JP2004352889A - Thermoplastic polyester resin and resin composition, insulated wire, cable and tube using the same, and method of manufacturing insulated wire and cable - Google Patents

Abstract

The present invention relates to a thermoplastic polyester resin or the like capable of sufficiently preventing the occurrence of scratches during extrusion molding and imparting heat aging resistance and flexibility to an insulated wire and the like, and a method of manufacturing the insulated wire and the like using the same. To provide.
The thermoplastic polyester resin of the present invention is a thermoplastic polyester resin obtained by subjecting all carboxylic acid components including a dicarboxylic acid component and a diol component to a polycondensation reaction. A substituted aromatic dicarboxylic acid of 75 mol% or less, a dicarboxylic acid having a carbon-carbon double bond of 0.5 to 15 mol%, a hydroxycarboxylic acid unit, and a diol component having 2 to 8 carbon atoms; Contains aliphatic diol. Even if the conductor is covered with this resin, the occurrence of scratches can be sufficiently prevented, so that it can be wound around a bobbin at a linear speed of 150 m / min or more. In addition, the resin can impart heat aging resistance and flexibility to the coating material.
[Selection diagram] None

Description

【００８２】
なお、結晶融解エネルギー及び融点は、ＤＳＣ（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製ＤＳＣ２９２０）を用い、−６０℃と２２０℃との間で昇・降温速度１０℃／分にして測定した。結晶融解エネルギー及び融点の値としては、セカンドランで得られた値を採用した。
【００８３】
さらに熱可塑性ポリエステル樹脂について次のようにして耐熱老化性を調べた。即ち厚さがそれぞれ０．２０ｍｍ及び０．５ｍｍ（長さはいずれも２００ｍｍ）で熱可塑性ポリエステル樹脂からなる絶縁体について、アレニウス法により１万時間老化における温度定格を求めた。アレニウス法は、たとえば１４０℃、１６０℃、１８０℃の３温度に設定したギヤオーブン内に絶縁体を吊り下げ、絶縁体の伸びが５０％に低下する老化時間を求め、横軸に温度（Ｋ）の逆数、縦軸に寿命（時間）の対数をとり、上記３温度の寿命をプロットし、直線外挿にて老化時間が１万時間となる温度定格を推定するものである。なお、推定された温度定格が１２５℃以上である場合には、耐熱老化性が優れていると判断して、表１において「○」と表示した。
【００８４】
続いて、上記熱可塑性ポリエステル樹脂１００重量部に対し、ビス（ペンタブロモフェニル）エタン１０重量部、三酸化アンチモン５重量部、ヒンダードフェノール酸化防止剤（商品名：チバガイギー社製イルガノックス１０１０）１重量部、トリメチロールプロパントリアクリレート５重量部の割合でヘンシェルミキサーで予備混合したものを、２軸混合機を用いて溶融混合し、溶融ストランドを冷却切断してペレット化した。このペレットを溶融押出機を用いて押出し、この押出物で直径０．１８ｍｍの錫めっき軟銅体素線１２本から構成される撚線導体（外径０．７２ｍｍ）を被覆して未硬化樹脂層を形成した後、冷却槽に通し、２５０ｍ／ｍｉｎの線速でボビンに巻き取った。このとき、未硬化樹脂層の厚さが０．３０ｍｍとなるようにした。また冷却槽における水冷長は９ｍとし、水温は２０℃とした。
【００８５】
次に、未硬化樹脂層に２４０ｋＧｙの線量で加速電子線を照射して外径１．３２ｍｍの絶縁電線を得た。
【００８６】
この絶縁電線について次のようにして柔軟性を調べた。すなわちまず、絶縁電線を用いて内径３００ｍｍの輪を形成し、次いでその輪における最低点に１０ｇの重りをかけた。その後、変形した輪の短径を測定した。結果を表１に示す。
【００８７】
なお、短径が小さいほど、絶縁電線として柔軟性が優れていることになる。具体的には、短径長が１８５ｍｍ以下である場合に柔軟性が優れているものと評価して、表１の短径長に「○」を併記した。
【００８８】
また被覆材における耐傷性についても調べた。結果を表１に示す。耐傷性は、１ｍの被覆材において発生した傷の長さを測定することにより評価した。表１中、傷の長さが１００ｍｍ以上になる場合、絶縁電線の耐電圧性が著しく低くなることから、耐傷性が劣るものと評価して傷の長さに「×」を併記し、傷の長さが１００ｍｍ未満の場合には、耐傷性が良好であると評価して傷の長さに「○」を併記した。
【００８９】
表１に示すように、本実施例によれば、柔軟性が優れており、傷の発生も見られず、耐傷性にも優れることが分かった。
【００９０】
（実施例２，３）
熱可塑性ポリエステル樹脂の組成及び結晶融解エネルギーを表１に示す通りとした以外は、実施例１と同様にして絶縁電線を得た。そして熱可塑性ポリエステル樹脂について、実施例１と同様にして耐熱老化性を調べると共に、絶縁電線について、実施例１と同様にして柔軟性及び耐傷性を調べた。結果を表１に示す。なお、表１中、１．６ＨＧは１，６−ヘキサンジオールを表す。
【００９１】
表１に示すように、実施例２，３によれば、耐熱老化性及び柔軟性が優れており、傷の発生も見られず、耐傷性にも優れることが分かった。
【００９２】
（比較例１〜８）
熱可塑性ポリエステル樹脂、結晶融解エネルギー及びガラス転移点を表１に示す通りとした以外は実施例１と同様にして絶縁電線を得た。そして熱可塑性ポリエステル樹脂について、実施例１と同様にして耐熱老化性を調べると共に、絶縁電線について、実施例１と同様にして柔軟性及び耐傷性を調べた。結果を表２に示す。なお、推定された温度定格が１２５℃未満である場合には耐熱老化性に劣ると判断して表２において「×」と表示した。また、柔軟性については、短径長が１８５ｍｍを超える場合には柔軟性に劣るものと評価して表２において短径長に「×」を併記した。
【００９３】
【表２】

【００９４】
表２に示すように、比較例１〜８によれば、耐熱老化性、柔軟性及び耐傷性のうちいずれかひとつが劣っており、耐熱老化性、柔軟性及び耐傷性がともに優れたものはないことが分かった。
【００９５】
【発明の効果】
以上説明したように本発明の熱可塑性ポリエステル樹脂及び樹脂組成物、並びに絶縁電線及びケーブルの製造方法によれば、導体又は絶縁電線を被覆材で被覆してボビンに巻き取る場合でも、傷の発生を十分に防止することが可能となるため、１５０ｍ／分以上の線速でボビンに巻き取ることができ、絶縁電線又はケーブルの製造効率を著しく向上させることができる。また絶縁電線の歩留まりを十分に向上させることができる。更に熱可塑性ポリエステル樹脂を架橋させることで、被覆材に耐熱老化性及び柔軟性を付与することができる。
【００９６】
また本発明の絶縁電線、ケーブル及びチューブは、耐電圧性、耐熱老化性及び柔軟性に優れるため、電磁調理器、炊飯器又は電子レンジなどの民生用電子機器のような狭い配線スペースを有する機器における配線作業が容易となる。また本発明の絶縁電線、ケーブル及びチューブは耐電圧性及び耐熱老化性に優れるため、これらを使用することにより、上記機器のような高耐電圧が求められるような機器を安定且つ安全に使用することも可能である。
【図面の簡単な説明】
【図１】本発明に係る絶縁電線の製造方法の一工程を示す図である。
【符号の説明】
１…溶融押出機、３…導体、４…冷却槽、７…ボビン。[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyester resin and a resin composition, an insulated wire, a cable and a tube using the same, and a method for producing an insulated wire and a cable.
[0002]
[Prior art]
Insulated wires, cables, heat-shrinkable tubes, and the like are used for in-machine wiring of microwave ovens, ovens, rice cookers, gas stoves, electric cookers, and automobiles. Insulated wires and the like may generate heat due to application of a high voltage or need to be arranged in a narrow space, so that insulated wires, cables and heat-shrinkable tubes are required to have heat aging resistance and flexibility.
[0003]
As such a covering material of an insulated wire or cable or a material of a heat-shrinkable tube, for example, a material disclosed in JP-A-2000-95846 is known. The publication contains (A1) an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid, (A2) an aliphatic oxycarboxylic acid, and an aliphatic dicarboxylic acid having a carbon-carbon unsaturated bond in a molecule as a monomer unit, And (B) an insulation obtained by crosslinking a resin composition mainly composed of a thermoplastic polyester resin having a melt index of 1 to 50, which is a thermoplastic polyester resin containing an aliphatic diol as a monomer unit as a glycol component. A coating is disclosed.
[0004]
[Patent Document 1]
JP 2000-95846 A
[0005]
[Problems to be solved by the invention]
However, the covering material of the insulated wire or cable or the material of the tube described in the above-mentioned conventional publication has the following problems, although it has heat aging resistance and flexibility.
[0006]
That is, since the resin composition mainly composed of the thermoplastic polyester resin does not have sufficient crystallinity, scratches are likely to occur during extrusion molding, and the withstand voltage characteristics may decrease. Here, in order to improve the withstand voltage characteristics, it is conceivable to increase the crystallinity of the resin composition. However, in this case, there is a problem that the flexibility is reduced and the wiring operation becomes difficult.
[0007]
The present invention has been made in view of the above circumstances, and is a thermoplastic polyester that can sufficiently prevent the occurrence of scratches during extrusion molding and can provide heat-resistant aging and flexibility to insulated wires, cables, and tubes. An object of the present invention is to provide a resin and a resin composition, and an insulated wire, a cable and a tube using the same, and a method of manufacturing the insulated wire and a cable.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by setting the carboxylic acid composition to a specific composition, and have completed the present invention.
[0009]
That is, the thermoplastic polyester resin of the present invention is a thermoplastic polyester resin obtained by subjecting all carboxylic acid components including a dicarboxylic acid component to a polycondensation reaction with a diol component. 75 mol% or less of a substituted aromatic dicarboxylic acid, 0.5 to 15 mol% of a dicarboxylic acid having a carbon-carbon double bond, and a hydroxycarboxylic acid unit, an o-substituted aromatic dicarboxylic acid, an m-substituted aromatic It contains at least one member selected from the group consisting of dicarboxylic acids and aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and the diol component contains at least one or more aliphatic diols having 2 to 8 carbon atoms. Is a thermoplastic polyester resin. In the present invention, the hydroxycarboxylic acid unit refers to a unit containing a hydroxyl group and a carboxyl group at both ends of a molecule, and specifically, a monomer of an aliphatic hydroxycarboxylic acid and / or an aliphatic hydroxycarboxylic acid. Refers to acid polymers. Here, the aliphatic hydroxycarboxylic acid includes its acid anhydride. Further, in the present invention, the carboxylic acid includes its ester.
[0010]
The hydroxycarboxylic acid unit is caprolactone or polycaprolactone, and the content of the hydroxycarboxylic acid unit in all carboxylic acid components is preferably 35 mol% or less.
[0011]
In order to sufficiently prevent the occurrence of scratches during extrusion molding, the crystal melting energy is 10 J / g or more, the melting point is 200 ° C. or less, the second modulus (Secant Modulus) is 400 MPa or less, and the glass transition temperature is 15 ° C. or less. It is preferable that In this case, there is an advantage that the flexibility of the thermoplastic polyester resin is improved.
[0012]
Further, the present invention is an insulated wire and cable coated with a resin composition mainly composed of the above-mentioned thermoplastic polyester resin, and a tube obtained by subjecting the resin composition to melt extrusion molding.
[0013]
These insulated wires, cables, and tubes have excellent withstand voltage characteristics, heat aging resistance, and flexibility, and are devices with narrow wiring space such as microwave ovens, ovens, rice cookers, gas stoves, electric cookers, and automobiles. The wiring work in is easy. In addition, since withstand voltage characteristics and heat aging resistance are excellent, it is possible to use equipment requiring high withstand voltage stably and safely.
[0014]
Furthermore, a resin composition mainly composed of a thermoplastic polyester resin can be made flame-retardant by using a known flame-retardant compounding formulation, and the fire safety can be enhanced.
[0015]
In addition, the resin composition mainly composed of a thermoplastic polyester resin can be crosslinked by means such as peroxide crosslinking or electron beam crosslinking, regardless of the non-flame retardant or flame retardant composition, and can be used to coat insulated wires and cables. When used as a material, not only can the heat deformation characteristics be significantly improved, but when used as a tube material, a heat-shrinkable tube can be obtained.
[0016]
In addition, in this specification, the glass transition point is a glass transition point (second run) measured at the time of the second temperature rise using a differential scanning calorimeter (DSC2920 type manufactured by TA Instruments). Further, the second modulus means a value obtained by multiplying a 2% modulus measured according to JIS K 7113 by 50.
[0017]
DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.
[0018]
First, an embodiment of the thermoplastic polyester resin of the present invention will be described.
[0019]
The thermoplastic polyester resin of the present invention can be easily produced by polycondensing all carboxylic acid components (A) including the following dicarboxylic acid components and diol components (B) by means known per se. The total carboxylic acid component (A) contains, as dicarboxylic acid components, (A1) a p-substituted aromatic dicarboxylic acid and (A2) a dicarboxylic acid having a carbon-carbon double bond, and (A3) o-substituted. It contains at least one member selected from the group consisting of aromatic dicarboxylic acids, m-substituted aromatic dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and hydroxycarboxylic acid units.
[0020]
Examples of the p-substituted aromatic dicarboxylic acid (A1) include terephthalic acid and 2,6-naphthalenedicarboxylic acid.
[0021]
Examples of the dicarboxylic acid having a carbon-carbon double bond of (A2) include fumaric acid, maleic acid, citraconic acid, mesaconic acid and the like.
[0022]
As the component (A3), an o-substituted aromatic dicarboxylic acid, an m-substituted aromatic dicarboxylic acid, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and a hydroxycarboxylic acid unit may be used alone or in combination of two or more. You can also.
[0023]
Examples of the o-substituted aromatic dicarboxylic acid include phthalic acid.
[0024]
Examples of the m-substituted aromatic dicarboxylic acid include isophthalic acid.
[0025]
Examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms include adipic acid, sebacic acid and dodecanedicarboxylic acid.
[0026]
Examples of the hydroxycarboxylic acid unit include caprolactone and polycaprolactone. Examples of caprolactone include 1,6-lactone ε-caprolactone 6-hydroxyhexanoate (Placcel M, manufactured by Daicel Corporation). Examples of polycaprolactone include Placcel PCL220, manufactured by Daicel Corporation.
[0027]
As the diol component (B), an aliphatic diol having 2 to 8 carbon atoms is used. Examples of such an aliphatic diol include 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like. . In particular, 1,4-butanediol and 1,6-hexanediol are preferably used.
[0028]
When polycondensing the dicarboxylic acid component and the diol component, the carboxylic acid component containing the dicarboxylic acid component is reacted with the diol component. Here, the content of the p-substituted aromatic dicarboxylic acid in all carboxylic acid components is 75 mol% or less, and preferably 70 mol% or less. When the content exceeds 75 mol%, the heat aging resistance of the thermoplastic polyester resin decreases. Further, the content of the dicarboxylic acid having a carbon-carbon double bond in all the carboxylic acid components is 0.5 to 15 mol%, preferably 1 to 10 mol%. If the amount is less than 0.5 mol%, the crosslinking becomes insufficient and the heat aging resistance decreases. If the amount exceeds 15 mol%, the amount of unreacted double bond components increases and the heat aging resistance decreases.
[0029]
The content of the component (A3) in all the carboxylic acid components is preferably from 10 to 60 mol%, more preferably from 10 to 50 mol%. If it exceeds 60 mol%, the crystallinity of the resin tends to decrease, and the number of scratches tends to increase. If it is less than 10 mol%, the flexibility and processability tend to decrease.
[0030]
The hydroxycarboxylic acid unit is preferably caprolactone or polycaprolactone, and the content of the hydroxycarboxylic acid unit in all carboxylic acid components is preferably 35 mol% or less. When the content of the hydroxycarboxylic acid unit exceeds 35 mol%, the hot water tends to decrease.
[0031]
In all the carboxylic acid components, the molar ratio of the hydroxycarboxylic acid unit to the aromatic dicarboxylic acid is preferably 0.5 or less. In this case, the thermoplastic polyester resin has excellent hot water resistance.
[0032]
The thermoplastic polyester resin is subjected to a transesterification reaction between the components (A) and (B) under heating and reduced pressure using a catalyst such as an organic titanium compound such as n-butyl titanate. After the polymer is obtained, the above-mentioned aliphatic hydroxycaprolactone polymer is further added to carry out a transesterification reaction, or the above-mentioned components (A1), (A2), (A3) and all of the components (B) are batch-processed. It can be obtained by a batch charging method of charging and transesterification, a direct polymerization method, or the like.
[0033]
In producing the thermoplastic polyester resin, an alkyl ester thereof (for example, dimethyl terephthalate) may be used instead of the p-substituted aromatic dicarboxylic acid. Further, in place of the dicarboxylic acid having a carbon-carbon double bond, an acid anhydride thereof can be used.In addition, in place of the above o-substituted aromatic dicarboxylic acid or m-substituted aromatic dicarboxylic acid, aliphatic dicarboxylic acid, These alkyl esters (for example, dimethyl phthalate, dimethyl isophthalate) can also be used.
[0034]
ADVANTAGE OF THE INVENTION According to the thermoplastic polyester resin of this invention, generation | occurrence | production of a damage | wound can be sufficiently prevented at the time of extrusion-molding the resin composition containing this as a main component, and it gives heat-resistant aging property and flexibility to an insulated wire, cable, and tube. Can be done.
[0035]
The thermoplastic polyester resin of the present invention preferably has a crystal melting energy of 10 J / g or more, a melting point of 200 ° C. or less, a second modulus of 400 MPa or less, and a glass transition temperature of 15 ° C. or less.
[0036]
When the crystal melting energy is less than 10 J / g, wires and tubes formed by extruding the resin composition containing the thermoplastic polyester resin as a main component are likely to have many scratches during molding and have a tendency to lower withstand voltage characteristics. is there. On the other hand, when the glass transition temperature exceeds 15 ° C., the flexibility of electric wires and tubes tends to decrease, and workability such as wiring work tends to decrease. When the melting point exceeds 200 ° C. and the second modulus exceeds 400 MPa, the flexibility of a molded article composed of a resin composition mainly composed of a thermoplastic polyester resin tends to decrease.
[0037]
In addition, the crystal melting energy of the thermoplastic polyester resin is preferably 20 J / g or more. The crystal melting energy of the thermoplastic polyester resin is preferably 30 J / g or less. If the crystal melting energy exceeds 30 J / g, the flexibility tends to decrease.
[0038]
Further, the glass transition point of the thermoplastic polyester resin is preferably 10 ° C or lower, more preferably 0 ° C or lower.
[0039]
Further, the melting point of the thermoplastic polyester resin is preferably 60 ° C. or higher. If the melting point is lower than 60 ° C., many scratches due to insufficient cooling may occur during molding.
[0040]
Next, embodiments of the resin composition of the present invention will be described.
[0041]
When the thermoplastic polyester resin of the present invention is used as a covering material of an insulated wire or a raw material of a tube, a resin composition mainly composed of the thermoplastic polyester resin is used. Here, “mainly composed of a thermoplastic polyester resin” means that the thermoplastic polyester resin component is contained in an amount of 50% by weight or more of the resin components in the resin composition.
[0042]
According to this resin composition, it is possible to sufficiently prevent the occurrence of scratches during extrusion molding, and to impart heat aging resistance and flexibility to insulated wires, cables, and tubes.
[0043]
If necessary, a compounding agent such as a flame retardant, a hydrolysis inhibitor, an antioxidant, a crosslinking aid, a filler, or a pigment may be appropriately added to the resin composition.
[0044]
A flame retardant is used to make a flammable thermoplastic polyester resin flame-retardant, and is necessary when an insulated wire is used as a wire for a vehicle or a wire for an electronic device.
[0045]
Examples of the flame retardant include a halogen-based flame retardant and a non-halogen-based flame retardant, and any flame retardant may be used.
[0046]
Examples of the halogen-based flame retardants include brominated flame retardants such as polybromodiphenyl ether, ethylene bisbrominated phthalimide, bis (brominated phenyl) ethane and bis (brominated phenyl) terephthalamide, and chlorine-based flame retardants such as perchloropentacyclodecane. Although a flame retardant is used, when these halogen-based flame retardants are used, antimony trioxide, aluminum hydroxide, magnesium hydroxide and the like may be used in combination.
[0047]
Among these, those using ethylene bisbrominated phthalimide, bis (brominated phenyl) ethane, and bis (brominated phenyl) terephthalamide do not impair the heat aging resistance of the thermoplastic polyester resin, and furthermore, the coating material surface It is a flame retardant that can be preferably applied without problems such as bleeding of the flame retardant into the flame retardant.
[0048]
The amount of the flame retardant depends on the type of the compound and the required flame retardancy. For example, in the case of a halogen-based flame retardant, 5 to 50 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the thermoplastic polyester resin. What is necessary is just to mix | blend within 30 weight part. In this case, by using an appropriate amount of antimony trioxide, flame retardation can be more effectively achieved.
[0049]
Examples of non-halogen flame retardants include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, nitrogen flame retardants such as melamine, melamine cyanurate, guanidine, cyanuric acid, and phosphorus such as polyphosphoric acid, ammonium polyphosphate, and red phosphorus. There are flame retardants, which may be used alone or in combination. Further, when using these non-halogen flame retardants, a flame retardant auxiliary such as silica, zinc borate, zinc stannate and the like may be used in combination.
[0050]
The amount of the flame retardant depends on the type of the flame retardant to be blended and the required flame retardancy. For example, in the case of a metal hydroxide flame retardant, 50 to 200 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. And more preferably 70 to 150 parts by weight. In the case of a nitrogen-based flame retardant, it may be blended in an amount of 10 to 150 parts by weight, more preferably 20 to 75 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin. Further, when a nitrogen-based flame retardant is used, the use of a phosphorus-based flame retardant, silica, or the like in an appropriate amount enables more effective flame retardation.
[0051]
As the hydrolysis inhibitor, for example, carbodiimide is used.
[0052]
The above antioxidant is necessary for maintaining heat aging resistance, and as the antioxidant, amine antioxidants and hindered phenol antioxidants can be suitably used. These can be used alone or in combination. Further, when using an antioxidant, weather resistance can be more effectively improved by using a metal deactivator, an ultraviolet absorber, an ultraviolet stabilizer and the like in combination.
[0053]
The cross-linking aid is used to increase the cross-linking efficiency upon irradiation with ionizing radiation, and polyfunctional monomers and oligomers are used as the cross-linking aid. Examples of the polyfunctional monomer include 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentamethylolpropane triacrylate, ethylene glycol dimethacrylate triallyl cyanurate, triallyl isocyanurate and the like. Can be mentioned.
[0054]
Next, an embodiment of the insulated wire of the present invention will be described.
[0055]
The insulated wire includes a conductor and a covering material. The coating material is composed of the resin composition described above.
[0056]
The conductor may be a single-wire conductor or a stranded conductor formed by twisting a single-wire conductor. As the single-wire conductor, for example, tin-plated soft copper, tin-plated soft steel, soft copper, nickel-plated soft copper, nickel and the like can be used. When the conductor is a stranded conductor, the outer diameter of the stranded conductor is usually 0.72 to 15.2 mm, preferably 0.72 to 9.1 mm.
[0057]
Further, the thickness of the coating material is usually 0.3 to 2.0 mm, preferably 0.3 to 1.4 mm.
[0058]
It is preferable that the coating material is flame retarded. In this case, heat aging resistance is improved. Further, it is preferable that the coating material is crosslinked. In this case, the scratch resistance is improved.
[0059]
In the insulated wire, the coating material may be coated directly on the conductor, or may be coated on another coating material.
[0060]
Next, an embodiment of a method for manufacturing an insulated wire according to the present invention will be described.
[0061]
First, a conductor and a resin composition mainly composed of the thermoplastic polyester resin are prepared.
[0062]
Then, as shown in FIG. 1, the conductor 3 is extrusion-coated with the resin composition extruded from the melt extruder 1 to form an uncured resin layer. After that, it is wound around the bobbin 7 (first step). The accumulator 6 can be omitted. When it is intended to impart flame retardancy to the covering material of the insulated wire, the resin composition needs to contain a flame retardant.
[0063]
Here, the wire speed of the conductor 3 varies depending on the extrusion temperature, the conductor size, and the cooling bath capacity, but for example, a 0.2 mm insulated wire is laid on a stranded wire conductor composed of twelve 0.18 mm tinned soft copper conductor wires. In the case of coating with a coating material, the speed is 50 m / min or more, and in this case, generation of scratches in the coating material can be sufficiently prevented. The linear velocity of the conductor 3 is preferably 150 m / min or more from the viewpoint of greatly improving the productivity of the insulated wire. However, the linear velocity is preferably set to 350 m / min or less. When the linear velocity exceeds 350 m / min, productivity is greatly improved, but crystallization is insufficient, and large scratches tend to occur in the covering material of the insulated wire.
[0064]
Further, the water temperature in the cooling tank 4 is preferably 5 to 30C. If the water temperature is lower than 5 ° C., the physical properties (elongation) of the insulator tend to decrease. If the water temperature exceeds 30 ° C., even if the length of the cooling bath 4 is increased, the generation of scratches tends to be impossible. The water cooling length in the cooling tub 4, that is, the length of the cooling tub 4 along the winding direction of the conductor also depends on the water temperature in the cooling tub 4, but is usually 3 to 15 m.
[0065]
At this time, it is also possible to extrude into a tube without using a conductor. The processing conditions vary depending on the extrusion size, but processing can be performed using existing tube processing equipment.
[0066]
Next, the uncured resin layer is crosslinked to obtain a coating material that is a cured resin layer (second step). As a method for crosslinking, there are a crosslinking method by irradiation with active energy rays and a chemical crosslinking method. From the viewpoint of the crosslinking speed, a crosslinking method by irradiation with active energy rays is preferable.
[0067]
Examples of the active energy ray include an electron beam, an accelerated electron beam, γ-ray, X-ray, α-ray, β-ray, ultraviolet ray, and the like. From the viewpoint of effective use, an accelerated electron beam can be most preferably used. The irradiation dose of the active energy ray may be set to, for example, 30 to 500 kGy, preferably 50 to 250 kGy in the case of an electron beam. If the irradiation dose is less than 30 kGy, the heat resistance tends to decrease, and if it exceeds 500 kGy, the physical properties (elongation) of the insulator tend to decrease.
[0068]
In crosslinking the uncured resin layer, the resin composition preferably contains a crosslinking aid. In this case, the cross-linking proceeds efficiently, and the cross-linking can be completed in a shorter time than when no cross-linking aid is contained.
[0069]
When the uncured resin layer is to be chemically crosslinked, an organic peroxide may be previously blended in the resin composition, and the uncured resin layer may be heated. Examples of the organic peroxide include dicumyl peroxide and bis (t-butylperoxyisopropyl) peroxide.
[0070]
Thus, the manufacture of the insulated wire is completed. Since the insulated wire manufactured in this way has excellent flexibility, wiring work in a device having a narrow wiring space such as a consumer electronic device such as an electromagnetic cooker, a rice cooker or a microwave oven becomes easy. Further, since the insulated wire has excellent voltage resistance and heat aging resistance, by using this insulated wire, it is also possible to use equipment such as the above-described equipment requiring high voltage stably and safely. .
[0071]
Next, an embodiment of a cable according to the present invention will be described.
[0072]
A cable according to the present invention includes one or a plurality of insulated wires and a covering material, and the covering material includes the resin composition. In addition, the shape of the coating material may be a cylindrical shape or a tape shape.
[0073]
Next, a method for manufacturing a cable according to the present invention will be described.
[0074]
The method for manufacturing a cable according to the present invention is the same as the above-described method for manufacturing an insulated wire, except that one or more insulated wires are used instead of the conductor. Since the cable obtained by this manufacturing method is excellent in flexibility, wiring work in a device having a narrow wiring space such as a consumer electronic device such as an electromagnetic cooker, a rice cooker or a microwave oven becomes easy. Further, since the cable has excellent voltage resistance and heat aging resistance, by using this cable, it is possible to stably and safely use equipment such as the above-described equipment requiring high voltage.
[0075]
Next, an embodiment of the tube according to the present invention will be described.
[0076]
The tube of this embodiment is made of a resin composition mainly composed of the above-mentioned thermoplastic polyester resin. Such a tube can be obtained by forming into a tube-shaped product by a method such as melt extrusion, cross-linking by irradiation with an accelerated electron beam, expanding the tube-shaped product in the radial direction under heating conditions, and cooling. Here, the resin composition preferably contains the above-mentioned crosslinking aid, as described in the method for producing an insulated wire.
[0077]
【Example】
Hereinafter, the contents of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0078]
(Example 1)
First, 0.67 mol of dimethyl terephthalate (DMT) as an alkyl ester of p-substituted aromatic dicarboxylic acid, 0.27 mol of dimethyl isophthalate (DMI) as an alkyl ester of m-substituted aromatic dicarboxylic acid, and dimethyl sebacate 0.06 mol of (DMS), 0.060 mol of fumaric acid as a dicarboxylic acid having a carbon-carbon double bond, and polycaprolactone as a polymer of an aliphatic hydroxycarboxylic acid (Placcel PCL220 manufactured by Daicel Chemical Industries, Ltd .: molecular weight 2000) 028 moles and 1.4 moles of 1,4-butanediol (1.4BG) as a diol component were put into a reactor equipped with a nitrogen introducing device, a stirrer, a torque meter and a rectification column. Esterification (exchange) was performed at ~ 240 ° C.
[0079]
Next, the rectification column was removed, and a polycondensation reaction was performed at 250 ° C. and 0.1 Torr or less until a predetermined stirring torque was reached.
[0080]
The viscosity of the thus obtained thermoplastic polyester resin was measured at 250 ° C. using a flow tester, and the viscosity was 60 Pa · s. Further, the crystal melting energy, glass transition point, melting point and second modulus (Secant Modulus) of the thermoplastic polyester resin were measured. Table 1 shows the results.
[0081]
[Table 1]

[0082]
The crystal melting energy and melting point were measured using DSC (DSC2920, manufactured by TA Instruments) at a temperature increase / decrease rate of 10 ° C./min between −60 ° C. and 220 ° C. As the values of the crystal melting energy and the melting point, the values obtained in the second run were adopted.
[0083]
Further, the heat aging resistance of the thermoplastic polyester resin was examined as follows. That is, with respect to an insulator made of a thermoplastic polyester resin having a thickness of 0.20 mm and a thickness of 0.5 mm (all lengths are 200 mm), the temperature rating after 10,000 hours aging was determined by the Arrhenius method. In the Arrhenius method, an insulator is suspended in a gear oven set to, for example, three temperatures of 140 ° C., 160 ° C., and 180 ° C., an aging time at which the elongation of the insulator decreases to 50% is obtained, and the temperature (K ), The logarithm of the life (hour) is plotted on the vertical axis, the life at the above three temperatures is plotted, and the temperature rating at which the aging time is 10,000 hours is estimated by linear extrapolation. In addition, when the estimated temperature rating was 125 ° C. or more, it was judged that the heat aging resistance was excellent, and “○” was displayed in Table 1.
[0084]
Subsequently, 10 parts by weight of bis (pentabromophenyl) ethane, 5 parts by weight of antimony trioxide, and a hindered phenol antioxidant (trade name: Irganox 1010 manufactured by Ciba Geigy Co., Ltd.) are added to 100 parts by weight of the thermoplastic polyester resin. The mixture preliminarily mixed with a Henschel mixer at a ratio of 5 parts by weight of trimethylolpropane triacrylate by weight was melt-mixed using a twin-screw mixer, and the molten strand was cooled and cut into pellets. The pellets are extruded using a melt extruder, and the extrudate is used to cover a stranded conductor (outer diameter 0.72 mm) composed of 12 tin-plated annealed copper wires with a diameter of 0.18 mm to form an uncured resin layer. Was formed and passed through a cooling tank, and wound around a bobbin at a linear speed of 250 m / min. At this time, the thickness of the uncured resin layer was set to 0.30 mm. The water cooling length in the cooling tank was 9 m, and the water temperature was 20 ° C.
[0085]
Next, the uncured resin layer was irradiated with an accelerated electron beam at a dose of 240 kGy to obtain an insulated wire having an outer diameter of 1.32 mm.
[0086]
The flexibility of this insulated wire was examined as follows. That is, first, a ring having an inner diameter of 300 mm was formed using an insulated wire, and then a 10 g weight was applied to the lowest point of the ring. Thereafter, the minor axis of the deformed ring was measured. Table 1 shows the results.
[0087]
The smaller the minor diameter, the better the flexibility as an insulated wire. Specifically, when the minor axis length was 185 mm or less, it was evaluated as having excellent flexibility, and "「 "was also written in the minor axis length in Table 1.
[0088]
The scratch resistance of the coating material was also examined. Table 1 shows the results. The scratch resistance was evaluated by measuring the length of a scratch generated in a 1 m coating material. In Table 1, when the length of the flaw is 100 mm or more, the withstand voltage of the insulated wire is remarkably reduced. Therefore, it is evaluated that the flaw resistance is inferior. When the length was less than 100 mm, the scratch resistance was evaluated as being good, and "○" was also written along with the length of the scratch.
[0089]
As shown in Table 1, it was found that according to this example, the flexibility was excellent, no flaw was generated, and the flaw resistance was also excellent.
[0090]
(Examples 2 and 3)
An insulated wire was obtained in the same manner as in Example 1 except that the composition of the thermoplastic polyester resin and the crystal melting energy were as shown in Table 1. The thermoplastic polyester resin was examined for heat aging resistance in the same manner as in Example 1, and the insulated wire was examined for flexibility and scratch resistance in the same manner as in Example 1. Table 1 shows the results. In Table 1, 1.6HG represents 1,6-hexanediol.
[0091]
As shown in Table 1, according to Examples 2 and 3, it was found that heat aging resistance and flexibility were excellent, no scratches were generated, and the scratch resistance was also excellent.
[0092]
(Comparative Examples 1 to 8)
An insulated wire was obtained in the same manner as in Example 1 except that the thermoplastic polyester resin, the crystal melting energy and the glass transition point were as shown in Table 1. The thermoplastic polyester resin was examined for heat aging resistance in the same manner as in Example 1, and the insulated wire was examined for flexibility and scratch resistance in the same manner as in Example 1. Table 2 shows the results. In addition, when the estimated temperature rating was less than 125 ° C., it was judged to be inferior to the heat aging resistance, and “×” was displayed in Table 2. Regarding the flexibility, when the minor axis length exceeded 185 mm, it was evaluated as inferior in flexibility, and "x" was also described in Table 2 along with the minor axis length.
[0093]
[Table 2]

[0094]
As shown in Table 2, according to Comparative Examples 1 to 8, one of heat aging resistance, flexibility and scratch resistance is inferior, and heat aging resistance, flexibility and scratch resistance are both excellent. I knew it was not.
[0095]
【The invention's effect】
As described above, according to the thermoplastic polyester resin and the resin composition of the present invention, and the method for producing an insulated wire and a cable, even when the conductor or the insulated wire is covered with the covering material and wound up on a bobbin, the generation of scratches occurs. Can be sufficiently prevented, it can be wound around a bobbin at a linear speed of 150 m / min or more, and the production efficiency of an insulated wire or cable can be significantly improved. Further, the yield of the insulated wires can be sufficiently improved. Further, by crosslinking the thermoplastic polyester resin, the coating material can be given heat aging resistance and flexibility.
[0096]
Further, the insulated wires, cables and tubes of the present invention are excellent in withstand voltage, heat aging resistance and flexibility, and therefore have a narrow wiring space, such as consumer electronic devices such as electromagnetic cookers, rice cookers and microwave ovens. The wiring work in is easy. Further, the insulated wires, cables and tubes of the present invention are excellent in withstand voltage and heat aging resistance. Therefore, by using these, devices such as the above-mentioned devices requiring high withstand voltage can be used stably and safely. It is also possible.
[Brief description of the drawings]
FIG. 1 is a view showing one step of a method for manufacturing an insulated wire according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Melt extruder, 3 ... Conductor, 4 ... Cooling tank, 7 ... Bobbin.

Claims (16)

In a thermoplastic polyester resin obtained by a polycondensation reaction of all carboxylic acid components including a dicarboxylic acid component and a diol component,
The total carboxylic acid component, as the dicarboxylic acid component,
75 mol% or less of the p-substituted aromatic dicarboxylic acid,
A hydroxycarboxylic acid unit, an o-substituted aromatic dicarboxylic acid, an m-substituted aromatic dicarboxylic acid and a fatty acid having 4 to 12 carbon atoms, containing 0.5 to 15 mol% of a dicarboxylic acid having a carbon-carbon double bond; At least one selected from the group consisting of aromatic dicarboxylic acids,
The diol component,
A thermoplastic polyester resin comprising at least one kind of aliphatic diol having 2 to 8 carbon atoms. The thermoplastic polyester according to claim 1, wherein the hydroxycarboxylic acid unit is caprolactone or polycaprolactone, and a content of the hydroxycarboxylic acid unit in the total carboxylic acid components is 35 mol% or less. resin. The thermoplastic polyester resin according to claim 2, wherein the molar ratio of the hydroxycarboxylic acid unit to the aromatic dicarboxylic acid is 0.5 or less in all the carboxylic acid components. The heat according to any one of claims 1 to 3, wherein the crystal melting energy is 10 J / g or more, the melting point is 200 ° C or less, the second modulus is 400 MPa or less, and the glass transition temperature is 15 ° C or less. Plastic polyester resin. A resin composition mainly comprising the thermoplastic polyester resin according to claim 1. In an insulated wire including a conductor and a covering material,
An insulated wire, wherein the covering material includes the resin composition according to claim 5. The insulated wire according to claim 6, wherein the resin composition contained in the covering material is made flame retardant. The insulated wire according to claim 6 or 7, wherein the resin composition contained in the covering material is cross-linked. A cable comprising a plurality of insulated wires according to any one of claims 6 to 8. A tube comprising the resin composition according to claim 5. The tube according to claim 10, wherein the resin composition is flame retarded. The tube according to claim 10, wherein the resin composition is cross-linked. In a method for manufacturing an insulated wire including a conductor and a covering material,
A first step of coating the conductor with the resin composition according to claim 5 to form an uncured resin layer, and winding the conductor around a bobbin at a linear speed of 50 m / min or more;
A second step of crosslinking the uncured resin layer to obtain the coating material that is a cured resin layer;
A method for producing an insulated wire, comprising: The method for manufacturing an insulated wire according to claim 13, wherein in the second step, the uncured resin layer is crosslinked by irradiation with active energy rays. An insulated wire manufactured by the method for manufacturing an insulated wire according to claim 13. In a method for manufacturing a cable including one or a plurality of insulated wires and a covering material,
A first step of coating one or more insulated wires with the resin composition according to claim 5 to form an uncured resin layer, and winding the bobbin at a linear speed of 50 m / min or more;
A second step of crosslinking the uncured resin layer to obtain the coating material that is a cured resin layer;
A method for manufacturing a cable, comprising:

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