JP2009301777A - Insulation wire and wire harness - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulation wire with enough flame resistance, and excellent in low-temperature resistance and abrasion resistance. <P>SOLUTION: The insulation wire includes conductors 12 and an insulation coating layer coating an outer periphery of the conductors 12. The insulation coating layer is structured of a plurality of layers consisting of an inner layer 14 and an outer layer 16, either of them 14, 16 being a layer containing a kind or two selected from polyphenylene ether resin and polyphenylene sulfide resin, and the other being a layer containing olefin system resin and metal hydroxide. That other layer is preferred to contain 0.1 to 10% by mass of resin with a glass transition temperature of -20°C or less. Further, a thickness of the other layer is preferred to be not less than half that of the insulation coating layer as a whole. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an insulated wire and a wire harness, and more particularly to an insulated wire and a wire harness that are suitably used for vehicle parts, electrical / electronic device parts, and the like.

  Conventionally, as an insulated wire used for wiring of vehicle parts such as automobile parts and electrical / electronic equipment parts, generally, the outer periphery of a conductor is widely coated with a vinyl chloride resin composition to which a halogen-based flame retardant is added. Has been used.

  However, since this type of vinyl chloride resin composition contains a halogen element, it releases harmful halogen-based gases to the atmosphere during combustion such as in the event of a vehicle fire or incineration and disposal of electrical and electronic equipment. There was a problem of causing environmental pollution.

  Therefore, from the standpoint of reducing the burden on the global environment, replacement with a so-called non-halogen flame retardant composition that does not generate harmful halogen-based gas during combustion such as incineration and disposal is being promoted. .

  For example, in Patent Document 1, magnesium hydroxide as a non-halogen flame retardant is added to an olefin liquid resin or rubber that does not contain halogen, such as ethylene-ethyl acrylate copolymer (EEA), polyethylene, and ethylene propylene rubber. An insulated wire in which a flame retardant composition is coated on the outer periphery of a conductor is disclosed.

  For example, Patent Document 2 discloses an insulated wire in which a conductor composition containing a polyolefin resin, a polyphenylene ether resin, and two kinds of specific organic compounds is coated on the outer periphery of a conductor.

  Patent Document 3 discloses an insulated wire in which the outer periphery of a conductor is coated with a resin composition containing a polyphenylene sulfide resin and a polyolefin resin.

Japanese Patent No. 3339154 JP 2002-265698 A JP 2006-12659 A

  However, olefin-based resins and the like are basically flammable, and non-halogen flame retardants are inferior in flame retardancy compared to halogen-based flame retardants. Therefore, in the flame retardant composition shown in Patent Document 1 or the like, it is necessary to add a large amount of magnesium hydroxide in order to ensure sufficient flame retardancy. Therefore, the conventional insulated wire has a problem that mechanical properties such as wear resistance are remarkably deteriorated.

  Further, the insulated wires shown in Patent Document 2 and Patent Document 3 do not satisfy both cold resistance and wear resistance.

  The problem to be solved by the present invention is to provide an insulated wire and a wire harness that have sufficient flame retardancy and are excellent in cold resistance and wear resistance.

  In order to solve the above problems, an insulated wire according to the present invention is an insulated wire having a conductor and an insulation coating layer covering the outer periphery of the conductor, and the insulation coating layer is composed of a plurality of layers. The gist is to have a first layer containing one or more selected from a polyphenylene ether resin and a polyphenylene sulfide resin, and a second layer containing an olefin resin and a metal hydroxide. Is.

  In this case, the second layer preferably contains a resin having a glass transition temperature of −20 ° C. or lower.

  The resin having a glass transition temperature of −20 ° C. or lower preferably has a functional group.

  In this case, the functional group preferably represents one or more selected from a carboxylic acid group, an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, an alkenyl cyclic imino ether group, and a silane group. it can.

  Moreover, the content rate of the resin whose glass transition temperature is -20 degrees C or less is good in the range of 0.1-10 mass%.

  The thickness of the second layer is preferably 1/2 or more of the total thickness of the insulating coating layer.

  The first layer is preferably an inner layer of the insulating coating layer.

  Moreover, the wire harness which concerns on this invention makes it a summary to contain the said insulated wire.

  The insulated wire according to the present invention has a plurality of insulating coating layers, a first layer containing one or more selected from a polyphenylene ether resin and a polyphenylene sulfide resin, an olefin resin, And a second layer containing a metal hydroxide. Therefore, it is excellent in flame retardancy, cold resistance, and wear resistance.

  At this time, when the second layer contains a resin having a glass transition temperature of −20 ° C. or lower, the second layer becomes more flexible. Thereby, the insulated wire is further excellent in cold resistance.

  And when resin with the said glass transition temperature of -20 degrees C or less has a functional group, adhesiveness with the metal hydroxide used together becomes high. Thereby, since the dispersibility of the metal hydroxide is improved, the cold resistance and wear resistance of the second layer are further improved, and the cold resistance and wear resistance of the insulated wire are improved. In addition, when the second layer is a layer in contact with the conductor, the adhesion between the second layer and the conductor is improved. This also improves mechanical properties such as wear resistance.

  Further, when the content of the resin having a glass transition temperature of −20 ° C. or lower is within the above range, the balance between cold resistance and wear resistance is excellent.

  And when the thickness of said 2nd layer is 1/2 or more of the thickness of the whole insulation coating layer, the cold resistance improvement effect is high. Moreover, cost can be reduced.

  When the first layer is an inner layer of the insulating coating layer, the first layer made of a material having a high melting temperature can be formed first. Therefore, there is no possibility that a layer made of a material having a melting temperature lower than that of the first layer is melted by the heat of fusion when the first layer is formed. Thereby, productivity becomes high and it is excellent also in the dimensional stability and external appearance of an insulated wire.

  On the other hand, according to the wire harness which concerns on this invention, since the said insulated wire is included, deterioration of an insulation coating layer is suppressed and high reliability can be ensured over a long term.

  Next, an embodiment of the present invention will be described in detail. The insulated wire according to the present invention includes a conductor and an insulating coating layer that covers the outer periphery of the conductor, and the insulating coating layer includes a plurality of layers. The insulating coating layer may be composed of two or more layers, and may be three or more layers. From the viewpoint of ease of manufacture, the insulating coating layer is preferably two layers or three layers. More preferably, there are two layers.

  The insulating coating layer has a first layer containing one or more selected from a polyphenylene ether resin and a polyphenylene sulfide resin, and a second layer containing an olefin resin and a metal hydroxide. .

  When the insulating coating layer is composed of two layers, the insulating coating layer includes the first layer and the second layer. In this case, the first layer may be an inner layer and the second layer may be an outer layer, or the first layer may be an outer layer and the second layer may be an inner layer. More preferably, the first layer is an inner layer and the second layer is an outer layer from the viewpoint of productivity, dimensional stability, appearance, and the like of the insulated wire. That is, since the first layer is formed of a material having a higher melting temperature than the second layer, if the first layer is formed on the inner side before the second layer, the second layer is When forming, there is no possibility that the second layer is melted by the heat of fusion when forming the first layer. Thereby, productivity is improved and the dimensional stability and appearance of the insulated wire are also excellent.

  On the other hand, when the insulating coating layer is composed of three or more layers, the insulating coating layer includes the first layer, the second layer, and one or more other layers. In this case, the first layer and the second layer may be located at any position on the insulating coating layer, and are not particularly limited. More preferably, the first layer made of a material having a high melting temperature can be formed inside first, and a layer made of a material having a lower melting temperature than the first layer forms the first layer. The first layer is preferably an inner layer of the insulating coating layer from the viewpoint that there is no possibility of being melted by the heat of fusion.

  Since the first layer contains a polyphenylene ether resin or a polyphenylene sulfide resin, the wear resistance is improved. It also has flame retardancy.

  The polyphenylene ether resin contained in the first layer is generally obtained by polymerizing phenols. The polyphenylene sulfide resin is generally obtained by polymerizing thiophenols. The polymerization method is not particularly limited.

  Phenols and thiophenols may have a substituent on the aromatic ring. At this time, the number and position of the substituents are not particularly limited. Suitable substituents include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, pri-butyl group, sec-butyl group, tert-butyl group, hydroxyethyl group, hydroxymethyl group, phenylethyl Examples thereof include a group, benzyl group, carboxyethyl group, methoxycarbonylethyl group, cyanoethyl group, phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, and allyl group. These may be used alone or in combination of two or more.

  The polyphenylene ether resin may be composed of the same type of phenols or may be a copolymer of different types of phenols. In addition, the polyphenylene sulfide resin may be made of the same kind of thiophenol or may be a copolymer made of different kinds of thiophenols.

  The polyphenylene ether resin or polyphenylene sulfide resin may be functionalized. Examples of the compound used for functionalization include maleic anhydride, maleic acid, fumaric acid, itaconic acid, (meth) acrylic acid, methyl (meth) acrylate, glycidyl (meth) acrylate, and styrene.

  The first layer may contain other polymer materials that can be alloyed other than polyphenylene ether resin and polyphenylene sulfide resin. Examples of other polymer materials include olefin resin, polystyrene, polyamide resin, styrene thermoplastic elastomer, thermoplastic elastomer, rubber, and the like. The other polymer material is more preferably an olefin resin from the viewpoint of improving fluidity and chemical resistance. From the viewpoint of improving dimensional accuracy and flame retardancy, it is polystyrene.

  In the first layer, the total mass of the polyphenylene ether resin and the polyphenylene sulfide resin is preferably in the range of 10 to 90% by mass with respect to the total mass of the first layer. More preferably, it exists in the range of 20-80 mass%, More preferably, it exists in the range of 30-70 mass%. When the content is less than 10% by mass, the effect of enhancing wear resistance and flame retardancy tends to be lowered. On the other hand, if the content exceeds 90% by mass, the first layer becomes too hard, and the flexibility of the insulated wire tends to decrease.

  Examples of the olefin resin that can be contained in the first layer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1- Examples thereof include ethylene (co) polymers such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and vinyl acetate, and α-olefin (co) polymers. . These can be used alone or in combination of two or more. In this case, examples of the polyethylene include low density polyethylene, high density polyethylene, and linear low density polyethylene.

  Examples of the styrenic thermoplastic elastomer that can be contained in the first layer include styrene-butadiene block copolymers and styrene-ethylene-styrene copolymers (SES), which are hydrogenated or partially hydrogenated derivatives thereof, and styrene-ethylene- Butylene-styrene copolymer (SEBS), maleic anhydride-modified styrene-ethylene-butylene-styrene copolymer, styrene-isoprene block copolymer and its hydrogenated or partially hydrogenated styrene-ethylene-propylene copolymer Polymer (SEP), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), maleic anhydride modified styrene-ethylene-propylene-styrene copolymer Coalescence etc. can be illustrated . These may be used alone or in combination of two or more.

  Examples of the thermoplastic elastomer that can be contained in the first layer include 1,2-polybutadiene. Examples of the rubber that can be contained in the first layer include butadiene rubber and isoprene rubber. These rubbers may be acid-modified. For example, a modified butadiene rubber having a core-shell structure, a modified isoprene rubber having a core-shell structure, and the like can be exemplified.

  Examples of the olefin resin contained in the second layer include the resins described as the olefin resin that can be contained in the first layer.

  Examples of the metal hydroxide contained in the second layer include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and the like. These may be used alone or in combination of two or more. More preferred are magnesium hydroxide and aluminum hydroxide.

  The content of the metal hydroxide is preferably in the range of 30 to 250 parts by mass, more preferably in the range of 50 to 200 parts by mass with respect to 100 parts by mass of the polymer component contained in the second layer. More preferably, it is in the range of 60 to 180 parts by mass.

  The average particle diameter of the metal hydroxide is preferably in the range of 0.1 to 20 μm. More preferably, it exists in the range of 0.2-10 micrometers, More preferably, it exists in the range of 0.5-5 micrometers. If the average particle diameter is less than 0.1 μm, the particles are likely to aggregate, and thus the mechanical properties are likely to deteriorate. In addition, productivity is reduced. On the other hand, when the average particle diameter exceeds 20 μm, the low temperature characteristics are liable to deteriorate. In addition, the appearance tends to be poor.

  The metal hydroxide may be surface-treated. As the surface treatment agent, for example, a general surface treatment agent such as a silane coupling agent, a fatty acid, a fatty acid derivative, a higher alcohol, or a wax may be used, or 1-heptene, 1-octene, 1-nonene, 1 -It may be a homopolymer of α-olefin such as decene or a mutual copolymer. These can be used alone or in combination of two or more.

  The surface treatment agent may be functionalized. Compounds used for functionalization include unsaturated carboxylic acids and their derivatives. Specific examples include maleic anhydride, maleic acid, maleic acid monoester, maleic acid diester, and fumaric acid. These can be used alone or in combination of two or more. Of these, maleic anhydride and maleic acid are preferred.

  As a method for introducing an acid or the like into the surface treatment agent, there are a graft method and a direct method (copolymerization method). Moreover, as an introduction amount, Preferably, it exists in the range of 0.1-20 mass%, More preferably, it exists in the range of 0.2-10 mass%, More preferably, it exists in the range of 0.2-5 mass%. It is.

  It is preferable that a surface treating agent exists in the range of 0.1-10 mass parts with respect to 100 mass parts of metal hydroxides. More preferably, it exists in the range of 0.5-3 mass parts. If the amount is less than 0.1 parts by mass, the effect of improving the electric wire characteristics tends to be reduced, and if the amount exceeds 10 parts by mass, excessively added impurities are likely to remain as impurities, and the physical properties of the wires are likely to be reduced.

  The second layer may contain a resin having a glass transition temperature of −20 ° C. or lower. A resin having a glass transition temperature of −20 ° C. or lower makes an insulated wire having a first layer containing a polyphenylene ether resin or a polyphenylene sulfide resin more flexible. Examples of the resin having a glass transition temperature of −20 ° C. or lower include olefin resins. Specifically, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, vinyl acetate, and other ethylene (co) polymers and α-olefin (co) polymers. These can be used alone or in combination of two or more.

  The glass transition temperature (Tg) of the resin can be measured by, for example, thermal analysis (DSC method).

  The resin having a glass transition temperature of −20 ° C. or lower may be functionalized. When functionalized, the adhesion to the metal hydroxide used together increases. Thereby, since the dispersibility of the metal hydroxide is improved, the cold resistance and wear resistance of the second layer are further improved, and the cold resistance and wear resistance of the insulated wire are improved. In addition, when the second layer is a layer in contact with the conductor, the adhesion between the second layer and the conductor is improved. Thereby, mechanical properties such as wear resistance are improved.

  Examples of functional groups that can be introduced include carboxylic acid groups, acid anhydride groups, epoxy groups, hydroxyl groups, amino groups, alkenyl cyclic imino ether groups, and silane groups. These can be used alone or in combination of two or more.

  The ratio of the functional group in the resin is preferably in the range of 0.05 to 10% by mass. When the ratio of the functional group is less than 0.05% by mass, the above-described adhesion improving effect tends to be lowered. On the other hand, when the proportion of the functional group exceeds 10% by mass, the covering strip property at the time of end processing of the electric wire tends to deteriorate. More preferably, it is 0.1-10 mass%, More preferably, it exists in the range of 0.2-5 mass%.

  As a method for introducing a functional group into the resin, a normal graft polymerization method or copolymerization method can be used. That is, a method of graft polymerization of a compound that forms a functional group to the resin using a radical polymerization initiator or the like, and a method of copolymerizing the resin and a compound that forms a functional group are exemplified.

  Specific examples of the compound that introduces a carboxylic acid group or an acid anhydride group into the resin include, for example, α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, and acids thereof. Examples include anhydrides, unsaturated monocarboxylic acids such as (meth) acrylic acid, furanic acid, crotonic acid, vinyl acetic acid and pentenoic acid, and ester compounds thereof.

  Specific examples of the compound for introducing an epoxy group into the resin include, for example, (meth) acrylic acid glycidyl, itaconic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, and maleic acid. Glycidyl esters of acids such as crotonic acid and fumaric acid, glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyl oxyethyl vinyl ether, styrene-p-glycidyl ether, and p-glycidyl styrene Can do.

  Specific examples of the compound that introduces a hydroxyl group into the resin include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, and the like. it can.

  Specific examples of the compound for introducing an amino group into the resin include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Examples include dibutylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, and the like.

  Specific examples of the compound for introducing an alkenyl cyclic imino ether group into the resin include, for example, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-vinyl-5,6-dihydro- Examples thereof include 4H-1,3-oxazine and 2-isopropenyl-5,6-dihydro-4H-1,3-oxazine.

  Specific examples of the compound that introduces a silane group into the resin include unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetylsilane.

  The content of the resin having a glass transition temperature of −20 ° C. or lower is preferably in the range of 0.1 to 10% by mass. When the content is less than 0.1% by mass, it is difficult to obtain sufficient cold resistance. On the other hand, if the content exceeds 10% by mass, the wear resistance tends to decrease. When it is within the above range, the balance between cold resistance and wear resistance is excellent. More preferably, it is in the range of 0.3 to 8% by mass, and still more preferably in the range of 0.5 to 5% by mass.

  The second layer may contain a polymer material other than the olefin resin and a resin having a glass transition temperature of −20 ° C. or lower. Examples of other polymer materials include styrenic thermoplastic elastomers, thermoplastic elastomers, and rubbers. These can be exemplified by the materials described as styrenic thermoplastic elastomers, thermoplastic elastomers, and rubbers that can be contained in the first layer.

  When there are three or more insulating coating layers, the material for forming the other layers is not particularly limited. For example, olefin resin, styrene thermoplastic elastomer, thermoplastic elastomer, rubber and the like can be exemplified. From the standpoint of ensuring adhesion with the first layer and the second layer, the same compounding material as that for the second layer may be used.

  In the first layer, the second layer, and other layers, additives may be blended as necessary. For example, general fillers used for wire covering materials, pigments, antioxidants, anti-aging agents, flame retardants, and the like may be blended.

  The thickness of the second layer is preferably 1/2 or more of the total thickness of the insulating coating layer from the viewpoint of high cold resistance improvement effect and cost reduction. More preferably, it exists in the range of 1 / 2-9 / 10, More preferably, it exists in the range of 3 / 5-4 / 5. On the other hand, the thickness of the first layer is preferably in the range of 1/10 to 1/2 of the total thickness of the insulating coating layer from the viewpoint of a high effect of improving wear resistance. More preferably, it exists in the range of 1/5-2/5, More preferably, it exists in the range of 1/4-7/20. Further, the thickness of the entire insulating coating layer is not particularly limited, but is preferably 0.5 mm or less.

  FIG. 1 shows an insulated wire 10 according to an embodiment of the present invention. 1 shows that the outer periphery of the conductor 12 is covered with an insulating coating layer composed of two layers of an inner layer 14 and an outer layer 16. The inner layer 14 may be the first layer or the second layer.

  Examples of the conductor include a single metal wire, a twisted wire in which a plurality of metal strands are twisted together, and a material in which a twisted wire is compressed. FIG. 1 (a) shows an example of a conductor 12 made of a stranded wire in which a plurality of metal strands are twisted together. FIG. 1 (b) shows a conductor 12 formed by compressing a stranded wire. An example is shown. The diameter, material, and the like of the conductor 12 are not particularly limited, and can be appropriately selected depending on the application.

  For example, copper is generally used as the conductor material, but aluminum, magnesium, or the like may be used in addition to copper. Moreover, it is good also as an alloy which contained other metals in metals, such as copper. Examples of other metals include iron, nickel, magnesium, and silicon. In addition, a metal widely used as a conductor may be added to copper or the like or used alone.

  According to the insulated wire having the above structure, the wear resistance of the insulated wire is improved by the first layer containing the polyphenylene ether resin or the polyphenylene sulfide resin, and the cold resistance is improved by the second layer containing the olefin resin. In addition to the improvement, the first layer and the second layer each have flame retardancy, and as a whole, are excellent in flame retardancy, cold resistance, and abrasion resistance in a well-balanced manner.

  Further, by providing the second layer in combination with the first layer, the flexibility of the insulated wire is increased, and other wire characteristics such as formability and workability are also satisfied.

  And since the insulation coating layer is comprised from the several layer which has said 1st layer and said 2nd layer, in order to obtain desired performance, it is convenient on the material surface. In other words, compared to an insulated wire having an insulating coating layer composed of a single layer, the first layer material and the second layer material do not need to be blended so that they can be alloyed. There is an advantage that the combination of materials for satisfying both the cold resistance and the wear resistance is more free. Moreover, since it comprises a plurality of layers having the first layer, the increase in hardness due to the first layer can be mitigated by another layer.

  Next, the manufacturing method of an insulated wire is demonstrated. First, a resin composition that forms the first layer, a resin composition that forms the second layer, and a resin composition that forms another layer as necessary are prepared. In order to prepare each composition, the respective materials are blended individually, and these are dry blended with a normal tumbler or the like, or a usual product such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin screw extruder, a roll, etc. The composition can be obtained by melt-kneading with a kneader and uniformly dispersing.

  Next, using a normal extruder or the like, the resin composition for forming the inner layer is extruded (extruded) on the outer periphery of the conductor, and the resin composition for forming the outer layer is extruded on the outer periphery of the inner layer. Can be manufactured. At this time, the inner layer and the outer layer may be extruded by coextrusion molding, or the outer layer may be extruded after the inner layer is extruded. Further, in the case of an insulated wire having an intermediate layer between the inner layer and the outer layer, a resin composition for forming the outer layer is formed on the outer periphery of the intermediate layer by extruding the resin composition forming the intermediate layer on the outer periphery of the inner layer. What is necessary is just to extrude a thing.

  Next, the wire harness according to the present invention will be described. The wire harness which concerns on this invention comprises the said insulated wire. It may be a wire bundle composed only of the above insulated wires, or may include insulated wires coated with other resin compositions, such as vinyl chloride-based insulated wires or other insulated wires not containing halogen elements. The wire bundle comprised by may be sufficient. For example, the wire bundle may be covered with a wire harness protective material. The number of electric wires can be determined arbitrarily and is not particularly limited.

  A wire harness protective material has a role which covers the outer periphery of the electric wire bundle in which the multiple insulated electric wire was bundled, and protects an internal electric wire bundle from the external environment. Although it does not specifically limit as a base material which comprises a wire harness protective material, Polyolefin-type resin compositions, such as polyethylene and a polypropylene, are preferable. A flame retardant may be appropriately added to the resin composition.

  For wire harness protection materials, for example, those with adhesive applied to at least one surface of a tape-shaped substrate, or those having a substrate formed in a tube shape, sheet shape, etc. It can be appropriately selected and used accordingly.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(Test material and manufacturer)
The test materials used in this example are shown together with the manufacturer, product name, physical property values, and the like.

-Polyphenylene ether resin (PPE) [Asahi Kasei Chemicals Co., Ltd., "Zylon 200H"]
Polyphenylene sulfide resin (PPS) [manufactured by Polyplastics Co., Ltd., “Fortron 0220A9”]
Polypropylene (PP <1>) [Nippon Polypro Co., Ltd., “Novatech PP EC7”, Tg = −10 ° C.]
-Maleic anhydride modified polypropylene (PP <2>) [Mitsui Chemicals, “NF556”, Tg = −80 ° C.]
Polyethylene <1> (PE <1>) [Nippon Polyethylene Co., Ltd., “HY420”, Tg = −80 ° C.]
Polyethylene <2> (PE <2>) [Nippon Polyethylene Co., Ltd., “HY430”, Tg = −100 ° C.]
Polyethylene <3> (PE <3>) [Nippon Polyethylene Co., Ltd., “HY520”, Tg = −90 ° C.]
・ Magnesium hydroxide [Kyowa Chemical Co., Ltd., “Kisuma 5A”]

(Production of insulated wires)
The components shown in the examples and comparative examples were mixed in the indicated amounts and kneaded at 200 ° C. by a twin screw extruder. The obtained composition was extruded at a thickness of 0.2 mm around a stranded conductor (cross-sectional area of 0.5 mm ² ) obtained by twisting seven annealed copper wires with an extrusion molding machine. Each such insulated wire was produced.

(Flame retardance evaluation)
It carried out based on JASO D611-94. That is, first, each insulated wire according to the example and the comparative example was cut out to a length of 300 mm to obtain each test piece. Next, each test piece is put in an iron test box and supported horizontally, and the tip of the reducing flame is applied using a Bunsen burner having a diameter of 10 mm until it burns within 30 seconds from the lower side of the center of the test piece. The afterflame time after removal was measured. At this time, those with a residual flame time of 15 seconds or less were regarded as acceptable “◯”, and those with an afterflame exceeding 15 seconds were regarded as unacceptable “x”.

(Cold resistance evaluation)
It implemented based on JISC3005. That is, each manufactured insulated wire was cut into a length of 38 mm to obtain each test piece. Next, each test piece was put on a testing machine, hit with a striking tool while cooling, and the temperature when all five pieces were cracked was defined as the cold resistant temperature. A sample having a cold resistant temperature of −20 ° C. or lower was evaluated as “good”, and a sample having a cold resistant temperature exceeding −20 ° C. was determined as “failed”.

(Abrasion resistance evaluation)
In accordance with JASO D611-94, the test was performed by a blade reciprocation method. That is, each insulated wire according to the example and the comparative example was cut into a length of 750 mm to obtain each test piece. Next, the blade is reciprocated at a speed of 50 times per minute on the surface of the covering material of each test piece at a length of 10 mm or more in the axial direction at a room temperature of 23 ± 5 ° C., and the number of reciprocations until the blade contacts the conductor It was measured. At this time, the load applied to the blade was set to 7N, and the minimum value of 4 times of the test was 200 times or more as a pass “◯”. On the other hand, if the minimum value of the number of test times of 4 is less than 200 times, the failure was judged as “x”.

  Tables 1 and 2 show the blending ratio of the resin composition used for the wire covering material of each insulated wire and the evaluation results. At this time, the blending ratio is expressed in parts by mass.

  Comparative Examples 1 to 3 are insulated wires having a single insulating coating layer. Comparative Examples 1 and 3 are composed of a layer made of only polyolefin and do not contain a flame retardant. Therefore, it is inferior in flame retardancy. Moreover, the comparative example 2 is comprised by the layer which consists of polyolefin containing magnesium hydroxide. Therefore, although it has a flame retardance, abrasion resistance is falling by containing magnesium hydroxide.

  And Comparative Examples 4-6 is an insulated wire with two insulation coating layers. In Comparative Examples 4 to 6, either one of the layers is a layer in which the polymer component is an olefin resin, but does not contain a flame retardant and does not contain PPE or PPS. Therefore, it is inferior in flame retardancy and inferior in wear resistance.

  On the other hand, Examples 1-6 are the insulated wires which have the insulation coating layer formed with the layer structure and material which satisfy this invention. For this reason, it was confirmed that the insulated wire had excellent balance of flame retardancy, cold resistance, and wear resistance.

  Moreover, Examples 7-11 are carrying out the layer structure opposite to the layer structure of Examples 1-5, respectively. That is, the inner layers of Examples 7 to 11 are made of the same material as the outer layers of Examples 1 to 5, respectively, and the outer layers of Examples 7 to 11 are made of the same material as the inner layers of Examples 1 to 5, respectively. Even if the layer containing PPE or PPS is in the outer layer as in Examples 1 to 6 or in the inner layer as in Examples 7 to 11, flame retardancy, cold resistance, and abrasion resistance are achieved. It was confirmed that it was excellent.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

  The insulated wire according to the present invention is suitably used as an insulated wire used for wiring of, for example, vehicle parts, electrical / electronic equipment parts, and the like.

It is sectional drawing of the circumferential direction showing the insulated wire which concerns on one Embodiment of this invention.

Explanation of symbols

10 Insulated wire 12 Conductor 14 Inner layer 16 Outer layer

Claims (8)

An insulated wire having a conductor and an insulating coating layer covering the outer periphery of the conductor,
The insulating coating layer is composed of a plurality of layers,
A first layer containing one or more selected from a polyphenylene ether resin and a polyphenylene sulfide resin;
An insulated wire comprising a second layer containing an olefin resin and a metal hydroxide.   The insulated wire according to claim 1, wherein the second layer contains a resin having a glass transition temperature of -20 ° C or lower.   The insulated wire according to claim 2, wherein the resin having a glass transition temperature of -20 ° C or lower has a functional group.   The functional group is one or more selected from a carboxylic acid group, an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, an alkenyl cyclic imino ether group, and a silane group. The insulated wire as described in 1.   5. The insulated wire according to claim 2, wherein the content of the resin having a glass transition temperature of −20 ° C. or lower is in a range of 0.1 to 10% by mass.   The insulated wire according to any one of claims 1 to 5, wherein the thickness of the second layer is ½ or more of the total thickness of the insulating coating layer.   The insulated wire according to any one of claims 1 to 6, wherein the first layer is an inner layer of the insulating coating layer.   A wire harness comprising the insulated wire according to claim 1.

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