JP2008239901A - Flame-retardant resin composition and insulated electric wire coated with the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition excellent in flame retardancy and abrasion resistance in particular, having mechanical characteristics or the like well-balanced with the above characteristics, and to provide an insulated electric wire coated with the resin composition. <P>SOLUTION: This flame-retardant resin composition of the present invention comprises 40-200 pts.mass magnesium hydroxide relative to 100 pts.mass resin mixture comprising 40-90 mass% polypropylene-based resin, 5-20 mass% ethylene-vinyl acetate copolymer whose vinyl acetate content is ≥50 mass% relative to the whole copolymer and whose structure contains three or more consecutive vinyl acetate components being the structural component of the copolymer, 5-20 mass% modified styrenic thermoplastic elastomer, and 0-20 mass% modified polyolefin, The composition is most suitable as, for example, an insulation coating material for insulated electric wires, especially as an insulation coating material for small diameter electric wires, mounted on automobiles and electric/electronic appliances. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition and an insulated wire coated with the resin composition. More specifically, the present invention relates to a flame retardant resin composition used for automobiles, electrical / electronic devices, and the like, and an insulated wire coated with the resin composition.

  Insulating coating materials for components such as automobiles, electrical / electronic devices, and insulated wires installed in these components include various materials such as flame resistance and wear resistance in addition to heat resistance, cold resistance, and moisture resistance. Characteristics are required. Polyvinyl chloride (PVC) resins and polyolefin resins containing halogen-based flame retardants containing bromine (Br) atoms or chlorine (Cl) atoms in the molecule are widely used as resin materials constituting them. It had been. When products using such materials are disposed of without proper treatment, various problems have occurred. For example, when these products are disposed of in landfills, they are included in the materials. There is a problem that lead compounds, etc. are eluted as phosphorus compounds and plasticizers / heavy metal stabilizers, and corrosive halogen gases and dioxins are generated when discarded by incineration. It was.

  For this reason, non-halogen flame retardant resin compositions that do not generate harmful heavy metals or corrosive halogen-based gases have been studied and some have been put into practical use. Non-halogen flame retardant resin compositions that have been studied or put into practical use are widely known to use a polyolefin resin as a base polymer and are filled with a large amount of metal hydrates such as magnesium hydroxide and aluminum hydroxide. In addition, as the base polymer of the resin composition, an ethylene-based copolymer that easily disperses a large amount of metal hydrate has been used.

  Since the mechanical properties and heat resistance of such a non-halogen flame retardant resin composition are lower than those of polyvinyl resin compositions that have been used so far, non-halogen having the same properties as polyvinyl chloride resin compositions. Development of a flame retardant resin composition is expected. And in order to solve such a problem, the resin composition which uses the polypropylene excellent in a mechanical characteristic and heat resistance as a base polymer (for example, refer patent document 1), the difficulty which uses an ethylene-type copolymer as a base polymer. A method of crosslinking a flammable resin composition by chemical crosslinking or electron beam crosslinking has been studied (for example, see Patent Document 2).

JP 2001-354826 A ([Claim 1], [0007]) JP 2002-332385 A ([Claim 3], [0019])

  However, the above-described conventional resin compositions are not only insufficient in flame retardancy and abrasion resistance, but also difficult to combine these properties with various properties such as mechanical properties, heat resistance, and cold resistance. . Insulated wires coated with a flame retardant resin composition that has been studied or put to practical use are inferior in wear resistance as compared to conventional insulated wires coated with a polyvinyl chloride resin by extrusion. It was. In recent years, there has been a demand for thinner insulated wires due to the narrowing of the installation location and the increase in the number of wires, etc., but the fineness coated with the flame retardant resin composition that has been studied or put to practical use so far is required. Since the diameter-insulated electric wire cannot provide sufficient flame retardancy and wear resistance, there has been a demand for its improvement.

  The present invention has been made in view of the above-mentioned problems, and is particularly excellent in flame retardancy and wear resistance. Further, the flame retardancy is balanced with respect to these properties and mechanical properties, heat resistance, cold resistance and the like. It is providing the insulated resin composition and the insulated wire which coat | covered the said resin composition.

  In order to solve the above-mentioned problems, the flame-retardant resin composition according to claim 1 of the present invention comprises (a) 40 to 90% by mass of a polypropylene-based resin and (b) vinyl acetate which is a constituent component of a copolymer. 5-20% by mass of an ethylene / vinyl acetate copolymer having a structure in which three or more components are continuous and the content of vinyl acetate is 50% by mass or more based on the whole copolymer, (c) modification (E) Magnesium hydroxide is contained in an amount of 40 to 200 parts by mass with respect to 100 parts by mass of a resin mixture composed of 5 to 20% by mass of a styrenic thermoplastic elastomer and (d) 0 to 20% by mass of a modified polyolefin. And

  The flame-retardant resin composition according to claim 2 of the present invention is characterized in that, in the above-described claim 1, the composition further comprises (f) 1-20 parts by mass of clay mineral with respect to 100 parts by mass of the resin mixture. And

  An insulated wire according to claim 3 of the present invention is characterized in that the flame-retardant resin composition according to claim 1 or 2 is extrusion-coated on a conductor.

  The insulated wire according to claim 4 of the present invention is characterized in that, in the above-described claim 3, the outer diameter of the conductor is φ0.6 mm or less.

  The flame retardant resin composition according to claim 1 of the present invention uses a polypropylene resin as a base polymer, and a resin mixture comprising an ethylene copolymer having a specific structure, a modified styrene thermoplastic elastomer and a modified polyolefin. And a specific amount of magnesium hydroxide is used for these, so it has excellent flame resistance and wear resistance, and has a good balance of mechanical properties, heat resistance, cold resistance, and other properties. It becomes the flame-retardant resin composition which combines.

  Since the flame retardant resin composition according to claim 2 of the present invention further contains a specific amount of clay mineral as an essential component of the resin composition, a flame retardant resin composition with further improved wear resistance is provided. Can be provided.

  Since the insulated wire according to claim 3 of the present invention is formed by extrusion-coating the above-described flame-retardant resin composition of the present invention on a conductor, the effect obtained by the above-described resin composition of the present invention is enjoyed, and the insulating layer As a result, the insulated wire is excellent in flame retardancy and wear resistance, and has a good balance of mechanical properties, cold resistance and heat resistance.

  In the insulated wire according to claim 4 of the present invention, the outer diameter of the conductor is 0.6 mm or less. The flame-retardant resin composition of the present invention is excellent in flame retardancy and abrasion resistance, and has various properties such as mechanical properties, heat resistance, cold resistance, etc., and the outer diameter of the conductor is φ0.6 mm or less. Even if it uses as an insulation coating material of what is called a diameter-reduced insulated wire, the effect can be suitably provided with respect to the said diameter-reduced insulated wire.

  Hereinafter, the flame retardant resin composition of the present invention will be described. The flame-retardant resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) is composed of (a) 40 to 90% by mass of a polypropylene resin and (b) acetic acid which is a constituent component of a copolymer. 5-20% by mass of an ethylene / vinyl acetate copolymer having a structure in which three or more vinyl components are continuous and the content of vinyl acetate is 50% by mass or more based on the whole copolymer, (c) (E) Magnesium hydroxide is contained in an amount of 40 to 200 parts by mass with respect to 100 parts by mass of the resin mixture composed of 5 to 20% by mass of the modified styrene thermoplastic elastomer and (d) 0 to 20% by mass of the modified polyolefin. Is.

(A) Polypropylene resin:
The polypropylene resin constituting the flame retardant resin composition of the present invention is a base polymer of the resin composition, and the resin composition has good mechanical properties, heat resistance and cold resistance. Examples of usable propylene-based resins include those obtained by polymerizing only propylene, and those obtained by copolymerizing propylene with an α-olefin such as ethylene and 1-butene. Specific examples include homopolypropylene, block polypropylene, random polypropylene, propylene-ethylene random copolymer, and propylene-butene random copolymer.

  In addition, as such a polypropylene-based resin, considering that the resin composition of the present invention is used as a material requiring wear resistance or a coating material for an insulated wire, the hardness (HRR) is 65 or more, bending It is preferable to use a polypropylene resin having an elastic modulus of 1000 MPa or more.

  In the present invention, these polypropylene resins have a melt flow rate (MFR) specified in JIS K7210 of 10.0 g / 10 min or less (230 ° C., 2 ° C.) from the viewpoint of improving the kneadability of the resin composition. .16 kgf load).

(B) An ethylene / vinyl acetate copolymer having a structure in which three or more vinyl acetate components as constituent components of the copolymer are continuous and the vinyl acetate content is 50% by mass or more based on the total copolymer. Polymer (hereinafter sometimes referred to as “ethylene / vinyl acetate copolymer having a specific structure”):
The ethylene / vinyl acetate copolymer having a specific structure constituting the flame-retardant resin composition of the present invention has a function of improving wear resistance in addition to the flame retardancy of the resin composition. Moreover, these effects are further improved by using an ethylene / vinyl acetate copolymer having such a specific structure in combination with (c) a modified styrene thermoplastic elastomer described later.

  In the present invention, the wear resistance of the composition can be improved by using an ethylene / vinyl acetate copolymer having a structure in which three or more vinyl acetate components as constituent components of the copolymer are continuous. When ethylene / vinyl acetate copolymer with a high vinyl acetate content is used, for example, it passes not only the horizontal combustion test of JIS C3005, which is a standard related to flame resistance of insulated wires, but also the ISO 6722 45 ° inclined combustion test It is possible to provide an insulated wire. Generally, ethylene / vinyl acetate copolymers with a high vinyl acetate content tend to have improved flame retardancy and lower mechanical properties, but the constituent vinyl acetate has a regular structure. By taking it, it is considered that both flame retardancy and mechanical properties are compatible.

The structure of the ethylene / vinyl acetate copolymer constituting the resin composition of the present invention can be calculated from the peak area ratio of the ¹³ C-NMR spectrum, and generally 3 or more vinyl acetate components at 65 to 70 ppm. It can be confirmed by a signal indicating a structure that is continuously included.

  Furthermore, the vinyl acetate content in the ethylene / vinyl acetate copolymer having a specific structure constituting the resin composition of the present invention is preferably 50% by mass or more based on the whole copolymer. By setting the vinyl acetate content to 50% by mass or more based on the entire copolymer, high flame retardancy can be imparted to the resin composition. The vinyl acetate content of the vinyl acetate copolymer is more preferably 50 to 80% by mass, and particularly preferably 50 to 70% by mass with respect to the entire copolymer.

  The ethylene / vinyl acetate copolymer having a specific structure constituting the resin composition of the present invention is defined in JIS K7210 from the viewpoint of improving the kneadability of the resin and the composition as in the case of the polypropylene resin. The melt flow rate (MFR) is preferably 10.0 g / 10 min or less (190 ° C., 2.16 kgf load). Examples of such an ethylene / vinyl acetate copolymer include “Levapren 800HV”, “Levapren 700HV”, “Levapren 600HV”, “Levapren 500HV” (all manufactured by Bayer) and the like.

(C) Modified styrenic thermoplastic elastomer:
The modified styrene thermoplastic elastomer constituting the flame retardant resin composition of the present invention is a styrene thermoplastic elastomer modified with an unsaturated carboxylic acid and / or a derivative thereof. Such a modified styrenic thermoplastic elastomer improves the mechanical properties and wear resistance of the resin composition when used in combination with the (b) ethylene / vinyl acetate copolymer having a specific structure.

  Styrenic thermoplastic elastomers that can be used include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene-butylene-styrene block copolymer (SEBS). ), Styrene-ethylene-propylene-styrene block copolymer (SEPS), and the like.

  In the present invention, these modified styrenic thermoplastic elastomers, in the same way as the polypropylene resin and the ethylene / vinyl acetate copolymer having a specific structure, improve the kneadability of the resin composition, in accordance with JIS K7210. The specified melt flow rate (MFR) is preferably 10.0 g / 10 min or less (230 ° C., 2.16 kgf load). Examples of such a modified styrene-based thermoplastic elastomer include “modified DYNARON” (JSR), “Tough Tech M” (manufactured by Asahi Kasei Co., Ltd.), “Clayton FG1901X” (manufactured by Kraton Polymer Co., Ltd.), and the like.

(D) Modified polyolefin:
The modified polyolefin constituting the flame retardant resin composition of the present invention is added to the resin composition of the present invention as necessary, and is added to the resin composition (e) magnesium hydroxide, which is a non-resin component described later, and if necessary, to the resin composition. (F) The dispersibility of the clay mineral in the resin composition can be improved, and further, it has a function of improving mechanical properties and wear resistance.

  The modified polyolefin is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid and / or a derivative thereof. Examples of the polyolefin-based resin that can be used include polypropylene, polyethylene, and ethylene / α-olefin copolymers. Examples of the unsaturated carboxylic acid include maleic acid, itaconic acid, and fumaric acid. Examples of the unsaturated carboxylic acid derivative include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, There are itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester and the like.

  In the present invention, these modified polyolefins have a melt flow rate defined in JIS K7210 of 10.0 g / 10 min (190 g) from the viewpoint of improving the kneadability of the resin composition, like polypropylene resins and the like. (° C., 2.16 kgf load) or less. Examples of such a modified polyolefin include “Polybond” (manufactured by Crompton), “Adtex” (Japanese polyethylene), “Orevac” (manufactured by Arkema), and the like.

(E) Magnesium hydroxide:
Magnesium hydroxide constituting the flame retardant resin composition of the present invention is used for the purpose of improving the flame retardancy of the flame retardant resin composition and the like. Moreover, you may use this magnesium hydroxide surface-treated with a silane coupling agent or a fatty acid. By subjecting magnesium hydroxide to a surface treatment with a silane coupling agent or a fatty acid, the insulation performance of the flame retardant resin composition or the insulated wire covered with the resin composition can be improved. Such surface treatment may be performed by using a silane coupling agent or a fatty acid alone or in combination.

  Magnesium hydroxide has an average particle size in the range of 0.3 to 1.5 μm, particularly preferably an average particle size of 0.5 to 1 in order to improve dispersibility in the resin mixture. Those having a thickness of 0.0 μm and little aggregation are preferred from the viewpoint of improving the mechanical properties of the resin composition. Examples of such magnesium hydroxide include “Kisuma 5”, “Kisuma 5A”, “Kisuma 5B”, “Kisuma 5J”, “Kisuma 5L”, “Kisuma 5P” (all Kyowa Chemical Industry Co., Ltd.) "MagnifinH7", "MagnifinH10", "MagnifinH10A", "MagnifinH7C", "MagnifinH10IV", "MagnifinH10MV" (all manufactured by Albemarle) and the like.

(F) Clay mineral:
In addition to the essential components (a) to (e) described above, it is preferable to further add (f) a clay mineral to the flame retardant resin composition of the present invention, if necessary. Such a clay mineral has the function of further improving the wear resistance by being contained in the resin composition. Examples of the clay mineral that can be used in the present invention include kaolinite, calcined kaolinite, and sepiolite, and it is particularly preferable to use calcined kaolinite. These clay minerals may be used alone or in combination of two or more.

  Moreover, in this invention, it is preferable to use this clay mineral which has an average particle diameter of the range of 0.3-2.0 micrometers, and hardly aggregates. In addition, some clay minerals have been surface treated with silane coupling agents, fatty acids, etc., and organically treated with alkylammonium salts, alkylsulfonium salts, alkylphosphonium salts, etc. It is preferable to employ a clay mineral that has not been treated. The wear resistance of the resulting resin composition can be further improved by not subjecting the clay mineral to surface treatment or organic treatment. Examples of such clay minerals include “SATINTONE” (manufactured by ENGELHARD), “PANGEL” (manufactured by TOLSA), and the like.

  Next, the content of each component in the flame retardant resin composition of the present invention will be described. The content of (a) polypropylene in the resin composition is such that the entire resin component, that is, (a) a polypropylene resin, (b) a structure in which three or more vinyl acetate components that are constituent components of the copolymer are continuous. And a resin mixture comprising an ethylene / vinyl acetate copolymer having a vinyl acetate content of 50% by mass or more based on the entire copolymer, (c) a modified styrene thermoplastic elastomer, and (d) a modified polyolefin. It is 40-90 mass% with respect to the whole. When the content of the polypropylene resin is less than 40% by mass, the wear resistance and heat resistance of the resin composition may be lowered. On the other hand, when the content exceeds 90% by mass, the mechanical properties of the resin composition are reduced. And cold resistance may decrease. The content of the polypropylene resin is preferably 60 to 80% by mass, and particularly preferably 70 to 80% by mass with respect to the entire resin mixture.

  In addition, (b) ethylene / vinyl acetate copolymer with a specific structure and (c) modified styrene thermoplastic elastomer are used individually in combination with polypropylene resin, so that mechanical properties and wear resistance can be improved by using them together. improves. (B) The content of the ethylene / vinyl acetate copolymer having a specific structure is 5 to 20% by mass with respect to the entire resin mixture, and the content of the (c) modified styrene thermoplastic elastomer is also the resin mixture. It is 5-20 mass% with respect to the whole. When the content of the (b) ethylene / vinyl acetate copolymer having a specific structure and (c) the modified styrene thermoplastic elastomer is less than 5% by mass with respect to the entire resin mixture, the mechanical properties and cold resistance are lowered. On the other hand, if these contents exceed 20% by mass, the wear resistance and heat resistance may decrease. The content of (b) the ethylene / vinyl acetate copolymer having a specific structure and (c) the modified styrene thermoplastic elastomer is preferably 5 to 15% by mass with respect to the entire resin mixture.

  The total content of (b) the ethylene / vinyl acetate copolymer having a specific structure and (c) the modified styrene thermoplastic elastomer is preferably 10 to 40% by mass relative to the entire resin mixture. If the total content is less than 10% by mass, the mechanical properties and cold resistance of the resin composition may be lowered. On the other hand, if it exceeds 40% by mass, the wear resistance and heat resistance of the resin composition may be reduced. May decrease. The total content of (b) the ethylene / vinyl acetate copolymer having a specific structure and (c) the modified styrene thermoplastic elastomer is preferably 10 to 30% by mass.

  Content of (d) modified polyolefin in a resin composition is 0-20 mass% with respect to the whole resin mixture. When the content of the modified polyolefin exceeds 20% by mass, the fluidity of the resin composition is lowered, and a problem may occur in molding processability. The content of the modified polyolefin is preferably 5 to 10% by mass with respect to the entire resin mixture.

  In the flame-retardant resin composition of the present invention, depending on the content of (a) polypropylene resin, (b) ethylene / vinyl acetate copolymer, and (c) modified styrene thermoplastic elastomer, d) A structure not containing the modified polyolefin may be adopted, but by containing (d) the modified polyolefin, (e) water compared to the flame retardant resin composition not containing (d) the modified polyolefin. Improvement of the dispersibility of magnesium oxide leads to improvement of wear resistance and flame retardancy.

  In addition, when (d) the modified polyolefin is not included, each characteristic is slightly inferior to that of the modified polyolefin, but the mechanical characteristics such as excellent tensile characteristics, wear resistance, and flame retardancy can still be maintained. .

  The content of (e) magnesium hydroxide in the resin composition is 40 to 200 parts by mass with respect to 100 parts by mass of the resin mixture. When the content of magnesium hydroxide is less than 40 parts by mass, sufficient flame retardancy cannot be imparted to the resin composition. On the other hand, when the content exceeds 200 parts by mass, mechanical properties and cold resistance of the resin composition are not obtained. The specific gravity is adversely affected and the specific gravity is increased. The content of magnesium hydroxide is preferably 60 to 200 parts by mass with respect to 100 parts by mass of the resin mixture. In particular, in order to use it for an insulated wire using a conductor having an outer diameter of φ0.6 mm or less, it is preferably 120 to 200 parts by mass with respect to 100 parts by mass of the resin mixture.

  It is preferable that content of (f) clay mineral added to a resin composition as needed is 1-20 mass parts with respect to 100 mass parts of resin mixtures. When the content of the clay mineral is less than 1 part by mass, the wear resistance of the resin composition is not improved. On the other hand, when it exceeds 20 parts by mass, the mechanical properties of the resin composition may be deteriorated. The content of the clay mineral is particularly preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin mixture.

  It should be noted that various resin components and rubber components other than those described above and various additives may be appropriately added to the resin composition of the present invention as necessary within the range not hindering the object and effect of the present invention. it can. As additives, conventionally known ones can be used, for example, lubricants, antioxidants, light stabilizers, process oils, silicon oils, ultraviolet absorbers, carbon black, dispersants, pigments, dyes, antiblocking agents. Agents, cross-linking agents, cross-linking aids, etc., and depending on the application, conventionally used red phosphorus, polyphosphate compounds, zinc hydroxystannate, zinc stannate, zinc borate, calcium carbonate, hydrotalcite A flame retardant aid such as antimony oxide may be added.

  The flame-retardant resin composition of the present invention is obtained by melt-kneading the above-described components and additives added as necessary with a conventionally known kneading apparatus such as a twin-screw kneading extruder, a Banbury mixer, a kneader, or a roller. It can manufacture more simply. Moreover, when a biaxial kneading extruder is used, a process can be implemented continuously.

  In the production of the flame-retardant resin composition, a melt-kneaded product in which a polypropylene-based resin, magnesium hydroxide and, if necessary, a clay mineral and an additive are melt-kneaded in advance is manufactured, and the remaining in the melt-kneaded product. These materials (ethylene-vinyl acetate copolymer having a specific structure, modified styrenic thermoplastic elastomer, modified polyolefin, and additives as required) may be further melt-kneaded. By doing in this way, the dispersibility of the magnesium hydroxide in a resin composition improves, and abrasion resistance and a mechanical characteristic further improve.

  The kneading temperature is preferably set to (e) the decomposition temperature of magnesium hydroxide or lower (for example, 340 ° C. or lower). About other manufacturing conditions, such as extrusion amount, it can determine suitably with kinds, such as a resin component to be used.

Moreover, you may make it perform the crosslinking process as needed for the flame-retardant resin composition of this invention.
As a crosslinking method, a conventional electron beam irradiation crosslinking method or chemical crosslinking method can be employed.
In the case of the electron beam irradiation cross-linking method, the cross-linking can be performed by irradiating an electron beam by a conventional method after molding the flame retardant resin composition of the present invention. On the other hand, in the case of the chemical crosslinking method, an organic peroxide or the like may be added to the resin composition as a conventionally known crosslinking agent, and after the molding, heat treatment may be performed by a conventional method for crosslinking.

  The flame retardant resin composition of the present invention uses a polypropylene resin as a base polymer, and a resin mixture containing specific amounts of an ethylene copolymer having a specific structure, a modified styrene thermoplastic elastomer and a modified polyolefin as other components On the other hand, since the composition containing a specific amount of magnesium hydroxide is adopted, it has excellent wear resistance in addition to heat resistance and cold resistance, and also has good flame resistance and mechanical properties. It becomes a flame retardant resin composition having a good balance of properties.

  And it is easy to recycle even after disposal, and even if it is disposed of such as buried, it does not cause environmental pollution problems due to lead-based compounds or phosphorus compounds, and even if it is incinerated, harmful halogen gas, dioxin, etc. And adaptability to the environment is good.

  Further, the flame-retardant resin composition of the present invention is extruded into a metal conductor such as a copper wire, a tin-plated copper wire, an aluminum wire, or an optical fiber (hereinafter, these may be collectively referred to as “conductor” in some cases). The coated insulated wire can be widely used as an insulated wire having mechanical properties such as flame retardancy, wear resistance, and tensile properties, and adaptability to the environment. In particular, insulated wires that are extrusion-coated with the flame-retardant resin composition of the present invention are used in automobiles and electrical / electronic devices that require high wear resistance, flame resistance, mechanical properties, etc. When used as, the effect can be maximized. Such an insulated wire can be easily obtained by extrusion-coating the resin composition of the present invention on the outer periphery of the conductor using a known extrusion molding method.

  In addition, in the insulated wire of the present invention, the thickness of the insulating coating material is not particularly limited and can be formed as a desired thickness. However, the flame-retardant resin composition of the present invention has a so-called reduced diameter. Even if it is a case where it uses as a covering material of an insulated wire, the effect can be given to the diameter-reduced insulated wire. Specifically, even when the outer diameter of the conductor is φ0.6 mm or less (preferably φ0.3 to 0.6 mm), the flame retardant resin composition is extrusion coated and the insulated wire is kneaded and extruded. As with the insulated wire, a thin-diameter insulated wire that is excellent in flame retardancy and wear resistance, and can suitably exhibit the effects of having various properties such as mechanical properties, heat resistance, and cold resistance in a well-balanced manner. Become. In addition, the thickness of the flame retardant resin composition serving as an insulating coating material in the case of such a reduced-diameter insulated wire is preferably 0.5 mm or less, more preferably 0.3 mm or less, and 0 It is particularly preferable that the thickness be 15 to 0.3 mm.

  Further, the insulated wire has no problem even if the insulating layer has a multi-layer structure, such as separately providing an intermediate layer between the insulating coating material made of the resin composition of the present invention and the conductor.

  And even if it uses the flame-retardant resin composition of this invention as a constituent material of a resin molding, the resin molding which enjoys the above-mentioned outstanding effect can be provided. There is no restriction | limiting in particular in the shape and structure of this resin molding, For example, a power plug, a connector, a sleeve, a box, a tape base material, a tube, a sheet | seat etc. can be mentioned. These resin moldings can be obtained by molding the resin composition of the present invention by a conventionally known molding method such as an extrusion molding method or an injection molding method.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to these.

[Examples 1-8, Comparative Examples 1-5]
The structure of the flame retardant resin composition of Examples 1-8 is shown in Table 1, and the structure of the flame retardant resin composition of Comparative Examples 1-5 is shown in Table 2. The flame retardant resin composition was manufactured by using a Banbury mixer as a kneading machine, melt-kneading polypropylene resin, magnesium hydroxide, clay mineral, and additives (lubricant, antioxidant), and then remaining materials ( (Ethylene / vinyl acetate copolymer, modified styrene thermoplastic elastomer, modified polyolefin) were further melt-kneaded and pelletized.

  The details of the materials used are as follows. The melt flow rate (MFR) was measured under the following temperature and load conditions in accordance with JIS K7210. Here, the content in Table 1 shows the resin mixture consisting of (1) to (7) when the entire resin mixture consisting of (1) to (7) is 100 parts by mass. About each resin material to do, it becomes the content (mass%) when the whole resin mixture is 100 mass% and agrees.)

(1) Polypropylene (polypropylene resin)
Product name: PS201A (manufactured by Sun Aroma)
MFR: 0.5 g / 10 min (230 ° C., 2.16 kgf load)

(2) Ethylene / vinyl acetate copolymer 80
(Ethylene / vinyl acetate copolymer having a structure in which the vinyl acetate content is 80% by mass with respect to the entire copolymer and three or more vinyl acetate components are continuous)
Product name: Levapren 800HV (manufactured by Bayer)
MFR: 4.0 g / 10 min (190 ° C., 2.16 kgf load)

(3) Ethylene / vinyl acetate copolymer 60
(Ethylene / vinyl acetate copolymer having a vinyl acetate content of 60% by mass based on the entire copolymer and having a structure in which three or more vinyl acetate components are continuous)
Product name: Levapren 600HV (manufactured by Bayer)
MFR: 3.0 g / 10 min (190 ° C., 2.16 kgf load)

(4) Ethylene / vinyl acetate copolymer 50
(Ethylene / vinyl acetate copolymer having a vinyl acetate content of 50% by mass with respect to the entire copolymer and having a structure in which three or more vinyl acetate components are continuous)
Product name: Levapren 500HV (manufactured by Bayer)
MFR: 3.0 g / 10 min (190 ° C., 2.16 kgf load)

(5) Ethylene / vinyl acetate copolymer 33
(Ethylene / vinyl acetate copolymer having a vinyl acetate content of 33% by mass with respect to the total copolymer)
Product name: Everflex EV180 (Mitsui DuPont Polychemical Co., Ltd.)
MFR: 0.2 g / 10 min (190 ° C., 2.16 kgf load)

(6) Modified styrenic thermoplastic elastomer:
Product name: Clayton FG1901X (Clayton Polymer Co., Ltd.)
MFR: 6.4 g / 10 min (230 ° C., 2.16 kgf load)

(7) Modified polyolefin:
Product name: Adtex L6100M (manufactured by Nippon Polyethylene)
MFR: 1.1 g / 10 min (190 ° C., 2.16 kgf load)

(8) Magnesium hydroxide:
Product Name: Kisuma 5L (Kyowa Chemical Industry Co., Ltd.)
Surface treatment: Yes (Surface treatment with silane coupling agent)
Average particle size: 0.8μm

(9) Clay mineral Product name: Satintone SP33 (manufactured by ENGELHARD)
Surface treatment and organic treatment: None Average particle size: 1.4 μm

(10) Additives (Lubricants, antioxidants)
Product name: Irganox 1010 (Ciba) (lubricant)
Product name: Neowax ACL (manufactured by Yasuhara Chemical)
(Tables 1 and 2 are the combined doses)

(Composition of resin composition: Examples)

(Composition of resin composition: Comparative example)

  Examples 1-8 and Comparative Examples 1-5 are the results of comparing and evaluating the insulated wires obtained by kneading the resin compositions with a Banbury mixer and coating the conductors with an extruder.

  In Examples 1 to 7 and Comparative Examples 1 to 4, the insulated wire in which the outer periphery of the annealed copper wire having a diameter of φ0.3 mm was coated with the resin composition with a thickness of 0.2 mm, Example 8 and Comparative Example 5 were For insulated wires coated with a resin composition with a thickness of 0.2 mm on the outer periphery of an annealed copper wire with a diameter of φ0.85 mm, the following criteria are used for “tensile properties”, “flame resistance”, “wear resistance” “Sex” was compared and evaluated. The results are shown in Table 3.

(Tensile properties)
The tensile strength (MPa) and tensile elongation (%) of the insulation coating material of the obtained insulated wire were measured at a standard line of 25 mm and a tensile speed of 200 mm / min in accordance with JIS C3005. The tensile strength was 16 MPa or more, and the tensile elongation was 125% or more.

(Flame retardance)
The 45 degree inclination flame retardant test prescribed | regulated to ISO 6722 was implemented, and the flame retardance was confirmed. If the flame disappeared within 70 seconds, it was determined to be acceptable.

(Abrasion resistance)
A predetermined load was applied to the blade with a piano wire having a diameter of 0.45 mm attached to the tip, the surface of the insulated wire was reciprocated at 60 times / minute, and the number of reciprocations until the blade penetrated the coating and contacted the conductor was measured. . In addition, about Examples 1-7 and Comparative Examples 1-4, it passed 150 times or more by load 5N, and Example 8 and Comparative Example 5 made 150 times or more acceptable by load 7N.

(result)

  From the results in Table 3, the insulated wire obtained by extrusion-coating the flame-retardant resin composition of the present invention shown in the examples showed excellent tensile properties, flame retardancy and wear resistance. In addition, Example 3 which does not contain a modified polyolefin showed excellent tensile properties, wear resistance and flame retardancy although the tensile properties were slightly inferior to those of Example 2.

  The flame retardant resin composition of the present invention is a flame retardant resin composition that is particularly excellent in flame retardancy and wear resistance, and is well balanced in various properties such as mechanical properties. It can be advantageously used as an insulating coating material for an insulated wire disposed in an electric / electronic device, a constituent member of the automobile or the like.

Claims (4)

  (A) 40 to 90% by mass of a polypropylene resin, (b) a structure in which three or more vinyl acetate components that are constituent components of the copolymer are continuous, and the content of vinyl acetate in the entire copolymer A resin comprising 5 to 20% by mass of an ethylene / vinyl acetate copolymer of 50% by mass or more, (c) 5 to 20% by mass of a modified styrene thermoplastic elastomer, and (d) 0 to 20% by mass of a modified polyolefin. (E) 40-200 mass parts of magnesium hydroxide is contained with respect to 100 mass parts of mixtures, The flame-retardant resin composition characterized by the above-mentioned.   Furthermore, (f) 1-20 mass parts of clay minerals are contained with respect to 100 mass parts of said resin mixtures, The flame-retardant resin composition of Claim 1 characterized by the above-mentioned.   An insulated wire obtained by extrusion-coating a flame retardant resin composition according to claim 1 or 2 on a conductor.   The insulated wire according to claim 3, wherein an outer diameter of the conductor is φ0.6 mm or less.