JP2007052983A - Insulated electric wire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulated electric wire having high insulating characteristics, high scratch resistance, and high flame retardancy. <P>SOLUTION: The insulated electric wire is constituted by forming on a conductor 1 in order a first insulator layer made of PE or polyolefin resin in which volume resistivity after immersion in water for 100 hours is 1×10<SP>14</SP>Ωcm or more, a second insulator layer 3 made of a flame retardant resin composition obtained by blending magnesium hydroxide of 250-350 pts.mass to base resin of 100 pts.mass comprising EVA of 45-55 pts.mass, AEM of 35-45 pts.mass, and SEB elastomer of 5-10 pts.mass, and a third insulator layer 4 made of the scratch resistant composition obtained by blending flame retardant agent of 60-130 pts.mass comprising magnesium hydroxide of 50-100 pts.mass and melamine cyanurate of 10-30 pts.mass to base resin of 100 pts.mass comprising EVA of 60-80 pts.mass, SEEPS of 15-25 pts.mass, AEM of 5-10 pts.mass, and acid modified LLDPE of 5-10 pts.mass. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an insulated wire having high insulation, external resistance, and high flame resistance.

  In recent years, coating materials for flame-retardant insulated wires have been switched to so-called halogen-free coating materials that do not generate halogen gas during combustion in place of conventional PVC and halogen-based flame retardants due to environmental problems. ing. As such a halogen-free coating material, an ethylene homopolymer, an ethylene copolymer, ethylene / acrylic rubber or the like is used as a base resin component, and magnesium hydroxide, aluminum hydroxide, hydrated aluminum silicate, etc. A compound containing a metal hydrate flame retardant is known. However, since the resin component such as the ethylene-based polymer has essentially no flame retardancy, a high amount of metal hydrate flame retardant should be blended when trying to make this highly flame-retardant. As a result, there is a problem in that the flexibility and mechanical properties of the coating material are lowered, or the coating material becomes brittle and easily damaged by contact between the wires and the corners of hard objects. Furthermore, there is a problem in electrical characteristics such as insulation characteristics.

  In order to improve the above problems, there is a proposal to improve flame retardancy, mechanical properties, and electrical insulation properties by blending a metal hydrate surface-treated with a fatty acid or a silane coupling agent into a polyolefin resin. It is described in Patent Document 1. In addition, an ethylene copolymer such as an ethylene / vinyl acetate copolymer, an ethylene / vinyl acetate copolymer suspended at least partially, and an unsaturated carboxylic acid-modified polyolefin resin are used as a base resin, and a crosslinkable silane is used as the base resin. Patent Document 2 describes a proposal to improve the flame retardancy and mechanical properties of an insulated wire by blending and coating a metal hydrate surface-treated with a coupling agent and a melamine cyanurate compound. . Further, Patent Document 3 proposes to improve mechanical properties by mixing an ethylene copolymer with a styrene elastomer or acrylic rubber, and to improve flame retardancy with a metal hydrate and a melamine cyanurate compound. Are listed.

The coated resin composition and the insulated wire described in the above-mentioned patent documents have flame retardancy conforming to the VW-1 standard of the vertical combustion test of UL standard 1581, and have a machine such as elongation at break and tensile break strength. It is said that the characteristics can be satisfied. However, these coating resin compositions and insulated wires are formed by blending 100 to 250 parts by mass or 150 to 280 parts by mass of a metal hydrate flame retardant with respect to 100 parts by mass of the base resin. If a large amount of a metal hydrate flame retardant is added as described above, it is effective for improving the flame retardancy, but it causes a decrease in flexibility and an increase in brittleness. There is a problem that the coating layer is easily damaged due to contact or the like, and the so-called trauma resistance is poor. There was also a problem in terms of insulation characteristics.
JP 2000-195336 A JP 2000-294036 A JP 2001-60414 A

  Therefore, the problem to be solved by the present invention is to provide an insulated wire having high insulation characteristics, damage resistance, and high flame resistance. In particular, an object of the present invention is to provide an insulated wire that has the above-described characteristics even when the insulator layer is a relatively thin layer and is useful for electronic devices.

The problem to be solved is an insulated wire in which an insulator layer having a three-layer structure is formed on a conductor as described in claim 1, and the polyethylene resin or the water-immersed 100 is sequentially formed on the conductor. First insulator layer made of polyolefin resin whose time volume resistivity does not fall below 1 × 10 ¹⁴ Ω · cm, 45 to 55 parts by mass of ethylene / vinyl acetate copolymer, 35 to 45 mass of ethylene / acrylic rubber Second insulator comprising a flame retardant resin composition in which 250 to 350 parts by mass of magnesium hydroxide is blended with 100 parts by mass of a base resin comprising 5 parts by mass of styrene / ethylene / butylene copolymer elastomer Layer, ethylene / vinyl acetate copolymer 60-80 parts by mass, styrene / ethylene / ethylene propylene / styrene copolymer 15-25 parts by mass, ethylene From 50 to 100 parts by weight of magnesium hydroxide and 10 to 30 parts by weight of melamine cyanurate, based on 100 parts by weight of base resin consisting of 5 to 10 parts by weight of acrylic rubber and 5 to 10 parts by weight of acid-modified linear low density polyethylene This is solved by forming an insulated electric wire on which a third insulator layer made of a damage resistant resin composition blended in a range where the total amount of the flame retardant becomes 60 to 130 parts by mass is formed.

  According to a second aspect of the present invention, the thickness of the insulator layer is such that when the total thickness of each insulator layer is T, the first insulator layer has a thickness of 0.05 mm or more and < The insulated wire according to claim 1, wherein 1 / 3T, the second insulator layer is> 1 / 3T, and the third insulator layer is formed to be <1 / 3T.

The present invention is an insulated wire in which an insulator layer having a three-layer structure is formed on a conductor, and the volume resistivity of polyethylene resin (hereinafter referred to as PE) or water immersion for 100 hours is 1 × 10 ¹⁴ Ω sequentially from the conductor.・ Because the first insulator layer made of polyolefin resin that does not fall below cm is formed, it has high insulation characteristics, and 45 to 55 parts by mass of ethylene / vinyl acetate copolymer (hereinafter EVA), ethylene / acrylic rubber (Hereinafter referred to as AEM) 35 to 45 parts by mass and styrene / ethylene / butylene copolymer elastomer (hereinafter referred to as SEB elastomer) 5 to 10 parts by mass, 100 to part by mass of magnesium hydroxide is blended in an amount of 250 to 350 parts by mass. Since the second insulator layer made of the flame retardant resin composition is formed, it has high flame retardancy, specifically non-halogen, VW- While passing the test, EVA 60 to 80 parts by mass, styrene / ethylene / ethylene propylene / styrene copolymer (hereinafter referred to as SEEPS) 15 to 25 parts by mass, AEM 5 to 10 parts by mass and acid-modified linear low density polyethylene (hereinafter referred to as acid). Modified LLDPE) The total amount of the flame retardant comprising 50 to 100 parts by mass of magnesium hydroxide and 10 to 30 parts by mass of melamine cyanurate is 60 to 130 parts by mass with respect to 100 parts by mass of the base resin comprising 5 to 10 parts by mass. Since the 3rd insulator layer which consists of a damage-resistant resin composition mix | blended in the range was formed, the insulated wire which has high damage resistance is obtained.

  The thickness of the insulator layer is such that when the total thickness of each insulator layer is T, the first insulator layer has a thickness of 0.05 mm or more and <1 / 3T, and the second insulator layer is Since it is formed so that> 1 / 3T and the third insulator layer is <1 / 3T, it is useful as an insulated wire for electronic devices having high insulation characteristics, scratch resistance and high flame resistance. Furthermore, since this insulated wire uses polyolefin resin as a 1st insulator layer, it is excellent also in extraction workability | operativity etc.

The present invention is described in detail below. The present invention described in claim 1 is an insulated wire in which an insulator layer having a three-layer structure is formed on a conductor, and the volume resistivity of 100 hours of PE or water immersion is 1 × 10 in order from the conductor. ¹⁴ base resin made of polyolefin resin not to fall below ¹⁴ Ω · cm, 45 to 55 parts by weight of EVA, 35 to 45 parts by weight of AEM and 5 to 10 parts by weight of SEB elastomer, Second insulator layer composed of a flame retardant resin composition containing 250 to 350 parts by weight of magnesium oxide, EVA 60 to 80 parts by weight, SEEPS 15 to 25 parts by weight, AEM 5 to 10 parts by weight, and acid-modified LLDPE 5 to 10 parts by weight Flame retardant comprising 50 to 100 parts by weight of magnesium hydroxide and 10 to 30 parts by weight of melamine cyanurate with respect to 100 parts by weight of the base resin Of the total weight of the third insulated wire insulator layer is formed consisting of external damage resin composition containing within an amount of 60 to 130 parts by weight. By setting it as the insulated wire of such a structure, it can be set as the insulated wire which has a high insulation characteristic, damage resistance, and a high flame retardance.

First, the first insulator layer formed on the conductor will be described. Since this 1st insulator layer provides a high insulation characteristic to an insulated wire, the resin material excellent in the insulation performance is used. That is, a resin whose volume resistivity after 100 hours of water immersion does not fall below 1 × 10 ¹⁴ Ω · cm is preferable, and polyolefin resins such as PE, polypropylene (hereinafter referred to as PP), and α-olefin copolymer are used. By forming the first insulator layer from such a resin, the obtained insulated wire has an insulation characteristic that the insulation resistance when immersed in tap water at 30 ° C. for 24 hours is 10 MΩ · km or more. can get.

  Next, a resin composition having excellent flame retardancy will be described as the second insulator layer. This 2nd insulator layer is for providing high flame retardance to an insulated wire, and the flame-retardant resin composition excellent in flame retardance is used. That is, 250 to 300 parts by mass of magnesium hydroxide preferably surface-treated with a silane coupling agent is added to 100 parts by mass of the base resin consisting of 45 to 55 parts by mass of EVA, 35 to 45 parts by mass of AEM and 5 to 10 parts by mass of SEB elastomer. Flame retardant resin composition. EVA used as one of the base resins preferably has a high vinyl acetate content from the viewpoint of flame retardancy, but is appropriately selected from the balance with mechanical properties. As an example, the vinyl acetate content is 22 to 47% by mass, preferably 25 to 42% by mass, and the MFR (melt mass flow rate) is 0.1 to 20 g / 10 min (190 ° C., 2.16 kg), preferably 0.1 EVA of ~ 3. Examples of such EVA include trade name EV180 manufactured by Mitsui DuPont Polychemical Co., Ltd. And EVA is mix | blended in 45-55 mass parts in base resin. When the blending amount is less than 45 parts by mass, the mechanical strength is insufficient, and when it exceeds 55 parts by mass, the flame retardancy is insufficient.

  Moreover, the compounding quantity of AEM used as base resin shall be 35-45 mass parts. If the blending amount is less than 35 parts by mass, the flame retardancy is insufficient, and if it exceeds 45 parts by mass, the mechanical strength is insufficient. Furthermore, the blending amount of the SEB elastomer used as the base resin is 5 to 10 parts by mass. When the blending amount is less than 5 parts by mass, the mechanical strength is insufficient, and when it exceeds 10 parts by mass, the flame retardancy is insufficient. Such SEB elastomer preferably has a styrene content of 15 to 35% by mass. As a specific example, trade name Dynalon 4630P manufactured by Nippon Synthetic Rubber Co., Ltd. can be mentioned.

  And in order to improve a flame retardance and a mechanical characteristic to the above-mentioned base resin, 250-300 mass parts of magnesium hydroxide is added with respect to 100 mass parts of base resins. The magnesium hydroxide is preferably one obtained by surface-treating fine magnesium hydroxide having an average particle size of 0.3 μm or less with a silane coupling agent. Further, 180 to 250 parts by mass of finely divided magnesium hydroxide having an average particle size of 0.3 μm or less and a surface treatment with a silane coupling agent, and 50 to 120 masses of fine particle magnesium hydroxide having an average particle size of 0.3 μm or less. The ratio may be in a range of 250 parts by weight to 300 parts by weight. Thus, by combining two types of magnesium hydroxide, magnesium hydroxide can be dispersed in the base resin without gaps, so that the occurrence of crazes (defects) during tension can be prevented, and the obtained flame-retardant resin composition is In particular, mechanical properties such as breaking strength and breaking elongation are greatly improved. In addition, when the blending amount of magnesium hydroxide is less than 250 parts by mass, high flame retardancy that passes the VW-1 test of UL standard 1581 cannot be obtained, and when it exceeds 300 parts by mass, mechanical properties such as flexibility are obtained. Is undesirably low.

  The above flame-retardant resin composition is prepared by dry blending a predetermined amount of each constituent component and melt-kneading with a commonly used kneader such as a twin-screw kneading extruder, Banbury mixer, kneader, roll, etc. The second insulator layer of the insulated wire can be formed by extrusion coating on the conductor using a machine. In addition, the flame retardant resin composition may contain, for example, an ultraviolet absorber, an antioxidant, an anti-aging agent, a copper damage inhibitor, a pigment, a lubricant, a compatibilizing agent, and the like, if necessary. If necessary, other flame retardant aids (red phosphorus, polyphosphoric acid compound, zinc hydroxytinate, etc.) may be used in combination.

  Next, a resin composition having excellent trauma resistance that forms the third insulator layer will be described. The trauma resistant resin composition preferably includes not only the trauma resistance but also the flame retardancy, and therefore is composed of a base resin and a flame retardant having excellent trauma resistance. EVA used as one of the base resins preferably has a high vinyl acetate content from the viewpoint of flame retardancy, but is appropriately selected from the balance with mechanical properties. As an example, the vinyl acetate content is 22 to 47% by mass, preferably 25 to 42% by mass, and the MFR (melt mass flow rate) is 0.1 to 20 g / 10 min (190 ° C., 2.16 kg), preferably 0.1 It is ˜3 g / 10 min EVA. Examples of such EVA include a trade name EV180 manufactured by Mitsui DuPont Polychemical Co., Ltd. And EVA is blended in the range of 60 to 80 parts by mass in the base resin. If the blending amount is less than 60 parts by mass, the mechanical strength is insufficient, and if it exceeds 80 parts by mass, the flame retardancy is insufficient. Since the flexibility is also lowered, the above range is set.

  Further, SEEPS used as one of the base resins preferably has a styrene content of 20% by mass or more. A specific example of such SEEPS is Kuraray's trade name Septon 4033. And the compounding quantity of SEEPS shall be 15-25 mass parts in base resin. If the blending amount is less than 15 parts by mass, the mechanical strength is insufficient, and if it exceeds 25 parts by mass, the flame retardancy is insufficient.

  Further, AEM used as a base resin is a block polymer composed of an ethylene polymer block and a methyl acrylate polymer block, and examples thereof include trade name VAMAC DP manufactured by Mitsui DuPont Polychemical Co., Ltd. And the compounding quantity of AEM shall be 5-10 mass parts in base resin. When the blending amount is less than 5 parts by mass, the flame retardancy is insufficient and the flexibility is lowered. On the other hand, if the amount exceeds 10 parts by mass, the mechanical strength is insufficient, so the above range is adopted.

In addition, acid-modified LLDPE, which is one of the base resins, is made of polyethylene having a density of 0.93 g / cm ³ or less, such as linear low density polyethylene and linear ultra-low density polyethylene, with maleic acid, maleic anhydride, etc. Of these, a product obtained by modifying a linear ultra-low density polyethylene with maleic acid is preferable. The blending amount of the acid-modified LLDPE is in the range of 5 to 10 parts by mass. If the blending amount is less than 5 parts by mass, the effect of improving the dispersibility of the magnesium hydroxide in the base resin is small, and the improvement on the mechanical properties and the like. We cannot expect effect. On the other hand, if it exceeds 10 parts by mass, the elongation at break will be insufficient, the flexibility will be lowered, the adhesiveness with the conductor will be too strong, and the lead-out property such as the connecting work of the insulated wire will be deteriorated. According to the above-mentioned trauma resistant composition, trauma resistance in which no whitening is observed even when a scratch test with a diamond finger of R = 0.5 and a load of 100 g is performed is obtained.

  In order to improve the flame retardancy of the above base resin, a flame retardant in a ratio range of 50 to 100 parts by mass of magnesium hydroxide and 10 to 30 parts by mass of melamine cyanurate with respect to 100 parts by mass of the base resin, It is set as the external damage-resistant resin composition which mix | blended 130 mass parts and also provided the flame retardance. As magnesium hydroxide, natural magnesium hydroxide, synthetic magnesium hydroxide, or the like is used, and among them, synthetic magnesium hydroxide is preferably used. The particle diameter is not particularly limited, but the particle diameter is preferably 5 μm or less and the average particle diameter is 2 to 4 μm from the viewpoint of dispersibility with respect to the resin. In addition, when the blending amount of magnesium hydroxide is less than 50 parts by mass, the flame retardancy is not sufficient, and when it exceeds 100 parts by mass, the trauma resistant resin composition becomes too hard and the trauma resistance as the third insulator layer. To lower the sex. Melamine cyanurate used together with magnesium hydroxide is blended in the range of 10 to 30 parts by mass. When the blending amount is less than 10 parts by mass, the effect of improving the flame retardancy cannot be expected. Thus, by using together magnesium hydroxide and melamine cyanurate, compared with the case where magnesium hydroxide is mix | blended independently, the higher flame retarding effect is acquired by the mixing | blending of the same number of parts. Moreover, both are mix | blended so that it may become 60-130 mass parts with respect to 100 mass parts of base resins in each compounding quantity range. The reason why such a blending amount is used is that when the amount is less than 60 parts by mass, the trauma resistance is good but the flame retardancy is inferior, and when it exceeds 130 parts by mass, the trauma resistance is inferior. .

  This magnesium hydroxide is also preferably surface-treated with a silane coupling agent. As silane coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Triethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane or the like can be used. As the surface treatment method, it can be carried out by mixing or kneading magnesium hydroxide and a silane coupling agent. Moreover, it is preferable to use the said silane coupling agent in 0.1-5 mass% with respect to magnesium hydroxide. Such surface-treated magnesium hydroxide has improved dispersibility in the scratch-resistant resin composition, has excellent extrudability when coated as an outer layer, and improves mechanical properties and further increases flame retardancy. become.

  The above-mentioned flame-resistant resin composition having flame retardancy is obtained by dry blending a predetermined amount of each base resin and flame retardant, and using a kneader usually used such as a twin-screw kneading extruder, a Banbury mixer, a kneader, and a roll. It can be obtained by melt-kneading. The trauma resistant resin composition may contain other additives such as UV absorbers, antioxidants, antioxidants, copper damage inhibitors, pigments, lubricants, compatibilizers, etc. as necessary. As long as the object of the invention is not impaired, it may be blended as appropriate, and in some cases, other flame retardant aids (red phosphorus, polyphosphate compound, zinc hydroxytinate, etc.) may be used in combination. The insulator layer having the above three-layer structure is generally set to about 0.9 mm or less as the total thickness of each layer. The insulated wire may be cross-linked by electron beam irradiation or the like. The mechanical properties are improved, and the heat resistance and the damage resistance can be further improved.

  As described in claim 2, the insulated wire in which the three insulator layers are formed has the first insulator layer when the total thickness of each insulator layer is T. However, by forming the thickness so that the thickness is 0.05 mm or less and <1 / 3T, the second insulator layer is> 1 / 3T, and the third insulator layer is <1 / 3T, It becomes useful as an insulated wire for electronic equipment having insulating properties, damage resistance and high flame resistance. In addition, since a polyolefin-based resin is used for the first insulator layer, the insulated wire has excellent lead-out workability and the like.

  That is, when the total thickness of the three insulator layers is T, particularly the second insulator layer is made sufficiently thicker than the other layers (thickness exceeding 1 / 3T), and thereby particularly high flame retardancy. Thus, it is possible to sufficiently maintain the insulation characteristics and the damage resistance together with the first insulator layer and the third insulator layer. Note that the thickness T of the insulator layer is usually about 0.09 mm or less. This will be described with reference to FIG. Reference numeral 1 denotes a conductor, which is composed of a single wire or a stranded wire such as copper or a copper alloy, and the conductor diameter is usually about 0.3 to 3.1 mm. Reference numeral 2 denotes an insulator layer of the first insulator layer, and the thickness thereof is 0.05 mm or more and thinner than 1 / 3T. As a result, as the insulation characteristic of the insulated wire, a characteristic that the insulation resistance when immersed in tap water at 30 ° C. for 24 hours is 10 MΩ · km or more is obtained. 3 is an insulator layer of the second insulator layer. By setting the thickness to more than 1 / 3T, high flame retardancy, specifically, flame retardance that passes the VW-1 test of UL standard 1581 is obtained. . 4 is an insulator layer of the third insulator layer. By forming the insulator layer to be thinner than 1 / 3T, no whitening is observed even when a scratch test is performed with a diamond finger of R = 0.5 and a load of 100 g. Sex will be obtained. Furthermore, by using a polyolefin-based resin for the first insulator layer, an insulated wire excellent in lead-out workability and the like is obtained.

  The effects of the present invention will be described below with reference to examples and comparative examples. The insulated wire of Table 1 which shows an Example, or Table 2 which shows a comparative example was produced. That is, the materials described in Table 1 and Table 2 were blended, melt-kneaded at 160 to 190 ° C. using a Banbury mixer, and the resin composition for the second insulator layer and the third insulator layer was converted to AWG26 ( 7 / 0.16TA) On the first insulator layer having a thickness of 0.08 mm formed on the conductor, the thicknesses are 0.27 mm (second insulator layer) and 0.05 mm (third insulator layer) in order. Coated. The PE of the first insulator layer is LLDPE of Nihon Unicar Co., Ltd., J232WA (PP, MFR is 1.5) of Prime Polymer Co., as the polyolefin resin, and for the second insulator layer and the third insulator layer. As the resin, EVA is a product name EV180 manufactured by Mitsui DuPont Chemical Co., Ltd., AEM is a product name VAMAC DP manufactured by Mitsui DuPont Chemical Co., Ltd., and SEB elastomer is a product name Dynalon 4630P manufactured by Nippon Synthetic Rubber Co., Ltd. The product name Adtex L6100M manufactured by Nippon Polyethylene Co., Ltd. was used as the product name Septon 4033 and acid-modified LLDPE manufactured by the company. As magnesium hydroxide, Kisuma 5P and Kisuma 5L manufactured by Kyowa Chemical Co., Ltd. were used as silane coupling agent surface-treated magnesium hydroxide. Further, Irganox 1010 manufactured by Ciba Specialty Chemicals was used as an antioxidant, and trade name MC-860 manufactured by Nissan Chemical Co., Ltd. was used for melamine cyanurate.

  About said insulated wire, breaking strength and breaking elongation were measured by UL specification 1581, and breaking strength was described as pass with the breaking strength being 10.3 MPa or more and breaking elongation of 150% or more, and others being rejected. Further, regarding the scratch resistance, a scratch test with a diamond finger of R = 0.5 mm and a load of 100 g was performed to determine whether or not the coating layer was whitened. Those in which whitening was not observed were described as acceptable, and those in which whitening was observed were described as rejected. Further, as flame retardancy, the VW-1 test of the vertical combustion test of UL standard 1581 was conducted, and the test that passed this test was regarded as acceptable. Moreover, the insulation resistance after being immersed in 30 degreeC tap water for 24 hours as an insulation characteristic was measured, and the insulation resistance set 10 Mohm * km or more as the pass. The results of the examples are shown in Table 1, and the results of the comparative examples are shown in Table 2.

As is apparent from the examples in Table 1, the volume resistivity of 100 hours of PE or water immersion on the conductor is 1 × 10 ¹⁴ as an insulated wire in which an insulator layer having a three-layer structure is formed on the conductor. A first insulator layer made of polyolefin resin that does not fall below Ω · cm is formed, and 100 parts by mass of base resin consisting of 45 to 55 parts by mass of EVA, 35 to 45 parts by mass of AEM and 5 to 10 parts by mass of SEB elastomer On the other hand, a second insulator layer made of a flame retardant resin composition containing 250 to 350 parts by weight of magnesium hydroxide is formed, EVA 60 to 80 parts by weight, SEEPS 15 to 25 parts by weight, AEM 5 to 10 parts by weight, and acid Magnesium hydroxide 50-100 parts by weight and melamine cyanurate 10 with respect to 100 parts by weight of the base resin consisting of 5-10 parts by weight of modified LLDPE Since the third insulator layer made of the scratch-resistant resin composition blended in the range where the total amount of the flame retardant consisting of 30 parts by mass is 60 to 130 parts by mass, it has excellent high insulation characteristics, and high It can be seen that an insulated wire having flame resistance, specifically, non-halogen and having passed the VW-1 test of UL standard 1581 and having high damage resistance can be obtained.

This will be described in detail. As shown in Examples 1 to 12, PE is applied to the first insulator layer, and as the second insulator layer, 45 to 55 parts by mass of EVA, 35 to 45 parts by mass of AEM, and 5 to 10 of SEB elastomer are used. A flame retardant resin composition in which Kisuma 5L is blended in a range of 250 to 300 parts by mass is used as parts by mass, and as the third insulator layer, EVA is 60 to 80 parts by mass, SEEPS is 15 to 25 parts by mass, 5-10 parts by mass of AEM, 5-10 parts by mass of acid-modified LLDPE, 50-100 parts by mass of Kisuma 5P and 10-30 parts by mass of melamine cyanurate, total amount of 60-130 parts by mass The insulated wire formed with the conductive resin composition has an insulation resistance of 10 MΩ · km or more, and no damage or whitening due to scratches is observed with respect to the damage resistance, and the breaking strength is 10.3 MPa or more. It was equal to or greater than 50%. Furthermore, regarding flame retardancy, excellent flame retardancy that passed the VW-1 standard defined in UL standard 1581 was exhibited. In addition, an insulated wire using a polyolefin-based resin whose volume resistivity does not fall below 1 × 10 ¹⁴ Ω · cm for the first insulator layer described as Example 13 also has an insulation resistance of 10 MΩ · km or more, VW-1 standard as defined in UL standard 1581 with respect to flame resistance, having a scratch resistance that does not cause whitening due to scratches or scratches, has a breaking strength of 10.3 MPa or more, a breaking elongation of 150% or more It was an excellent flame retardant insulated wire that passed Moreover, these insulated wires were excellent in lead-out workability.

  On the other hand, in the case of an example outside the scope of the present invention shown in Comparative Examples 1 to 11 in Table 2, any of the insulating properties, breaking strength, breaking elongation, flame retardancy and trauma resistance is rejected. became. That is, when the compounding quantity of magnesium hydroxide in the second insulator layer was as small as 240 parts by mass as in Comparative Example 1, the flame retardancy was not passed. Moreover, when the total amount of magnesium hydroxide was 360 parts by mass as in Comparative Example 2, the elongation at break failed. Further, as in Comparative Example 3, when the amount of EVA in the second insulator layer was as small as 45 parts by mass and the amount of AEM was as large as 50 parts by mass, the fracture strength was rejected. Further, as shown in Comparative Example 4, when the AEM is as small as 30 parts by mass, the flame retardancy is rejected. Further, as shown in Comparative Example 5, the EVA of the third insulator layer is 45 parts by mass, and the acid modification When there is much LLDPE as 20 mass, elongation at break will be disqualified. Moreover, when acid-modified LLDPE is not added to the third insulator layer as in Comparative Example 6, the breaking strength is rejected. Further, as in Comparative Examples 7 and 8, when the added amount of SEEPS in the third insulator layer is small, the trauma resistance and the breaking strength are rejected. In addition, as in Comparative Example 9, when the amount of Kisuma 5P added to the third insulator layer is large and the amount of melamine cinnurate added is small, the trauma resistance is rejected. Moreover, when there is much addition amount of the SEB elastomer of a 2nd insulator layer like the comparative example 10, a flame retardance will be disqualified. Furthermore, as in Comparative Example 11, when the first insulator layer is a polyolefin-based resin, the amount of EVA added to the third insulator layer is small, and if the amount of SEEPS added is large, the flame retardancy is rejected. I understood.

  Next, the insulated wire which changed the thickness of each insulator layer described in Table 3 variously was produced, and the characteristic was investigated. That is, the PE of the first insulator layer is LLDPE manufactured by Nihon Unicar, and the resin for the second insulator layer and the third insulator layer is EVA as trade names EV180 and AEM manufactured by Mitsui DuPont Chemical Co., Ltd. Trade name VAMAC DP manufactured by Mitsui DuPont Chemical Co., trade name Dynalon 4630P manufactured by Nippon Synthetic Rubber Co., Ltd. as SEB elastomer, trade name Septon 4033 manufactured by Kuraray Co., Ltd., and acid-modified LLDPE manufactured by Nippon Polyethylene Co., Ltd. Adtex L6100M was used. As magnesium hydroxide, Kisuma 5P and Kisuma 5L manufactured by Kyowa Chemical Co., Ltd. were used as silane coupling agent surface-treated magnesium hydroxide. Further, Irganox 1010 manufactured by Ciba Specialty Chemicals was used as an antioxidant, and various resin compositions using the product name MC-860 manufactured by Nissan Chemical Co., respectively, were used as melamine cyanurate, and the entire insulator layer (T) A thickness of 0.8 mm was used, and various insulated wires were manufactured by changing the thicknesses of the first insulator layer, the second insulator layer, and the third insulator layer. As with Tables 1 and 2, the insulated wires were tested for breaking strength, breaking elongation, damage resistance, flame retardancy, and insulating properties. The results are shown in Table 3.

  As is clear from the examples in Table 3, when the total thickness of each insulator layer is T (0.8 mm), the first insulator layer is <1 / 3T and the second insulator layer is> 1 / It can be seen that by forming 3T and the third insulator layer to be <1 / 3T, it is possible to obtain an insulated wire having high insulation characteristics, damage resistance, and high flame resistance. That is, as described in Examples 14 to 19, when the thickness of each insulator layer is within the range of the above conditions, the insulation resistance is 10 MΩ · km or more, and the resistance to trauma is whitening due to scratches or scratches. The breaking strength was 10.3 MPa or more, and the breaking elongation was 150% or more. Furthermore, regarding flame retardancy, excellent flame retardancy that passed the VW-1 standard defined in UL standard 1581 was exhibited. Furthermore, this insulated wire was also excellent in lead workability. On the other hand, if the thicknesses of the first insulator layer, the second insulator layer, and the third insulator layer are all the same as in Comparative Example 12, the flame retardancy is rejected. Further, as in Comparative Example 13, if the thickness of the first insulator layer is made larger than the thickness of the second insulator layer, the flame retardancy is also rejected. Further, as in Comparative Example 14, if the thickness of the third insulator layer is made larger than the thickness of the second insulator layer, the flame retardancy is rejected as in Comparative Examples 1 and 2.

  Furthermore, the thickness of the first insulating layer was examined in order to particularly confirm the insulating characteristics. That is, an insulated wire having the configuration shown in Table 4 was produced and its characteristics were examined. For each insulator layer, the insulating material shown in Table 3 was used, the thickness of the third insulator layer was kept constant at 0.2 mm, and the thickness of the first insulator layer was changed to produce an insulated wire. Further, the thickness of the second insulator layer was adjusted so that the total thickness of the first and second insulator layers was 0.6 mm. The insulated wire was tested in the same manner as in Table 3 for breaking strength, breaking elongation, damage resistance, flame retardancy, and insulating properties. The results are shown in Table 4.

  As is clear from Examples 20 and 21 in Table 4, it can be seen that the thickness of the first insulator layer is preferably 0.05 mm or more. That is, as shown in Comparative Example 15, when the thickness of the first insulator layer is 0.04 mm, the insulation resistance becomes less than 10 MΩ · km, which is rejected.

  The insulated wire of the present invention has excellent insulation characteristics and non-halogen high flame retardancy, and is also excellent in damage resistance. Therefore, the insulated wire is particularly useful as an insulated wiring used in electronic devices and the like.

It is a schematic sectional drawing of the insulated wire of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductor 2 1st insulator layer 3 2nd insulator layer 4 3rd insulator layer

Claims (2)

An insulated wire in which an insulator layer having a three-layer structure is formed on a conductor, and the volume resistivity after 100 hours of immersion in polyethylene resin or water does not fall below 1 × 10 ¹⁴ Ω · cm sequentially from the conductor. First insulator layer made of polyolefin resin, 45 to 55 parts by mass of ethylene / vinyl acetate copolymer, 35 to 45 parts by mass of ethylene / acrylic rubber, and 5 to 10 parts by mass of styrene / ethylene / butylene copolymer elastomer. Second insulator layer comprising a flame retardant resin composition in which 250 to 350 parts by mass of magnesium hydroxide is blended with respect to 100 parts by mass of base resin, 60 to 80 parts by mass of ethylene / vinyl acetate copolymer, styrene / ethylene・ 15-25 parts by mass of ethylene propylene / styrene copolymer, 5-10 parts by mass of ethylene / acrylic rubber, and acid-modified linear low density polymer In a range where the total amount of the flame retardant consisting of 50 to 100 parts by mass of magnesium hydroxide and 10 to 30 parts by mass of melamine cyanurate is 60 to 130 parts by mass with respect to 100 parts by mass of the base resin consisting of 5 to 10 parts by mass of ethylene. An insulated electric wire characterized in that a third insulator layer made of a blended trauma resistant resin composition is formed.   As for the thickness of the insulator layer, when the total thickness of each insulator layer is T, the first insulator layer has a thickness of 0.05 mm or more and <1 / 3T, the second insulator layer> 2. The insulated wire according to claim 1, wherein the insulated wire is formed to be 1 / 3T and the third insulator layer is <1 / 3T.

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