JP2017137378A - Resin composition and insulated wire and cable using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of being molded without causing aggregation of an additive, and to provide an insulated wire and a cable using the same.SOLUTION: There is provided a resin composition where a content of a first additive is 5 pts.mass or more and 300 pts.mass or less and a content of a second additive is less than 5 pts.mass with respect to 100 pts.mass of a polyolefin resin; and the first additive is an additive that is a powder shape and has a ratio (D/D) between an average particle ratio (D) obtained when volume distribution of the additive is measured at a crushing pressure of 0.3 MPa by a dry method using a laser diffraction type particle distribution measuring instrument and an average particle ratio (D) obtained when volume distribution of the additive is measured without the crushing pressure by the dry method is 20 or more and 3 or less, and the second additive is a powder shape and has the ratio (D/D) of more than 3 and less than 20.SELECTED DRAWING: None

Description

The present invention relates to a resin composition and an insulated wire and cable using the same.
To do.

  As a resin composition used for an electric wire / cable insulator, sheath, etc., it is common to use a resin in which various additives are dispersed. As additives, for example, flame retardants, antioxidants, fillers, colorants and the like are often used (see, for example, Patent Document 1).

  Examples of the flame retardant include metal hydroxides such as magnesium hydroxide and aluminum hydroxide, phosphorus flame retardants, nitrogen flame retardants such as melamine cyanurate, halogen flame retardants such as bromine flame retardants, and antimony trioxide. Etc.

JP 2007-103247 A

  These additives may be aggregated without being uniformly dispersed in the polymer during kneading and molding. When aggregation occurs, problems such as poor appearance due to irregularities on the surface of the molded product and reduced tensile strength are caused.

  In order to prevent the occurrence of aggregation without reducing the addition amount, it has been performed to increase the particle shape, or to perform surface treatment.

  However, when the particle shape is increased, for example, a flame retardant causes a reduction in flame retardancy at the same addition amount, and a filler causes a reduction in reinforcing effect. In addition, when the surface treatment is performed, the number of steps increases and the cost of the additive increases. Some additives cannot perform surface treatment such as general silane treatment and fatty acid treatment.

  Even when the particle shape is increased or the surface treatment can be performed, it is difficult to determine the presence or absence of occurrence of aggregation unless it is evaluated using a manufacturing apparatus. Therefore, a large amount of sample is required to determine the optimal filler size and surface treatment amount, and enormous time and cost are required for the study.

  Further, the ease of aggregation of the additive differs depending on the molecular structure, the shape of the particle, the particle size, and the amount added, and thus it has been difficult to uniformly define the additive.

  Therefore, an object of the present invention is to provide a resin composition that can be molded without causing aggregation of additives, and an insulated wire and a cable using the same.

  In order to achieve the above object, the present invention provides the following resin composition, and an insulated wire and cable using the same.

[1] A resin composition in which the content of the following first additive is 5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the polyolefin resin, and the content of the following second additive is less than 5 parts by mass. .
First additive: powder and an average particle diameter _{(D50 (P0.3} ) when the volume distribution of the additive is dry measured at a crushing pressure of 0.3 MPa using a laser diffraction particle size distribution analyzer. ₎ ) And the ratio _{(D50 (P0)} / _{D50 (P0.3)} ) of the average particle diameter (D50 _(P0) ) when dry-measured without crushing pressure, the following formula (1) or formula ( additives which satisfies 2) second additive: powdery in and the ratio _{(D 50 (P0) / D} 50 (P0.3)) additives _{D 50} which satisfies the following formula (3) _{(P0 ) / D 50 (P0.3) ≧} 20 ··· formula (1)
D _{50 (P0)} / D _{50 (P0.3)} ≦ 3 (2)
3 <D _{50 (P0)} / D _{50 (P0.3)} <20 Formula (3)
[2] The resin composition according to [1], wherein the first additive is an additive satisfying the formula (1).
[3] The resin composition according to [1], wherein the first additive is an additive satisfying the formula (2).
[4] The resin composition according to [1], wherein the first additive is an additive having a hydroxyl group, an ester group, an amide group, or an amino group in a molecule.
[5] The resin composition according to [1], wherein the first additive is melamine cyanurate.
[6] The resin composition according to [1], wherein the first additive is melamine cyanurate that has not been surface-treated.
[7] The resin composition according to [1], wherein the first additive is melamine cyanurate and magnesium hydroxide.
[8] The above-mentioned [1] to [7], wherein the first additive has an average particle diameter _{(D50 (P0.3)} ) of 5 μm or less when dry measured at a crushing pressure of 0.3 MPa. The resin composition as described in any one.
[9] An insulated wire comprising a conductor and an insulating layer made of the resin composition according to any one of [1] to [8], which is coated on an outer periphery of the conductor.
[10] A cable including a sheath made of the resin composition according to any one of [1] to [8].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can be shape | molded without aggregation of an additive generate | occur | producing, an insulated wire and a cable using the same can be provided.

It is a cross-sectional view which shows an example of the insulated wire which concerns on embodiment of this invention. It is a cross-sectional view showing an example of a cable according to an embodiment of the present invention.

(Resin composition)
In the resin composition according to the embodiment of the present invention, the content of the following first additive with respect to 100 parts by mass of the polyolefin resin is 5 parts by mass or more and 300 parts by mass or less, and the content of the following second additive. Is less than 5 parts by mass.
First additive: powder and an average particle diameter _{(D50 (P0.3} ) when the volume distribution of the additive is dry measured at a crushing pressure of 0.3 MPa using a laser diffraction particle size distribution analyzer. ₎ ) And the ratio _{(D50 (P0)} / _{D50 (P0.3)} ) of the average particle diameter (D50 _(P0) ) when dry-measured without crushing pressure, the following formula (1) or formula ( additives which satisfies 2) second additive: powdery in and the ratio _{(D 50 (P0) / D} 50 (P0.3)) additives _{D 50} which satisfies the following formula (3) _{(P0 ) / D 50 (P0.3) ≧} 20 ··· formula (1)
D _{50 (P0)} / D _{50 (P0.3)} ≦ 3 (2)
3 <D _{50 (P0)} / D _{50 (P0.3)} <20 Formula (3)

(Polyolefin resin)
The resin composition according to the embodiment of the present invention contains a polyolefin resin as a base polymer.

  Examples of the polyolefin resin used in the embodiment of the present invention include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), linear very low density polyethylene (VLDPE), high density polyethylene (HDPE), polypropylene ( PP), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-styrene copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-butene-hexene terpolymer Polymer, ethylene-propylene-diene terpolymer (EPDM), ethylene copolymer polypropylene, ethylene-propylene copolymer (EPR), poly-4-methyl-pentene-1, maleic acid grafted low density polyethylene, hydrogenated Styrene-butadiene copolymer (H-SBR), maleic acid grafted linear low density polyethylene, ethylene Copolymers of ethylene and α-olefins having 4 to 20 carbon atoms such as ten-1 copolymer and ethylene-octene copolymer (EOR), maleic acid grafted ethylene-methyl acrylate copolymer, maleic acid grafted ethylene -Vinyl acetate copolymer, ethylene-maleic anhydride copolymer, ethylene-ethyl acrylate-maleic anhydride terpolymer, ethylene-propylene-butene-1 terpolymer having butene-1 as the main component More preferred is ethylene-vinyl acetate copolymer (EVA). These can be used alone or in combination of two or more.

(First additive)
The resin composition according to the embodiment of the present invention contains 5 parts by mass or more and 300 parts by mass or less of the first additive with respect to 100 parts by mass of the polyolefin resin.

The first additive for use in embodiments of the present invention has an average particle diameter (D ₅₀ at the time of dry measured at the solution砕圧force 0.3MPa the volume distribution of the filler by a laser diffraction particle size distribution measuring instrument _{( P0.3))} and the ratio of the average particle diameter at the time of dry measured without solution砕圧force _{(D 50 (P0)) (} D 50 (P0) / D 50 (P0.3)) satisfies the following formula (1) Or it is an additive which satisfies Formula (2). Here, D _{50 (P0)} is a value of 50% volume distribution at a crushing pressure of 0 MPa, and D _{50 (P0.3)} is a value of 50% volume distribution at a crushing pressure of 0.3 MPa.
D _{50 (P0)} / D _{50 (P0.3)} ≧ 20 (1)
D _{50 (P0)} / D _{50 (P0.3)} ≦ 3 (2)

  As the laser diffraction particle size distribution analyzer, for example, a Microtrac MT3300ExII particle size analyzer manufactured by Microtrac Bell Co., Ltd. can be used, and a dry measurement unit manufactured by the same company can be used for dry measurement.

In the first additive satisfying the above formula (1), the ratio (D _{50 (P0)} / D _{50 (P0.3)} ) is preferably 30 or more, more preferably 40 or more, More preferably, it is 50 or more, and most preferably 55 or more. The upper limit of the ratio ( _{D50 (P0)} / _{D50 (P0.3)} ) is not particularly limited, but is preferably 80 or less, more preferably 75 or less, and 70 or less. Is more preferred, and most preferred is 65 or less.

In the first additive satisfying the above formula (2), the ratio _{(D50 (P0)} / _{D50 (P0.3)} ) is preferably 2.5 or less, and is 2.2 or less. Is more preferable and 2 or less is still more preferable. The lower limit of the ratio ( _{D50 (P0)} / _{D50 (P0.3)} ) is not particularly limited, but is preferably 0.3 or more, more preferably 0.5 or more, and 0 More preferably, it is 7 or more.

As for the 1st additive used for embodiment of this invention, it is preferable that the said average particle diameter _{(D50 (P0.3)} ) at the time of dry-type measurement by the crushing pressure of 0.3 _Mpa is 5 _micrometers or less. It is more preferably 5 μm or less, and further preferably 4 μm or less. The lower limit of the average particle diameter (D _{50 (P0.3)} ) is not particularly limited, but is preferably 0.4 μm or more, more preferably 0.6 μm or more, and 0.8 μm or more. More preferably it is.

  The first additive used in the embodiment of the present invention is not particularly limited as long as it is powdery and satisfies the above formula (1) or formula (2). Metal hydroxides such as magnesium, aluminum hydroxide and calcium hydroxide, metal oxides such as aluminum oxide, zinc compounds such as silica, talc, clay, zinc stannate, zinc hydroxystannate, zinc borate, zinc oxide, etc. , Boric acid compounds such as calcium borate, barium borate and barium metaborate, phosphorus flame retardants, nitrogen flame retardants such as melamine cyanurate, halogen flame retardants such as bromine flame retardants, antimony trioxide, during combustion An intumescent flame retardant comprising a mixture of a foaming component and a solidifying component can be mentioned. These first additives are preferably silane coupling agents, titanate coupling agents, fatty acids such as stearic acid and calcium stearate, or those surface-treated with fatty acid metal salts. Among these, an additive having a hydroxyl group, an ester group, an amide group, or an amino group in the molecule is preferable. More preferred is melamine cyanurate. These can be used alone or in combination of two or more. A combination of melamine cyanurate and metal hydroxide is particularly preferred.

  The amount of the first additive is preferably 300 parts by mass or less with respect to 100 parts by mass of the polyolefin-based resin, and it is preferable because the properties such as tensile strength and elongation of the resin composition tend to decrease with the addition. Is 250 parts by mass or less, more preferably 220 parts by mass or less. Although the minimum of the addition amount of a 1st additive is 5 mass parts with respect to 100 mass parts of polyolefin resin, it is preferable that it is 50 mass parts, and it is more preferable that it is 100 mass parts.

  When blending two or more types, for example, when blending and using melamine cyanurate and a metal hydroxide such as magnesium hydroxide, the melamine cyanurate is 5 to 50 parts by mass, the metal hydroxide Are preferably blended within the range of 150 to 250 parts by mass.

(Second additive)
In the resin composition according to the embodiment of the present invention, the content of the second additive is less than 5 parts by mass with respect to 100 parts by mass of the polyolefin-based resin.

The second additive is an additive in which the aforementioned ratio (D _{50 (P0)} / D _{50 (P0.3)} ) satisfies the following formula (3).
3 <D _{50 (P0)} / D _{50 (P0.3)} <20 Formula (3)

  The second additive used in the embodiment of the present invention is not particularly limited as long as it is powdery and satisfies the above formula (3). Can be mentioned.

  The content of the second additive in the resin composition according to the embodiment of the present invention is preferably 3 parts by mass or less, and preferably 1 part by mass or less with respect to 100 parts by mass of the polyolefin resin. More preferably, it is more preferably 0.5 parts by mass or less, and most preferably 0 part by mass.

(Other additives)
In addition to the first additive, the resin composition according to the embodiment of the present invention includes the second additive, a flame retardant other than the above, an inorganic filler other than the above, and an antioxidant as necessary. It is possible to add additives such as agents, metal deactivators, crosslinking agents, crosslinking aids, lubricants, compatibilizers, stabilizers, carbon black, and colorants.

  Although it does not specifically limit as antioxidant, For example, a phenol type, sulfur type, amine type, and phosphorus antioxidant are mentioned. The type of phenolic antioxidant is not particularly limited. For example, dibutylhydroxytoluene (BHT), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl-4-hydroxy-benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like, more preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ]. The type of sulfur-based antioxidant is not particularly limited, but didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate , Tetrakis [methylene-3- (dodecylthio) propionate] methane, and the like, more preferably tetrakis [methylene-3- (dodecylthio) propionate] methane. These antioxidants can be used alone or in combination of two or more.

  The metal deactivator is not particularly limited as long as it has an effect of stabilizing metal ions by chelate formation and suppressing oxidative degradation, and its structure is not particularly limited, but N- (2H-1,2,4-triazole- 5-yl) salicylamide, dodecanedioic acid bis [N2- (2-hydroxybenzoyl) hydrazide], 2 ', 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl ]] Propionohydrazide and the like, and 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide is more preferable. These can be used alone or in a blend of two or more.

  The crosslinking aid is not particularly limited, but for example, use of trimethylolpropane trimethacrylate (TMPT) or triallyl isocyanurate (TAIC) is desirable.

  Examples of the lubricant include, but are not limited to, fatty acids, fatty acid metal salts, fatty acid amides, and the like, specifically, use of zinc stearate. These can be used alone or in a blend of two or more.

  Carbon black is not particularly limited, but carbon black for rubber (N900-N100: ASTM D 1765-01) is generally used.

  Although it does not specifically limit as a coloring agent, The color masterbatch for non-halogens etc. can be used.

  The resin composition according to the embodiment of the present invention may be crosslinked by an organic peroxide or by radiation such as an electron beam. A known method can be used as the crosslinking method, and there is no particular limitation.

[Insulated wire]
An insulated wire according to an embodiment of the present invention includes a conductor and an insulating layer made of the resin composition according to the embodiment of the present invention, which is coated on the outer periphery of the conductor.

FIG. 1 is a cross-sectional view showing an example of an insulated wire according to an embodiment of the present invention.
As shown in FIG. 1, the insulated wire 10 according to the present embodiment includes a conductor 1 and an insulating layer 2 covered on the outer periphery of the conductor 1. As the conductor 1 to be coated, for example, a conductor having an outer diameter of about 0.15 mm to 7 mmφ can be used. Although the conductor etc. which twisted the tin plating annealed copper wire can be used conveniently, it is not limited to this. The number of conductors 1 is not limited to one as shown in FIG. 1, and a plurality of conductors may be used.

  The insulating layer 2 is comprised from said resin composition which concerns on embodiment of this invention. After being coated as an electrically insulating insulating layer by molding means such as extrusion coating, the insulated wire 10 can be obtained by crosslinking by a method such as electron beam irradiation. For extrusion coating, the resin composition before cross-linking is kneaded with a roll, a banbury, an extruder, etc., and the obtained pellet compound and conductor are wire-coated extrusion using a conventionally known wire extruder equipped with a crosshead die. It can be performed by molding or the like.

  In the present embodiment, the insulating layer 2 may be a single layer or may have a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.

〔cable〕
The cable according to the embodiment of the present invention is characterized by using the resin composition according to the embodiment of the present invention as a coating material (sheath or insulating layer and sheath).

FIG. 2 is a cross-sectional view showing an example of a cable according to the embodiment of the present invention.
As shown in FIG. 2, the cable 20 according to the present embodiment includes a three-core stranded wire obtained by twisting together three insulated wires in which a conductor 1 is covered with an insulating layer 2 together with an interposition 4 such as paper, and a three-core stranded wire. The presser winding tape 5 is provided on the outer periphery, and the electrically insulating sheath 3 is extrusion-coated on the outer periphery. The insulated wire 10 may be a single core or a multi-core stranded wire other than a three-core.

  The sheath 3 is comprised from said resin composition which concerns on embodiment of this invention. The insulating layer 2 may also be comprised from said resin composition. The cable 20 can be obtained by coating as an insulating layer or a sheath layer by a molding means such as extrusion coating and then crosslinking by a method such as electron beam irradiation.

  In the present embodiment, the sheath 3 may be composed of a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.

  The outer diameter of the insulated wire 10 or the cable 20 according to the embodiment of the present invention is, for example, 0.4 mm to 11 mmφ. Examples of the use include wiring in a high-temperature part in equipment such as a dryer, a rice cooker, a transformer outlet, a lighting fixture, and an air conditioner.

  Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

  The insulated wire 10 having the structure shown in FIG. 1 was manufactured and evaluated by the following method.

<Preparation of resin composition>
The details of the additive (powder) used are shown in Table 1. Various components were blended at the blending ratios shown in Table 2, and after kneading at a start temperature of 40 ° C. and an end temperature of 190 ° C. by a pressure kneader, the kneaded material was pelletized to obtain resin compositions of Examples and Comparative Examples. .

<Manufacture of insulated wires>
A UL standard 26 AWG tinned annealed copper wire was used as the conductor 1. The resin composition produced above was extruded on the conductor 1 to obtain an insulated wire 10 (sample) in which the conductor 1 was covered with an insulating layer 2 made of each resin composition. Extrusion was performed at a preset temperature of 200 ° C., an insulation thickness of 0.25 mm, and a linear speed of 50 m / min. The produced electric wire was irradiated with an electron beam at an irradiation amount of 30 kGy to be crosslinked.

  The cohesiveness of the electric wires was evaluated by the method shown below. In addition, flame retardancy, elongation and tensile strength were also measured as additional characteristics. Table 2 shows the results.

(1) Cohesiveness test The insulated wire was produced 2000m by the above-mentioned method, and the presence or absence of the generation | occurrence | production of the particle | grains by the aggregation in the surface of an electric wire was evaluated visually. When there was an aggregated particle of 100 μm or more, it was evaluated as x (failed), when there was no aggregated particle, or when the aggregated particle was less than 100 μm, it was evaluated as “◯” (acceptable).

(2) Flame Retardancy Test A vertical combustion test (UL standard, VW-1) in the shape of an electric wire was performed. Those with a combustion time of less than 30 seconds were evaluated as。 (passed with tolerance), those with 30 seconds or longer but less than 1 minute were evaluated as ◯ (passed), and those with a duration of 1 minute or longer were evaluated as x (failed).

(3) Tensile test A tensile test was performed on the produced electric wires in accordance with JIS C 3005. Tensile strength of less than 10 MPa was evaluated as x (failed), 10 MPa or more and less than 13 MPa as ◯ (passed), and 13 MPa or more as ◎ (passed with tolerance). The elongation of less than 150% was evaluated as x (failed), 150% or more and less than 300% as ◯ (passed), and 300% or higher as ◎ (passed with tolerance).

(4) Judgment Judgment made the pass what the evaluation of the cohesion test was (circle), and made the thing unsatisfactory.

  In Examples 1 to 11, agglomeration did not occur and good results were obtained. Although the resin was changed in Examples 1 to 4, all the results were excellent. In Examples 6 to 7 and 10 to 11, the first additive was used alone, and in Examples 1 to 5 and 8 to 9, two first additives were used in combination. It was good without agglomeration. In addition, as the amount of the flame retardant added increases, the flame retardancy is improved. The flame retardant test is passed at 210 parts by mass or more, and Examples 8 to 11 in which 250 parts by mass or more are added show particularly excellent flame retardancy. It was.

  On the other hand, Comparative Example 1 in which the addition amount of the first additive is more than specified, Comparative Example 2 in which the addition amount of the second additive is more than specified, and Comparative Examples 3 to 4 in which only the second additive is added are Aggregated grains of 100 μm or more were observed on the surface of the electric wire, which was rejected.

  In addition, this invention is not limited to the said embodiment and Example, A various deformation | transformation implementation is possible.

10: insulated wire, 20: cable 1: conductor, 2: insulating layer 3: sheath, 4: intervening, 5: presser winding tape

Claims (10)

The resin composition whose content of the following 1st additive with respect to 100 mass parts of polyolefin resin is 5 mass parts or more and 300 mass parts or less, and whose content of the following 2nd additive is less than 5 mass parts.
First additive: powder and an average particle diameter _{(D50 (P0.3} ) when the volume distribution of the additive is dry measured at a crushing pressure of 0.3 MPa using a laser diffraction particle size distribution analyzer. ₎ ) And the ratio _{(D50 (P0)} / _{D50 (P0.3)} ) of the average particle diameter (D50 _(P0) ) when dry-measured without crushing pressure, the following formula (1) or formula ( additives which satisfies 2) second additive: powdery in and the ratio _{(D 50 (P0) / D} 50 (P0.3)) additives _{D 50} which satisfies the following formula (3) _{(P0 ) / D 50 (P0.3) ≧} 20 ··· formula (1)
D _{50 (P0)} / D _{50 (P0.3)} ≦ 3 (2)
3 <D _{50 (P0)} / D _{50 (P0.3)} <20 Formula (3)   The resin composition according to claim 1, wherein the first additive is an additive that satisfies the formula (1).   The resin composition according to claim 1, wherein the first additive is an additive that satisfies the formula (2).   The resin composition according to claim 1, wherein the first additive is an additive having a hydroxyl group, an ester group, an amide group, or an amino group in a molecule.   The resin composition according to claim 1, wherein the first additive is melamine cyanurate.   The resin composition according to claim 1, wherein the first additive is melamine cyanurate that has not been surface-treated.   The resin composition according to claim 1, wherein the first additive is melamine cyanurate and magnesium hydroxide. The said 1st additive has the said average particle diameter _{(D50 (P0.3)} ) at the time of dry-type measurement by the crushing pressure of 0.3 Mpa, 5 _micrometers or less, The any one of Claims 1-7. Resin composition.   The insulated wire provided with the conductor and the insulating layer which consists of a resin composition of any one of Claims 1-8 coat | covered on the outer periphery of the said conductor.   The cable provided with the sheath which consists of a resin composition of any one of Claims 1-8.

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