example 1 to obtain a flame retardant resin composition. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Example 8)
100 parts by mass of magnesium hydroxide (d1) is blended with 100 parts by mass of a resin component consisting of 20% by mass of ethylene / α-olefin copolymer (a1) and 80% by mass of ethylene / ethyl acrylate copolymer (b1) The resin composition was kneaded under the same conditions as in Reference Example 1 to obtain a flame retardant resin composition. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Example 9)
Water to 100 parts by mass of a resin component consisting of 20% by mass of ethylene / α-olefin copolymer (a1), 75% by mass of ethylene / ethyl acrylate copolymer (b1), 5% by mass of maleic anhydride-modified polyethylene (e1) A resin composition comprising 100 parts by mass of magnesium oxide (d1) was kneaded under the same conditions as in Reference Example 1 to obtain a flame retardant resin composition. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Comparative example 1)
Magnesium hydroxide (100 parts by mass of ethylene / 1-hexene copolymer (a4) (density: 0.918 g / cm ³ , MFR: 2.2 g / 10 min) produced by a vapor phase process using a metallocene catalyst d1) A resin composition formed by blending 70 parts by mass was kneaded under the same conditions as in Reference Example 1 to obtain a flame retardant resin composition. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Comparative example 2)
A resin composition comprising 100 parts by mass of low density polyethylene (a5) (density: 0.924 g / cm ³ , MFR: 0.7 g / 10 min) manufactured by a high pressure method and magnesium hydroxide (d1) parts by mass The mixture was kneaded under the same conditions as in Reference Example 1 to obtain a flame retardant resin composition. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Comparative example 3)
Commercially available metallocene polyethylene (a6) having long-chain branching (density: 0.922 g / cm ³ , MFR 0.3 g / 10 min, W ₂ + W ₃ 41% by mass, W ₂ -W ₄ 0% by mass, A resin composition prepared by blending 70 parts by mass of magnesium hydroxide (d1) with 100 parts by mass of Mw / Mn is 7.2 is kneaded under the same conditions as in Example 1 to obtain a flame retardant resin composition. The Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

(Comparative example 4)
Ethylene / acrylic acid 20 mass% ethylene / 1-hexene copolymer (a4) (density 0.918 g / cm ³ , MFR 2.2 g / 10 min) produced by vapor phase method using metallocene catalyst Resin composition obtained by blending 70 parts by mass of magnesium hydroxide (d1) with 100 parts by mass of resin component consisting of 80% by mass of ethyl copolymer (b1) is kneaded under the same conditions as in Example 1 to obtain a flame retardant resin The composition was obtained. Using the obtained flame retardant resin composition, a press sheet was prepared and tested in the same manner as in Reference Example 1 . The evaluation results of the above flame retardant resin composition are shown in Table 2.

The flame-retardant resin compositions described in Examples 4 , 5 , 8 and 9 satisfy the requirements of the present invention, and the strand appearance of the extrusion-molded article is good and the moldability is excellent, and furthermore, the tensile elongation at break and elongation Excellent.
Further, as in the flame-retardant resin compositions of Examples 4 and 5 and Examples 8 and 9, ethylene / ethyl acrylate copolymer (b1) in the resin component, and further, maleic anhydride modified polyethylene (e1) By blending it, it is possible to significantly improve the tensile strength at break while maintaining a good strand appearance.
On the other hand, in the flame retardant resin composition of Comparative Example 1, the lowest value (gc) of the branching index (g ') of the ethylene / .alpha.-olefin copolymer (a4) at a molecular weight of 100,000 to 1,000,000 is Outside the requirements of the present invention, the strand appearance was not good and the formability was reduced.
In the flame retardant resin composition of Comparative Example 2, the minimum value (gc) of the branching index (g ') of the ethylene / α-olefin copolymer (a5) at a molecular weight of 100,000 to 1,000,000 is within the range of the present invention. Outside the requirement, the strand appearance was not good and the formability was reduced. The _W 2 + _{W 3} and _W 2 -W ₄ to be measured was reduced mechanical properties it is outside the requirements of the present invention by CFC.
In the flame retardant resin composition of Comparative Example 3, W ₂ -W ₄ measured by CFC of the ethylene / α-olefin copolymer (a6) deviates from the requirements of the present invention, and the mechanical physical property improvement effect is It was not enough.
The flame retardant resin composition of Comparative Example 4 has the lowest value (gc) of the branching index (g ') of the ethylene / α-olefin copolymer (a5) of 100,000 to 1,000,000 of the molecular weight of the present invention. Outside the requirement, the strand appearance was not good and the formability was reduced.

As is apparent from the above, the flame retardant resin composition for electric wire / cable coating of the present invention is excellent in molding processing characteristics, and at the same time excellent in mechanical strength such as tensile breaking strength, and further in appearance of molded articles. It is also possible to provide molded products economically economically.
Therefore, the industrial value of the flame retardant resin composition for electric wire / cable coating and electric wire / cable of the present invention which can economically and advantageously provide a molded product having such desirable characteristics is extremely large.

Claims (7)

50 to 5% by mass of ethylene / α-olefin copolymer (A) satisfying the following conditions (1) to (5) and ethylene / vinyl acetate copolymer and / or ethylene / ethyl acrylate copolymer 50 The flame retardant resin composition for electric wire and cable coating which contains 30-300 mass parts of magnesium hydroxide (D) with respect to 100 mass parts of resin components containing 95 mass% .
(1) The melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg exceeds 0.1 g / 10 min and is 10 g / 10 min or less.
(2) The density is 0.895 to 0.940 g / cm ³ .
(3) The lowest molecular weight of the branching index (g ') between 100,000 and 1,000,000 as measured by a gel permeation chromatography (GPC) measuring device combining a differential refractometer, a viscosity detector and a light scattering detector The value (gc) is 0.40 to 0.85.
(4) The weight of the ethylene / α-olefin copolymer among the components eluted below the temperature at which the elution amount determined from the integral elution curve measured by cross fractionation chromatography (CFC) is 50% by mass or less Among the components eluted at a temperature higher than the temperature at which the proportion of components above the average molecular weight (W ₂ ) and the elution amount determined from the integral elution curve becomes 50 mass%, the molecular weight is the weight of the ethylene / α-olefin copolymer The sum (W ₂ + W ₃ ) of the proportion (W ₃ ) of the components below the average molecular weight is 40 to 80% by mass.
(5) the ratio of the W ₂ and component molecular weight is more than the weight average molecular weight of the component elution amount obtained is eluted at a temperature higher than the temperature at which 50 mass% from the integrated elution curve measured by CFC (W ₄₎ The difference (W ₂ -W ₄ ) is more than 0% by mass and less than 20% by mass. The ethylene / α-olefin copolymer has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 3.0 to 7.0 as measured by GPC. Flame retardant resin composition for electric wire and cable coating of The flame retardant resin composition for electric wire / cable coating according to claim 1 or 2, wherein the ethylene / α-olefin copolymer (A) has 3 to 10 carbon atoms of α-olefin. 1 to 30 parts by mass of modified polyolefin resin (E) with respect to 100 parts by mass of ethylene / α-olefin copolymer (A) and ethylene / vinyl acetate copolymer and / or ethylene / ethyl acrylate copolymer The flame retardant resin composition for electric wire and cable coating according to any one of claims 1 to 3 comprising. The flame retardant resin composition for electric wire and cable coating according to any one of claims 1 to 4, which has a tensile elongation at break of 540% or more. The flame retardant resin composition for electric wire / cable coating according to any one of claims 1 to 5, which has a tensile elongation at break of 540 to 740%. The electric wire and cable which coat | cover the flame-retardant resin composition for electric wire and cable coating as described in any one of Claims 1-6.

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