WO2015125574A1 - Composition for electric wire protective materials, electric wire protective material and wiring harness - Google Patents

Composition for electric wire protective materials, electric wire protective material and wiring harness Download PDF

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Publication number
WO2015125574A1
WO2015125574A1 PCT/JP2015/052421 JP2015052421W WO2015125574A1 WO 2015125574 A1 WO2015125574 A1 WO 2015125574A1 JP 2015052421 W JP2015052421 W JP 2015052421W WO 2015125574 A1 WO2015125574 A1 WO 2015125574A1
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Prior art keywords
composition
electric wire
flame retardant
wire protective
wire
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PCT/JP2015/052421
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French (fr)
Japanese (ja)
Inventor
清水　亨
中野　正剛
達也 嶋田
諭 村尾
Original Assignee
株式会社オートネットワーク技術研究所
住友電装株式会社
住友電気工業株式会社
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Publication of WO2015125574A1 publication Critical patent/WO2015125574A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention is, for example, a wire protection material for protecting a bundle of wires such as a corrugated tube used for vehicle parts such as automobiles, electrical / electronic equipment parts, etc., a composition for a wire protection material used for the wire protection material, and
  • the present invention relates to a wire harness using the wire protective material.
  • a flame retardant corrugated tube formed by extruding a flame retardant polyolefin resin composition obtained by blending a flame retardant or the like into a polyolefin such as polypropylene is known as a protective material for automobile electric wires.
  • a flame retardant corrugated tube formed by extruding a flame retardant polyolefin resin composition obtained by blending a flame retardant or the like into a polyolefin such as polypropylene is known as a protective material for automobile electric wires.
  • the composition includes 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyl) phenyl] propane and tris (2,3-dibromopropyl) isocyanate per 100 parts by weight of polyolefin. 2.5 to 30 parts by weight of a flame retardant having a weight ratio to nurate of 8: 2 to 4: 6 and 0.5 to 20 parts by weight of antimony trioxide are blended.
  • a metal oxide, a metal hydroxide, or the like is used as a flame retardant for the flame retardant corrugated tube.
  • An object of the present invention is to provide a composition for an electric wire protection material, an electric wire protection material, and a wire harness that are capable of preventing the occurrence of heat resistance and excellent in heat resistance and flame retardancy of a molded product.
  • the wire protective material composition according to the present invention comprises a polypropylene resin and a polypropylene resin composition containing a brominated flame retardant and antimony trioxide as a flame retardant, and containing no metal oxide other than antimony trioxide,
  • the gist is that the brominated flame retardant has a melting point of 110 ° C. or higher.
  • composition for an electric wire protective material further contains a copper damage inhibitor.
  • the wire protective material composition further contains a phenolic antioxidant.
  • the wire protective material composition further contains a phosphorus-based heat stabilizer.
  • the gist of the wire protection material according to the present invention is that the wire is molded into a predetermined shape capable of protecting the wire using the composition for wire protection material.
  • the summary of the wire harness according to the present invention is that a wire bundle in which a plurality of insulated wires are bundled is covered with a wire protector formed using the above-described composition for a wire protector. Is.
  • the composition for an electric wire protective material according to the present invention comprises a polypropylene resin and a polypropylene resin composition containing a bromine-based flame retardant and antimony trioxide as a flame retardant, and containing no metal oxide other than the antimony trioxide. Since the brominated flame retardant has a melting point of 110 ° C. or higher, the flame retardant is difficult to melt and volatilize when the flame retardant polyolefin resin composition is extruded. It is possible to prevent the flame retardant component from adhering and depositing by suppressing the occurrence of the flame retardant component in the mouth. Furthermore, the operation of removing the flame retardant component adhering to the die opening during molding is not required, and the effect that the mass production moldability is good can be obtained.
  • the wire protection material of the present invention is formed by using the above-described composition for wire protection material into a predetermined shape capable of protecting the wire, there is no risk of poor appearance due to adhesion of the flame retardant.
  • the melting point of brominated flame retardants is 110 ° C or higher, the wire protective material prevents degradation of polypropylene resin and degradation of heat resistance due to decomposition products generated when the molded product is heated. can do.
  • the electric wire protective material of this invention can suppress generation
  • the wire harness according to the present invention employs a configuration in which the periphery of a wire bundle in which a plurality of insulated wires are bundled is covered with the above-described wire protective material, thereby suppressing the formation of eyes and good mass production formability.
  • a wire harness excellent in appearance, heat resistance, flame retardancy and the like can be obtained.
  • the composition for electric wire protection materials of this embodiment is an example of the composition for electric wire protection materials used for shaping
  • the wire protective material composition can be composed of, for example, the following components (A) to (E).
  • A Polypropylene resin is used as the resin component, (B-1) brominated flame retardant, (B-2) anti-monium trioxide (B) flame retardant imparting agent, (C) copper as the additive component Harm inhibitors, (D) phenolic antioxidants, (E) phosphorus heat stabilizers, and the like are used.
  • the wire protective material composition of the present invention contains no metal oxide other than antimony trioxide.
  • brominated flame retardants and antimony trioxide are sometimes used in combination with metal oxides in this type of flame retardant composition.
  • the metal oxide include zinc oxide, aluminum oxide, magnesium oxide, and tin oxide.
  • the present invention can suppress the deposition and adhesion of a flame retardant such as a metal oxide around the die opening by using a composition that does not contain the metal oxide.
  • inorganic fillers such as magnesium hydroxide and aluminum hydroxide may be added to this type of flame retardant composition as a flame retardant.
  • the composition for wire protection material of the present invention preferably does not contain these inorganic fillers for the same reason as that for not adding the metal oxide.
  • the (A) polypropylene resin may be either block polypropylene or random polypropylene.
  • the molecular structure of polypropylene may be any of syndiotactic polypropylene, isotactic polypropylene, and atactic polypropylene.
  • the wire protective material composition may contain a resin other than the polypropylene resin as a resin component. Specifically, it can be added in consideration of ease of kneading of the resin and the additive. Specific examples include polyethylene, chlorinated polyethylene, ethylene-propylene rubber, and various elastomers.
  • polyethylene examples include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), and metallocene ultra low density polyethylene. It can be illustrated. These may be used alone or in combination.
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • metallocene ultra low density polyethylene metallocene ultra low density polyethylene
  • a flame retardant imparting agent (hereinafter sometimes referred to as a flame retardant) is a combination of a brominated flame retardant and antimony trioxide.
  • the blending amount of the flame retardant is preferably in the range of 1.5 to 15 parts by mass with respect to 100 parts by mass of polypropylene, which is the total amount of the brominated flame retardant and antimony trioxide. If the blending amount of the flame retardant imparting agent is less than 1.5 parts by mass, the flame retardancy may be insufficient, and if it exceeds 15 parts by mass, the heat aging resistance may be reduced.
  • the brominated flame retardant is not particularly limited as long as it has a melting point of 110 ° C. or higher, and can be used.
  • Brominated flame retardants having a melting point of 110 ° C. or higher include, for example, ethylene bis (pentabromodiphenyl) (melting point 350 ° C.), ethylene bistetrabromophthalimide (melting point 456 ° C.), TBBA-bis (2,3-dibromopropyl ether) (Melting point 117 ° C), hexabromobenzene (melting point 315 ° C), pentabromotoluene (melting point 288 ° C), hexabromocyclododecane (melting point 180 ° C), decabromodiphenyl ether (melting point 300 ° C), decabromodiphenylethane (melting point 345) ° C), tetrabromobisphenol A (melting point
  • antimony trioxide for example, antimony trioxide produced as a mineral can be pulverized and atomized. By using antimony trioxide in combination with a brominated flame retardant, the amount of brominated flame retardant used can be reduced.
  • the addition of the copper damage inhibitor prevents the polypropylene resin from deteriorating when the wire protective material comes into contact with the metal, and contributes to the improvement of the heat aging characteristics of the wire protective material.
  • Copper deterrence love uses a metal deactivator.
  • metal deactivators include 3- (N-salicyloyl) amino-1,2,4-triazole, 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxy). Phenyl) propionyl] propionohydrazide, decamethylene dicarboxylic acid disalicyloyl hydrazide and the like. .
  • the blending amount of the copper damage inhibitor is not particularly limited, but is preferably within a range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the polypropylene resin. If the blending amount of the copper damage inhibitor is less than 0.1 parts by mass, the polypropylene resin deterioration preventing effect may not be sufficiently obtained when it comes into contact with the metal, and if it exceeds 3 parts by mass, a die mouth is formed during extrusion molding. There is a risk that the copper damage preventive agent will be deposited on the surface.
  • the phenolic antioxidant is not particularly limited, and hindered phenolic, monophenolic, diphenolic, triphenolic, polyphenolic, and the like can be used. Of these, hindered phenol antioxidants are preferred.
  • hindered phenol antioxidant examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert).
  • the blending amount of the phenolic antioxidant is not particularly limited, but is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the polypropylene resin. If the blending amount of the antioxidant is less than 0.1 parts by mass, the polypropylene-based resin may be deteriorated due to oxidative degradation, and if it exceeds 3 parts by mass, the antioxidant will precipitate at the die mouth during extrusion molding. There is a risk of becoming.
  • the phosphorus-based heat stabilizer is a processing heat stabilizer and is used in combination with the above-mentioned phenolic antioxidant.
  • Examples of the phosphorus heat stabilizer include diphenylnonylphenyl phosphite, tristridecyl phosphite, and tris (2,4-di-tert-butylphenyl) phosphite.
  • the blending amount of the phosphorus-based heat stabilizer is not particularly limited, but is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the polypropylene resin. If the amount of the phosphorous heat stabilizer is less than 0.1 parts by mass, the polypropylene resin may be deteriorated due to oxidative degradation, and if it exceeds 3 parts by mass, the heat stabilizer will precipitate at the die mouth during extrusion molding. There is a risk that it will become a disgusting eye.
  • the blending ratio can be appropriately selected according to the type of resin, processing conditions, and the like.
  • the wire protective material composition may contain components other than the above components as long as the effects of the present invention are not impaired.
  • Specific examples of these components include additives such as colorants, antistatic agents, lubricants, and nucleating agents.
  • additives such as colorants, antistatic agents, lubricants, and nucleating agents.
  • a known material added to this type of polypropylene resin composition can be used.
  • the above-described components may be mixed by a known mixing method.
  • a known mixing method There are no particular limitations on the blending order, mixing method, and the like during mixing.
  • Specific mixing methods include, for example, commonly used kneaders such as a tumbler-type blender, a V-type blender, a Henschel mixer, a ribbon mixer, an extruder (single screw, twin screw), a Banbury mixer, a pressure kneader, and a roll.
  • kneaders such as a tumbler-type blender, a V-type blender, a Henschel mixer, a ribbon mixer, an extruder (single screw, twin screw), a Banbury mixer, a pressure kneader, and a roll.
  • the method of mixing by using is mentioned.
  • the electric wire protective material of the present invention can be manufactured by molding using the above-mentioned composition for electric wire protective material.
  • a corrugated tube is extruded by melting the composition for wire protection material at about 180 to 250 ° C. and continuously extruding it from a die port of a forming nozzle into a tube shape.
  • the said composition for electric wire protection materials when a composition is extruded, it can suppress that a flame retardant component accumulates around a die mouth and adheres to a corrugate.
  • the wire protection material of the present invention is formed by molding the wire into a predetermined shape capable of protecting the wire using the above-described composition for wire protection material.
  • the shape of the wire protection material is not particularly limited as long as it is a shape that can protect the wire or the bundle of wires.
  • the shape of the wire protection member is formed so as to cover the outer periphery of the wire bundle and to protect the internal wire bundle from the external environment or the like.
  • a corrugated tube is a specific shape of the wire protection material.
  • the corrugated tube can be produced, for example, by extruding a polyolefin-based resin composition as a tubular tubular product and then molding the corrugated tube into a bellows-shaped corrugated tube using a mold.
  • the wire harness of the present invention is one in which the periphery of an electric wire bundle in which a plurality of insulated electric wires are bundled is covered with an electric wire protective material formed using the composition for an electric wire protective material.
  • the wire bundle used for the wire harness should be a single wire bundle in which only insulated wires are bundled together or a mixed wire bundle in which insulated wires and other insulated wires are bundled together. Can do.
  • the number of wires included in the single wire bundle and the mixed wire bundle is not particularly limited.
  • the wire protection material and the wire harness using the composition for the wire protection material of the above form can be suitably used as a wire protection material for automobiles and a wire harness for automobiles that require long-term heat resistance and flame retardancy. It is.
  • test materials and manufacturers The test materials used in the examples and comparative examples are shown together with the manufacturer, product name, and the like.
  • B Flame retardancy imparting agent
  • B-1 Brominated flame retardant / brominated flame retardant 1, ethylene bis (pentabromodiphenyl), manufactured by Albemarle, trade name “SAYTEX 8010”, melting point 350 ° C. -Brominated flame retardant 2, ethylenebistetrabromophthalimide, manufactured by Albemarle, trade name “SAYTEX BT-93”, melting point 456 ° C. -Brominated flame retardant 3, TBBA-bis (2,3-dibromopropyl ether), manufactured by Tosoh Corporation, trade name “Frame Cut 121K”, melting point 117 ° C.
  • Bromine flame retardant 4 bis [3,5-dibromopropoxyphenyl)] sulfone, manufactured by Maruhishi Oil Chemical Co., Ltd., trade name “Nonen PR2”, melting point 40-60 ° C.
  • B-2 Antimony trioxide, manufactured by Nippon Seiko Co., Ltd., trade name “PATOX-CF”
  • C Copper damage inhibitor (metal deactivator) 2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide, manufactured by ADEKA, trade name “Adeka Stub CDA-1”, melting point 315-325 ° C.
  • Phenol-based antioxidant manufactured by BASF, trade name “IRGANOX1010”
  • E Phosphorus heat stabilizer: manufactured by BASF, trade name “IRGAFOS168”
  • Example 1 Each component of Examples and Comparative Examples shown in Table 1 was mixed at a kneading temperature of 220 ° C. using a twin-screw kneader, and then molded into pellets with a pelletizer, and each composition according to Examples and Comparative Examples. A product pellet was obtained. Then, using each of the obtained pellets, a dumbbell test piece and a corrugated tube were formed, and (1) Presence / absence of deposition of flame retardant, (2) Long-term heat resistance, and (3) Flame resistance evaluation test were performed. .
  • the preparation method of the test piece and the evaluation test method are as follows.
  • dumbbell specimen preparation method The dumbbell test piece was prepared by punching a pellet from a 140 mm ⁇ 140 mm ⁇ 1 mm sheet obtained by heating and compressing the pellet at 220 ° C. with a JIS No. 3 dumbbell mold.
  • the corrugated tube was formed by blow extrusion molding with a resin temperature of 220 ° C. and a corrugated tube having an inner diameter of 10 mm to a length of 200 mm.
  • OI oxygen index
  • Examples 1 to 3 use a brominated flame retardant having a melting point of 110 ° C. or higher, and do not contain a metal oxide other than antimony trioxide. There was no deposition or adhesion, long-term heat resistance was good, and flame retardancy was satisfactory and satisfactory. On the other hand, Comparative Example 1 uses a brominated flame retardant having a melting point of 40-60 ° C. and has flame retardancy. However, there is deposition and adhesion of the flame retardant and poor long-term heat resistance. Met.

Abstract

Provided are: a composition for electric wire protective materials, which is capable of preventing deposition and adhesion of a flame retardant on a die orifice during extrusion molding of a flame-retardant polyolefin resin composition, and which provides a molded article having good heat resistance and flame retardancy, while having excellent productivity; an electric wire protective material; and a wiring harness. This composition for electric wire protective materials is configured of a polypropylene resin composition which contains a polypropylene resin, and a bromine-based flame retardant and antimony trioxide that serve as a flame retardancy-imparting agent, said bromine-based flame retardant having a melting point of 110°C or more, and which does not contain any metal oxide other than antimony trioxide. This electric wire protective material is obtained by molding the composition into a predetermined shape that is capable of protecting an electric wire. This wiring harness is configured by covering the circumference of an electric wire bundle, which is obtained by bundling a plurality of insulated wires together, with this electric wire protective material.

Description

電線保護材用組成物、電線保護材及びワイヤーハーネスComposition for wire protection material, wire protection material and wire harness
　本発明は、例えば自動車等の車両部品、電気・電子機器部品等に用いられるコルゲートチューブ等の電線束を保護するための電線保護材、該電線保護材に用いられる電線保護材用組成物、及び前記電線保護材を用いたワイヤーハーネスに関するものである。 The present invention is, for example, a wire protection material for protecting a bundle of wires such as a corrugated tube used for vehicle parts such as automobiles, electrical / electronic equipment parts, etc., a composition for a wire protection material used for the wire protection material, and The present invention relates to a wire harness using the wire protective material.
　従来、自動車用電線の保護材として、ポリプロピレン等のポリオレフィンに難燃剤等を配合してなる難燃性ポリオレフィン系樹脂組成物を管状に押出成形して形成された難燃性コルゲートチューブが公知である（例えば特許文献１参照）。 Conventionally, a flame retardant corrugated tube formed by extruding a flame retardant polyolefin resin composition obtained by blending a flame retardant or the like into a polyolefin such as polypropylene is known as a protective material for automobile electric wires. (For example, refer to Patent Document 1).
　上記組成物としては、ポリオレフィン１００重量部に対して、２，２－ビス〔３，５－ジブロモ－４－（２，３－ジブロモプロピル）フェニル〕プロパンとトリス（２，３－ジブロモプロピル）イソシアヌレートとの重量比が８：２～４：６の難燃剤を２．５～３０重量部、三酸化アンチモンを０．５～２０重量部配合されている。 The composition includes 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyl) phenyl] propane and tris (2,3-dibromopropyl) isocyanate per 100 parts by weight of polyolefin. 2.5 to 30 parts by weight of a flame retardant having a weight ratio to nurate of 8: 2 to 4: 6 and 0.5 to 20 parts by weight of antimony trioxide are blended.
　また難燃性コルゲートチューブの難燃剤としては、上記臭素系難燃剤と三酸化アンチモン以外に、金属酸化物、金属水酸化物等が用いられる。 In addition to the brominated flame retardant and antimony trioxide, a metal oxide, a metal hydroxide, or the like is used as a flame retardant for the flame retardant corrugated tube.
特許第３２４０５９０号公報Japanese Patent No. 3240590
　上記難燃性ポリオレフィン系樹脂組成物をチューブ状に押出し成形して、難燃性コルゲートチューブを成形する場合、ダイス口に難燃剤の析出物が発生して、堆積、付着するという問題があった。この析出物は、目ヤニと呼ばれ、成形品に付着して外観不良となったり、更には成形品の耐熱性等の物性低下を招いてしまう。また目ヤニが発生した場合、ダイス口から取り除く作業が必要となり、生産性が低下するという問題があった。 When the flame retardant polyolefin resin composition is extruded into a tube shape to form a flame retardant corrugated tube, there is a problem that a flame retardant deposit is generated at the die mouth and is deposited and adhered. . This precipitate is called “eyes” and adheres to the molded product, resulting in a poor appearance, and further deteriorates physical properties such as heat resistance of the molded product. In addition, when the spear is generated, it is necessary to remove it from the die opening, resulting in a problem that productivity is lowered.
　本発明は上記事情に鑑みてなされたもので、本発明が解決しようとする課題は、難燃性のポリオレフィン系樹脂組成物を押出し成形する際に、ダイス口に難燃剤が付着、堆積するのを防止することが可能であり、生産性に優れ、成形品の耐熱性、難燃性が良好である電線保護材用組成物、電線保護材及びワイヤーハーネスを提供することにある。 The present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is that when a flame retardant polyolefin resin composition is extruded, a flame retardant adheres to and deposits on a die opening. An object of the present invention is to provide a composition for an electric wire protection material, an electric wire protection material, and a wire harness that are capable of preventing the occurrence of heat resistance and excellent in heat resistance and flame retardancy of a molded product.
　上記課題を解決するために本発明に係る電線保護材用組成物は、
　ポリプロピレン系樹脂と、難燃性付与剤として臭素系難燃剤及び三酸化アンチモンを含み、前記三酸化アンチモン以外の金属酸化物を含有しないポリプロピレン系樹脂組成物から構成され、
　前記臭素系難燃剤の融点が１１０℃以上であることをことを要旨とするものである。 In order to solve the above problems, the wire protective material composition according to the present invention,
It comprises a polypropylene resin and a polypropylene resin composition containing a brominated flame retardant and antimony trioxide as a flame retardant, and containing no metal oxide other than antimony trioxide,
The gist is that the brominated flame retardant has a melting point of 110 ° C. or higher.
　上記電線保護材用組成物は、更に銅害防止剤が配合されていることが好ましい。 It is preferable that the composition for an electric wire protective material further contains a copper damage inhibitor.
　上記電線保護材用組成物は、更にフェノール系酸化防止剤が配合されていることが好ましい。 It is preferable that the wire protective material composition further contains a phenolic antioxidant.
　上記電線保護材用組成物は、更にリン系熱安定剤が配合されていることが好ましい。 It is preferable that the wire protective material composition further contains a phosphorus-based heat stabilizer.
　本発明に係る電線保護材は、上記の電線保護材用組成物を用いて電線を保護可能な所定の形状に成形してなることを要旨とするものである。 The gist of the wire protection material according to the present invention is that the wire is molded into a predetermined shape capable of protecting the wire using the composition for wire protection material.
　本発明に係るワイヤーハーネスは、上記の電線保護材用組成物を用いて形成された電線保護材により、複数本の絶縁電線が束ねられた電線束の周囲が被覆されていることを要旨とするものである。 The summary of the wire harness according to the present invention is that a wire bundle in which a plurality of insulated wires are bundled is covered with a wire protector formed using the above-described composition for a wire protector. Is.
　本発明に係る電線保護材用組成物は、ポリプロピレン系樹脂と、難燃性付与剤として臭素系難燃剤及び三酸化アンチモンを含み、前記三酸化アンチモン以外の金属酸化物を含有しないポリプロピレン系樹脂組成物から構成され、前記臭素系難燃剤の融点が１１０℃以上であることにより、難燃性のポリオレフィン系樹脂組成物を押出し成形する際に、難燃剤が溶融、揮発しにくくなるために、ダイス口に難燃剤成分が発生するのを抑制して、難燃剤の付着、堆積を防止することが可能である。更に、成形の際にダイス口に付着した難燃剤成分を取り除く作業等が不要となって、量産成形性が良好であるといった効果が得られる。 The composition for an electric wire protective material according to the present invention comprises a polypropylene resin and a polypropylene resin composition containing a bromine-based flame retardant and antimony trioxide as a flame retardant, and containing no metal oxide other than the antimony trioxide. Since the brominated flame retardant has a melting point of 110 ° C. or higher, the flame retardant is difficult to melt and volatilize when the flame retardant polyolefin resin composition is extruded. It is possible to prevent the flame retardant component from adhering and depositing by suppressing the occurrence of the flame retardant component in the mouth. Furthermore, the operation of removing the flame retardant component adhering to the die opening during molding is not required, and the effect that the mass production moldability is good can be obtained.
　また本発明電線保護材は、上記電線保護材用組成物を用いて電線を保護可能な所定の形状に成形してなるものであるから、難燃剤の付着による外観不良の虞が無い。また電線保護材は、臭素系難燃剤の融点が１１０℃以上であるから、成形品が加熱された際に生成する分解生成物によってポリプロピレン系樹脂が劣化して、耐熱性が低下するのを防止することができる。また本発明の電線保護材は、難燃剤の付着による目ヤニの発生を抑制することが可能であるから、量産成形性が良好であるという効果が得られる。 Moreover, since the wire protection material of the present invention is formed by using the above-described composition for wire protection material into a predetermined shape capable of protecting the wire, there is no risk of poor appearance due to adhesion of the flame retardant. In addition, since the melting point of brominated flame retardants is 110 ° C or higher, the wire protective material prevents degradation of polypropylene resin and degradation of heat resistance due to decomposition products generated when the molded product is heated. can do. Moreover, since the electric wire protective material of this invention can suppress generation | occurrence | production of the eye mist by adhesion of a flame retardant, the effect that mass-production moldability is favorable is acquired.
　本発明のワイヤーハーネスは、上記の電線保護材により、複数本の絶縁電線が束ねられた電線束の周囲が被覆されている構成を採用したことにより、目ヤニを抑制して量産成形性が良好で、外観及び耐熱性、難燃性等に優れたワイヤーハーネスが得られる。 The wire harness according to the present invention employs a configuration in which the periphery of a wire bundle in which a plurality of insulated wires are bundled is covered with the above-described wire protective material, thereby suppressing the formation of eyes and good mass production formability. Thus, a wire harness excellent in appearance, heat resistance, flame retardancy and the like can be obtained.
　以下、本発明の実施形態について詳細に説明する。本実施形態の電線保護材用組成物は、難燃剤が添加された自動車用コルゲートチューブの成形に用いられる電線保護材用組成物の例である。電線保護材用組成物は、例えば、下記の（Ａ）～（Ｅ）成分から構成することができる。 Hereinafter, embodiments of the present invention will be described in detail. The composition for electric wire protection materials of this embodiment is an example of the composition for electric wire protection materials used for shaping | molding of the corrugated tube for motor vehicles to which the flame retardant was added. The wire protective material composition can be composed of, for example, the following components (A) to (E).
　樹脂成分として（Ａ）ポリプロピレン系樹脂が用いられ、添加剤成分として（Ｂ－１）臭素系難燃剤、（Ｂ－２）三酸化アンチモン等の（Ｂ）難燃性付与剤、（Ｃ）銅害防止剤、（Ｄ）フェノール系酸化防止剤、（Ｅ）リン系熱安定剤等が用いられる。 (A) Polypropylene resin is used as the resin component, (B-1) brominated flame retardant, (B-2) anti-monium trioxide (B) flame retardant imparting agent, (C) copper as the additive component Harm inhibitors, (D) phenolic antioxidants, (E) phosphorus heat stabilizers, and the like are used.
　本発明の電線保護材用組成物は、三酸化アンチモン以外の金属酸化物を含まない。従来、この種の難燃性組成物には、臭素系難燃剤と三酸化アンチモンを金属酸化物と併用する場合がある。上記金属酸化物は、例えば、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化錫等である。しかし、これらの金属酸化物を添加すると、目ヤニ発生を引き起しやすいということが判った。金属酸化物は組成物中で相対的に比重が大きいため、ダイス口で外側に押し出され、堆積、付着するものと考えられる。そこで、本発明は、上記金属酸化物を含有しない組成物とすることで、ダイス口の周囲に、これら金属酸化物等の難燃剤が堆積、付着するのを抑制可能である。 The wire protective material composition of the present invention contains no metal oxide other than antimony trioxide. Conventionally, brominated flame retardants and antimony trioxide are sometimes used in combination with metal oxides in this type of flame retardant composition. Examples of the metal oxide include zinc oxide, aluminum oxide, magnesium oxide, and tin oxide. However, it has been found that the addition of these metal oxides tends to cause the generation of eyes. Since the metal oxide has a relatively large specific gravity in the composition, it is considered that the metal oxide is pushed out to the outside through a die port, and is deposited and adhered. Therefore, the present invention can suppress the deposition and adhesion of a flame retardant such as a metal oxide around the die opening by using a composition that does not contain the metal oxide.
　また、この種の難燃性組成物には、上記金属酸化物以外に、難燃剤として水酸化マグネシウム、水酸化アルミニウム等の無機充填剤が添加される場合がある。本発明電線保護材用組成物は、上記金属酸化物を添加しない理由と同様の理由から、これらの無機充填剤を含有しないことが好ましい。 In addition to the above metal oxides, inorganic fillers such as magnesium hydroxide and aluminum hydroxide may be added to this type of flame retardant composition as a flame retardant. The composition for wire protection material of the present invention preferably does not contain these inorganic fillers for the same reason as that for not adding the metal oxide.
 
　以下、電線保護材用組成物の各成分について説明する。上記（Ａ）ポリプロピレン系樹脂は、ブロックポリプロピレン、ランダムポリプロピレンのいずれでも良い。またポリプロピレンは、その分子構造は、シンジオタクチックポリプロピレン、アイソタクチックポリプロピレン、アタクチックポリプロピレンのいずれでも良い。
Hereinafter, each component of the composition for wire protective materials will be described. The (A) polypropylene resin may be either block polypropylene or random polypropylene. The molecular structure of polypropylene may be any of syndiotactic polypropylene, isotactic polypropylene, and atactic polypropylene.
　電線保護材用組成物は、樹脂成分として、上記ポリプロピレン系樹脂以外の樹脂を添加してもよい。具体的には、樹脂および添加剤の混練のしやすさを考慮して、添加することができる。具体的には、ポリエチレン、塩素化ポリエチレン、エチレン‐プロピレンゴム、各種エラストマー等が挙げられる。 The wire protective material composition may contain a resin other than the polypropylene resin as a resin component. Specifically, it can be added in consideration of ease of kneading of the resin and the additive. Specific examples include polyethylene, chlorinated polyethylene, ethylene-propylene rubber, and various elastomers.
　ポリエチレンとしては、高密度ポリエチレン（ＨＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、超低密度ポリエチレン（ＶＬＤＰＥ）、メタロセン超低密度ポリエチレンなどを例示することができる。これらは単独で用いてもよいし、併用しても良い。 Examples of polyethylene include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), and metallocene ultra low density polyethylene. It can be illustrated. These may be used alone or in combination.
　（Ｂ）難燃性付与剤（以下、難燃剤ということもある）は、臭素系難燃剤と三酸化アンチモンを併用する。臭素系難燃剤と三酸化アンチモンの配合比率は、通常、質量比で、臭素系難燃剤：三酸化アンチモン＝１：４～４：１の範囲が、添加効率の点から好ましい。 (B) A flame retardant imparting agent (hereinafter sometimes referred to as a flame retardant) is a combination of a brominated flame retardant and antimony trioxide. The blending ratio of brominated flame retardant to antimony trioxide is usually preferably in the range of bromine-based flame retardant: antimony trioxide = 1: 4 to 4: 1 in terms of addition efficiency.
　難燃剤の配合量は、ポリプロピレン１００質量部に対し、臭素系難燃剤と三酸化アンチモンの合計量で、１．５～１５質量部の範囲内であることが好ましい。難燃性付与剤の配合量が、１．５質量部未満では難燃性が不十分となる虞があり、１５質量部を超えると耐熱老化性が低下する虞がある。 The blending amount of the flame retardant is preferably in the range of 1.5 to 15 parts by mass with respect to 100 parts by mass of polypropylene, which is the total amount of the brominated flame retardant and antimony trioxide. If the blending amount of the flame retardant imparting agent is less than 1.5 parts by mass, the flame retardancy may be insufficient, and if it exceeds 15 parts by mass, the heat aging resistance may be reduced.
　（Ｂ‐１）臭素系難燃剤は、融点が１１０℃以上のものであれば特に限定されず、用いることができる。融点が１１０℃以上の臭素系難燃剤は、例えば、エチレンビス（ペンタブロモジフェニル）（融点３５０℃）、エチレンビステトラブロモフタルイミド（融点４５６℃）、ＴＢＢＡ－ビス（２，３‐ジブロモプロピルエーテル）（融点１１７℃）、ヘキサブロモベンゼン（融点３１５℃）、ペンタブロモトルエン（融点２８８℃）、ヘキサブロモシクロドデカン（融点１８０℃）、デカブロモジフェニルエーテル（融点３００℃）、デカブロモジフェニルエタン（融点３４５℃）、テトラブロモビスフェノールＡ（融点１８１℃）、テトラブロモビスフェノールＡビスアリルエーテル（融点１１５℃）、テトラブロモビスフェノールＡビスエトキシレート（融点１１５℃）、テトラデカブロモジフェノキシベンゼン（融点３８０℃）、テトラブロモ無水フタル酸（融点２８０℃）等が挙げられる。 (B-1) The brominated flame retardant is not particularly limited as long as it has a melting point of 110 ° C. or higher, and can be used. Brominated flame retardants having a melting point of 110 ° C. or higher include, for example, ethylene bis (pentabromodiphenyl) (melting point 350 ° C.), ethylene bistetrabromophthalimide (melting point 456 ° C.), TBBA-bis (2,3-dibromopropyl ether) (Melting point 117 ° C), hexabromobenzene (melting point 315 ° C), pentabromotoluene (melting point 288 ° C), hexabromocyclododecane (melting point 180 ° C), decabromodiphenyl ether (melting point 300 ° C), decabromodiphenylethane (melting point 345) ° C), tetrabromobisphenol A (melting point 181 ° C), tetrabromobisphenol A bisallyl ether (melting point 115 ° C), tetrabromobisphenol A bisethoxylate (melting point 115 ° C), tetradecabromodiphenoxybenzene (melting point 380 ° C) Tetra Romo phthalic anhydride (mp 280 ° C.), and the like.
　（Ｂ‐２）三酸化アンチモンは、例えば、鉱物として産出される三酸化アンチモンを粉砕処理して微粒化したものを用いることができる。三酸化アンチモンを臭素系難燃剤と併用することで、臭素系難燃剤の使用量を減らすことができる。 (B-2) As antimony trioxide, for example, antimony trioxide produced as a mineral can be pulverized and atomized. By using antimony trioxide in combination with a brominated flame retardant, the amount of brominated flame retardant used can be reduced.
　（Ｃ）銅害防止剤の添加は、電線保護材が金属と接触した際にポリプロピレン系樹脂が劣化するのを防止して、電線保護材の耐熱老化特性の向上に寄与する。銅害防止愛は金属不活性化剤が用いられる。金属不活性化剤としては、例えば、３－（Ｎ－サリチロイル）アミノ－１，２，４－トリアゾール、２’，３－ビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニル］プロピオノヒドラジド、デカメチレンジカルボン酸ジサリチロイルヒドラジド等が挙げられる。
。 (C) The addition of the copper damage inhibitor prevents the polypropylene resin from deteriorating when the wire protective material comes into contact with the metal, and contributes to the improvement of the heat aging characteristics of the wire protective material. Copper deterrence love uses a metal deactivator. Examples of metal deactivators include 3- (N-salicyloyl) amino-1,2,4-triazole, 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxy). Phenyl) propionyl] propionohydrazide, decamethylene dicarboxylic acid disalicyloyl hydrazide and the like.
.
　（Ｃ）銅害防止剤の配合量は、特に限定されないが、ポリプロピレン系樹脂１００質量部に対し、０．１～３質量部の範囲内であるのが好ましい。銅害防止剤の配合量が０．１質量部未満では金属と接触した際のポリプロピレン系樹脂劣化防止効果が十分に得られない虞があり、３質量部を超えると押出し成型の際にダイス口に銅害防止剤が析出して目ヤニとなる虞がある。 (C) The blending amount of the copper damage inhibitor is not particularly limited, but is preferably within a range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the polypropylene resin. If the blending amount of the copper damage inhibitor is less than 0.1 parts by mass, the polypropylene resin deterioration preventing effect may not be sufficiently obtained when it comes into contact with the metal, and if it exceeds 3 parts by mass, a die mouth is formed during extrusion molding. There is a risk that the copper damage preventive agent will be deposited on the surface.
　（Ｄ）フェノール系酸化防止剤としては、特に限定されないが、ヒンダードフェノール系、モノフェノール系、ジフェノール系、トリフェノール系、及びポリフェノール系等を用いることができる。中でもヒンダードフェノール系酸化防止剤が好ましい。 (D) The phenolic antioxidant is not particularly limited, and hindered phenolic, monophenolic, diphenolic, triphenolic, polyphenolic, and the like can be used. Of these, hindered phenol antioxidants are preferred.
　上記ヒンダードフェノール系酸化防止剤としては、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオンアミド）、ベンゼンプロパン酸，３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシ，Ｃ７－Ｃ９側鎖アルキルエステル、２，４－ジメチル－６－（１－メチルペンタデシル）フェノール、ジエチル［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ホスフォネート、３，３’，３”，５，５’５”－ヘキサ－ｔｅｒｔ－ブチル－ａ，ａ’，ａ”－（メシチレン－２，４，６－トリイル）トリ－ｐ－クレゾール、カルシウムジエチルビス［［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ホスフォネート］、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、エチレンビス（オキシエチレン）ビス［３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート］、ヘキサメチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、１，３，５－トリス［（４－ｔｅｒｔ－ブチル－３－ヒドロキシ－２，６－キシリル）メチル］－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、２，６－ｔｅｒｔ－ブチル－４－（４，６－ビス（オクチルチオ）－１，３，５－トリアジン－２－イルアミノ）フェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、３，９－ビス［２－（３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）－プロピノキ）－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ（５，５）ウンデカン等が挙げられる。これらは１種単独で用いても２種以上を併用してもいずれでも良い。 Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert). -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenylpropionamide), benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1- Methylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5′5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6 -Triyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl)- o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-tria -2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) Phenol, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propiyl NOKI) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5,5) undecane. These may be used alone or in combination of two or more.
　（Ｄ）フェノール系酸化防止剤の配合量は、特に限定されないが、ポリプロピレン系樹脂１００質量部に対し、０．１～３質量部の範囲内であるのが好ましい。酸化防止剤の配合量が０．１質量部未満では酸化劣化によりポリプロピレン系樹脂が劣化する虞があり、３質量部を超えると押出し成型の際にダイス口に酸化防止剤が析出して目ヤニとなる虞がある。 (D) The blending amount of the phenolic antioxidant is not particularly limited, but is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the polypropylene resin. If the blending amount of the antioxidant is less than 0.1 parts by mass, the polypropylene-based resin may be deteriorated due to oxidative degradation, and if it exceeds 3 parts by mass, the antioxidant will precipitate at the die mouth during extrusion molding. There is a risk of becoming.
　（Ｅ）リン系熱安定剤は、加工熱安定剤であり、上記フェノール系酸化防止剤と併用される。上記リン系熱安定剤としては、ジフェニルノニルフェニルホスファイト、トリストリデシルホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト等が挙げられる。 (E) The phosphorus-based heat stabilizer is a processing heat stabilizer and is used in combination with the above-mentioned phenolic antioxidant. Examples of the phosphorus heat stabilizer include diphenylnonylphenyl phosphite, tristridecyl phosphite, and tris (2,4-di-tert-butylphenyl) phosphite.
　（Ｅ）リン系熱安定剤の配合量は、特に限定されないが、ポリプロピレン系樹脂１００質量部に対し、０．１～３質量部の範囲内であるのが好ましい。リン系熱安定剤の配合量が、０．１質量部未満では酸化劣化によりポリプロピレン系樹脂が劣化する虞があり、３質量部を超えると押出し成型の際にダイス口に熱安定剤が析出して目ヤニとなる虞がある。 (E) The blending amount of the phosphorus-based heat stabilizer is not particularly limited, but is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the polypropylene resin. If the amount of the phosphorous heat stabilizer is less than 0.1 parts by mass, the polypropylene resin may be deteriorated due to oxidative degradation, and if it exceeds 3 parts by mass, the heat stabilizer will precipitate at the die mouth during extrusion molding. There is a risk that it will become a disgusting eye.
　上記フェノール系酸化防止剤とリン系熱安定剤の配合割合は、フェノール系酸化防止剤：リン系熱安定剤＝１：５～５：１の範囲内が好ましい。配合割合は、樹脂の種類や加工条件等に応じて、適宜選択することができる。 The blending ratio of the phenolic antioxidant and the phosphorus heat stabilizer is preferably in the range of phenolic antioxidant: phosphorus heat stabilizer = 1: 5 to 5: 1. The blending ratio can be appropriately selected according to the type of resin, processing conditions, and the like.
　電線保護材用組成物は、本発明の効果を損なわない範囲で、上記成分以外の成分を含有していてもよい。これらの成分として、具体的には、着色剤、帯電防止剤、滑剤、核剤等の添加剤が挙げられる。上記添加剤は、この種のポリプロピレン系樹脂組成物に添加される公知の材料が使用できる。 The wire protective material composition may contain components other than the above components as long as the effects of the present invention are not impaired. Specific examples of these components include additives such as colorants, antistatic agents, lubricants, and nucleating agents. As the additive, a known material added to this type of polypropylene resin composition can be used.
　本発明の電線保護材用組成物を調製するには、上記の各成分を公知の混合方法で混合すればよい。混合の際の配合順序、混合方法などは特に限定されない。具体的な混合方法としては、例えば、タンブラー式ブレンダー、Ｖ型ブレンダー、ヘンシェルミキサー、リボンミキサー、押出機（単軸、二軸）、バンバリミキサー、加圧ニーダー、ロールなどの通常用いられる混練機を用いて混合する方法等が挙げられる。 In order to prepare the wire protective material composition of the present invention, the above-described components may be mixed by a known mixing method. There are no particular limitations on the blending order, mixing method, and the like during mixing. Specific mixing methods include, for example, commonly used kneaders such as a tumbler-type blender, a V-type blender, a Henschel mixer, a ribbon mixer, an extruder (single screw, twin screw), a Banbury mixer, a pressure kneader, and a roll. The method of mixing by using is mentioned.
　本発明の電線保護材は、上記電線保護材用組成物を用いて成形することで製造可能である。例えばコルゲートチューブは、上記電線保護材用組成物を、１８０～２５０℃程度で溶融させて、成形ノズルのダイス口からチューブ状に連続的に押出して押出し成形を行う。上記電線保護材用組成物を用いることで、組成物が押し出される際に、ダイス口周囲に難燃剤成分が堆積してコルゲートに付着するのを抑制することができる。 The electric wire protective material of the present invention can be manufactured by molding using the above-mentioned composition for electric wire protective material. For example, a corrugated tube is extruded by melting the composition for wire protection material at about 180 to 250 ° C. and continuously extruding it from a die port of a forming nozzle into a tube shape. By using the said composition for electric wire protection materials, when a composition is extruded, it can suppress that a flame retardant component accumulates around a die mouth and adheres to a corrugate.
　本発明の電線保護材は、上記の電線保護材用組成物を用いて電線を保護可能な所定の形状に成形してなるものである。電線保護材の形状は、特に限定されず、電線、或いは電線束を保護可能な形状であればよい。電線保護材の形状としては、電線束の外周を覆い、内部の電線束を外部環境等から保護する役割を有するように形成されている。 The wire protection material of the present invention is formed by molding the wire into a predetermined shape capable of protecting the wire using the above-described composition for wire protection material. The shape of the wire protection material is not particularly limited as long as it is a shape that can protect the wire or the bundle of wires. The shape of the wire protection member is formed so as to cover the outer periphery of the wire bundle and to protect the internal wire bundle from the external environment or the like.
　具体的な電線保護材の形状としてコルゲートチューブが挙げられる。コルゲートチューブの製造は、例えばポリオレフィン系樹脂組成物をチューブ状の管状製品として押し出した後、金型により蛇腹状のコルゲートチューブに成形することができる。 A corrugated tube is a specific shape of the wire protection material. The corrugated tube can be produced, for example, by extruding a polyolefin-based resin composition as a tubular tubular product and then molding the corrugated tube into a bellows-shaped corrugated tube using a mold.
　本発明のワイヤーハーネスは、上記の電線保護材用組成物を用いて形成された電線保護材により、複数本の絶縁電線が束ねられた電線束の周囲が被覆されているものである。 The wire harness of the present invention is one in which the periphery of an electric wire bundle in which a plurality of insulated electric wires are bundled is covered with an electric wire protective material formed using the composition for an electric wire protective material.
　ワイヤーハーネスに用いられる電線束は、絶縁電線のみがひとまとまりに束ねられた単独電線束、あるいは、絶縁電線と他の絶縁電線とが混在状態でひとまとまりに束ねられた混在電線束等を用いることができる。単独電線束及び混在電線束に含まれる電線本数は、特に限定されるものではない。 The wire bundle used for the wire harness should be a single wire bundle in which only insulated wires are bundled together or a mixed wire bundle in which insulated wires and other insulated wires are bundled together. Can do. The number of wires included in the single wire bundle and the mixed wire bundle is not particularly limited.
　上記形態の電線保護材用組成物を用いた電線保護材及びワイヤーハーネスは、長期耐熱性、難燃性が要求される、自動車用電線保護材及び自動車用ワイヤーハーネスとして好適に利用することが可能である。 The wire protection material and the wire harness using the composition for the wire protection material of the above form can be suitably used as a wire protection material for automobiles and a wire harness for automobiles that require long-term heat resistance and flame retardancy. It is.
　以下、本発明の実施例、比較例を示す。尚、本発明はこれら実施例によって限定されるものではない。 Hereinafter, examples of the present invention and comparative examples will be shown. The present invention is not limited to these examples.
[供試材料及び製造元等]
　実施例及び比較例において使用した供試材料を製造元、商品名等と共に示す。 [Test materials and manufacturers]
The test materials used in the examples and comparative examples are shown together with the manufacturer, product name, and the like.
（Ａ）ポリプロピレン
・ブロックＰＰ、プライムポリマー社製、商品名「Ｊ３５６ＨＰ」 (A) Polypropylene block PP, manufactured by Prime Polymer Co., Ltd., trade name “J356HP”
（Ｂ）難燃性付与剤
（Ｂ‐１）臭素系難燃剤
・臭素系難燃剤１、エチレンビス(ペンタブロモジフェニル)、アルベマール社製、商品名「ＳＡＹＴＥＸ８０１０」、融点３５０℃
・臭素系難燃剤２、エチレンビステトラブロモフタルイミド、アルベマール社製、商品名「ＳＡＹＴＥＸ　ＢＴ‐９３」、融点４５６℃
・臭素系難燃剤３、ＴＢＢＡ‐ビス(２，３‐ジブロモプロピルエーテル)、東ソー社製、商品名「フレームカット　１２１Ｋ」、融点１１７℃
・臭素系難燃剤４、ビス［３，５‐ジブロモプロポキシフェニル)］スルフォン、丸菱油化工業社製、商品名「ノンネンＰＲ２」、融点４０‐６０℃
（Ｂ‐２）三酸化アンチモン、日本精鉱社製、商品名「ＰＡＴＯＸ‐ＣＦ」
（Ｃ）銅害防止剤（金属不活性化剤）
・２‐ヒドロキシ‐Ｎ‐１Ｈ‐１，２，４‐トリアゾール‐３‐イルベンズアミド、ＡＤＥＫＡ社製、商品名「アデカスタブＣＤＡ－１」、融点３１５‐３２５℃
（Ｄ）フェノール系酸化防止剤：ＢＡＳＦ社製、商品名「ＩＲＧＡＮＯＸ１０１０」
（Ｅ）リン系熱安定剤：ＢＡＳＦ社製、商品名「ＩＲＧＡＦＯＳ１６８」 (B) Flame retardancy imparting agent (B-1) Brominated flame retardant / brominated flame retardant 1, ethylene bis (pentabromodiphenyl), manufactured by Albemarle, trade name “SAYTEX 8010”, melting point 350 ° C.
-Brominated flame retardant 2, ethylenebistetrabromophthalimide, manufactured by Albemarle, trade name “SAYTEX BT-93”, melting point 456 ° C.
-Brominated flame retardant 3, TBBA-bis (2,3-dibromopropyl ether), manufactured by Tosoh Corporation, trade name “Frame Cut 121K”, melting point 117 ° C.
Bromine flame retardant 4, bis [3,5-dibromopropoxyphenyl)] sulfone, manufactured by Maruhishi Oil Chemical Co., Ltd., trade name “Nonen PR2”, melting point 40-60 ° C.
(B-2) Antimony trioxide, manufactured by Nippon Seiko Co., Ltd., trade name “PATOX-CF”
(C) Copper damage inhibitor (metal deactivator)
2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide, manufactured by ADEKA, trade name “Adeka Stub CDA-1”, melting point 315-325 ° C.
(D) Phenol-based antioxidant: manufactured by BASF, trade name “IRGANOX1010”
(E) Phosphorus heat stabilizer: manufactured by BASF, trade name “IRGAFOS168”
　以下、実施例、比較例の評価試験方法について説明する。表１に示す実施例、比較例の各成分を、二軸混練機を用いて、混練温度２２０℃にて混合した後、ペレタイザーにてペレット状に成形して実施例、比較例に係る各組成物のペレットを得た。次いで得られた各ペレットを用い、ダンベル試験片及びコルゲートチューブを成形して、（１）難燃剤の堆積付着の有無、（２）長期耐熱性、（３）難燃性の評価試験を行った。試験片の作成方法と、評価試験方法は下記の通りである。 Hereinafter, evaluation test methods of Examples and Comparative Examples will be described. Each component of Examples and Comparative Examples shown in Table 1 was mixed at a kneading temperature of 220 ° C. using a twin-screw kneader, and then molded into pellets with a pelletizer, and each composition according to Examples and Comparative Examples. A product pellet was obtained. Then, using each of the obtained pellets, a dumbbell test piece and a corrugated tube were formed, and (1) Presence / absence of deposition of flame retardant, (2) Long-term heat resistance, and (3) Flame resistance evaluation test were performed. . The preparation method of the test piece and the evaluation test method are as follows.
［ダンベル試験片作成方法］
　上記ダンベル試験片は、ペレットを２２０℃で加熱圧縮して得られた１４０ｍｍ×１４０ｍｍ×１ｍｍのシートからＪＩＳ３号ダンベル型で打ち抜いて作成した。 [Dumbell specimen preparation method]
The dumbbell test piece was prepared by punching a pellet from a 140 mm × 140 mm × 1 mm sheet obtained by heating and compressing the pellet at 220 ° C. with a JIS No. 3 dumbbell mold.
［コルゲートチューブ成形方法］
　上記コルゲートチューブは、樹脂温度２２０℃、ブロー押出成形で、内径１０ｍｍのコルゲートチューブを２００ｍｍの長さに成形した。 [Corrugated tube forming method]
The corrugated tube was formed by blow extrusion molding with a resin temperature of 220 ° C. and a corrugated tube having an inner diameter of 10 mm to a length of 200 mm.
（１）難燃剤の堆積、付着の有無の試験方法
　電線保護材用組成物を横型コルゲーターで押出成形した時に難燃剤が堆積して付着したかどうかを観察した。難燃剤の付着が見られた場合を有とし、付着が見られなかった場合を無として評価した。 (1) Test method for presence / absence of deposition and adhesion of flame retardant It was observed whether or not the flame retardant was deposited and adhered when the wire protective material composition was extruded using a horizontal corrugator. The case where the adhesion of the flame retardant was observed was evaluated as “Yes” and the case where the adhesion was not observed was evaluated as “No”.
（２）長期耐熱性の試験方法
　成形したコルゲートチューブの内部に、電線、編組線を通し、コルゲートチューブの両端をＥＰＤＭゴムで密封し、１５０℃‐１５０時間加熱処理を行った後、コルゲートチューブの割れの有無を観察した。割れが無かった場合を良好（○）とし、割れがあった場合を不良（×）とした。 (2) Test method for long-term heat resistance Wires and braided wires are passed through the molded corrugated tube, both ends of the corrugated tube are sealed with EPDM rubber, and after heat treatment at 150 ° C. for 150 hours, the corrugated tube The presence or absence of cracks was observed. The case where there was no crack was defined as good (◯), and the case where there was a crack was defined as defective (×).
（３）難燃性の試験方法
　厚さ１ｍｍのＪＩＳ３号ダンベル試験片を用いて、ＪＩＳ　Ｋ　７２０１に準拠して、酸素指数（oxygen index：ＯＩ）を測定した。試験片に点火してから４秒以内に消炎する最大酸素濃度を測定して酸素指数とした。ＯＩが２２以上であれば、難燃性を満足できると判断した。 (3) Flame Retardancy Test Method An oxygen index (OI) was measured according to JIS K 7201 using a JIS No. 3 dumbbell test piece having a thickness of 1 mm. The maximum oxygen concentration that extinguishes within 4 seconds after the test piece was ignited was measured as an oxygen index. If OI was 22 or more, it was judged that the flame retardancy could be satisfied.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１～３は、融点が１１０℃以上の臭素系難燃剤を用いたものであり、三酸化アンチモン以外の金属酸化物を含有しないものであるから、難燃剤の堆積、付着がなく、長期耐熱性が良好であり、難燃性も十分、満足するものであった。これに対し、比較例１は融点が４０‐６０℃の臭素系難燃剤を用いたものであり、難燃性を有するものであるが、難燃剤の堆積、付着が有り、長期耐熱性も不良であった。 As shown in Table 1, Examples 1 to 3 use a brominated flame retardant having a melting point of 110 ° C. or higher, and do not contain a metal oxide other than antimony trioxide. There was no deposition or adhesion, long-term heat resistance was good, and flame retardancy was satisfactory and satisfactory. On the other hand, Comparative Example 1 uses a brominated flame retardant having a melting point of 40-60 ° C. and has flame retardancy. However, there is deposition and adhesion of the flame retardant and poor long-term heat resistance. Met.
　以上、本発明の実施の形態について詳細に説明したが、本発明は上記実施の形態に何ら限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の改変が可能である。 The embodiments of the present invention have been described in detail above, but the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention.

Claims (6)

  1. 　ポリプロピレン系樹脂と、難燃性付与剤として臭素系難燃剤及び三酸化アンチモンを含み、前記三酸化アンチモン以外の金属酸化物を含有しないポリプロピレン系樹脂組成物から構成され、
    　前記臭素系難燃剤の融点が１１０℃以上であることを特徴とする電線保護材用組成物。     It comprises a polypropylene resin and a polypropylene resin composition containing a brominated flame retardant and antimony trioxide as a flame retardant, and containing no metal oxide other than antimony trioxide,
    The composition for a wire protective material, wherein the brominated flame retardant has a melting point of 110 ° C or higher.
  2. 　更に銅害防止剤が配合されていることを特徴とする請求項１に記載の電線保護材用組成物。 Furthermore, the copper damage prevention agent is mix | blended, The composition for electric wire protection materials of Claim 1 characterized by the above-mentioned.
  3. 　更にフェノール系酸化防止剤が配合されていることを特徴とする請求項１又は２に記載の電線保護材用組成物。 Furthermore, the phenolic antioxidant is mix | blended, The composition for electric wire protection materials of Claim 1 or 2 characterized by the above-mentioned.
  4. 　更にリン系熱安定剤が配合されていることを特徴とする請求項１～３のいずれか１項に記載の電線保護材用組成物。 The composition for a wire protective material according to any one of claims 1 to 3, further comprising a phosphorus-based heat stabilizer.
  5. 　請求項１～４のいずれか１項に記載の電線保護材用組成物を用いて電線を保護可能な所定の形状に成形してなることを特徴とする電線保護材。 An electric wire protection material, which is formed by using the composition for electric wire protection material according to any one of claims 1 to 4 into a predetermined shape capable of protecting an electric wire.
  6. 　請求項１～４のいずれか１項に記載の電線保護材用組成物を用いて形成された電線保護材により、複数本の絶縁電線が束ねられた電線束の周囲が被覆されていることを特徴とするワイヤーハーネス。
          A wire bundle formed by using the wire protective material composition according to any one of claims 1 to 4 covers a wire bundle in which a plurality of insulated wires are bundled. A characteristic wire harness.
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JPH07186293A (en) * 1993-12-27 1995-07-25 Tokuyama Corp Flame retardant corrugated tube
JPH08120117A (en) * 1994-10-26 1996-05-14 Dai Ichi Kogyo Seiyaku Co Ltd Flame-retardant thermoplastic resin composition
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JP2012500881A (en) * 2008-08-29 2012-01-12 アクゾ ノーベル ナムローゼ フェンノートシャップ Flame retardant polyolefin composition
JP2012025792A (en) * 2010-07-20 2012-02-09 Yazaki Corp Flame-retardant olefinic resin composition and flame-retardant tape
JP2013536312A (en) * 2010-09-03 2013-09-19 エクソンモービル ケミカル パテンツ インコーポレイテッド Flame retardant polyolefin composition and method for producing the same
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JPH07186293A (en) * 1993-12-27 1995-07-25 Tokuyama Corp Flame retardant corrugated tube
JPH08120117A (en) * 1994-10-26 1996-05-14 Dai Ichi Kogyo Seiyaku Co Ltd Flame-retardant thermoplastic resin composition
JP2002356591A (en) * 2001-05-30 2002-12-13 Yazaki Corp Electric wire protection tube
JP2012500881A (en) * 2008-08-29 2012-01-12 アクゾ ノーベル ナムローゼ フェンノートシャップ Flame retardant polyolefin composition
JP2012025792A (en) * 2010-07-20 2012-02-09 Yazaki Corp Flame-retardant olefinic resin composition and flame-retardant tape
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JP2013232310A (en) * 2012-04-27 2013-11-14 Auto Network Gijutsu Kenkyusho:Kk Composition for electric wire protection material, electric wire protection material, and wire harness

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