JP2008101069A - Polyphenylene sulfide resin composition - Google Patents

Polyphenylene sulfide resin composition Download PDF

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JP2008101069A
JP2008101069A JP2006283220A JP2006283220A JP2008101069A JP 2008101069 A JP2008101069 A JP 2008101069A JP 2006283220 A JP2006283220 A JP 2006283220A JP 2006283220 A JP2006283220 A JP 2006283220A JP 2008101069 A JP2008101069 A JP 2008101069A
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polyphenylene sulfide
polyamide
resin composition
sulfide resin
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JP4973118B2 (en
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Makoto Kobayashi
誠 小林
Keiko Ueno
敬子 上野
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Toray Industries Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide (PPS) resin composition having the heat resistance of class B level prescribed by ISO 6722 and excellent in abrasion resistance by blending the PPS, a polyamide resin and a specific aromatic compound. <P>SOLUTION: This polyphenylene sulfide resin composition is obtained by blending (A) 100 pts.wt. PPS resin, (B) 12 to 100 pts.wt. polyamide resin and (C) 6 to 12 pts.wt. aromatic compound expressed by structural formula [wherein, R1, R2 are each a 1-8C hydrocarbon group; R3, R4 are each a 9-18C acyl or hydrocarbon group; R5 to R12 are each H, a halogen atom or a ≤8C hydrocarbon group; and (m), (n) are each an integer of ≥1, and the (m), (n) may be the same or different]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、電線被覆用途に適した、耐摩耗性、耐熱性に優れる樹脂組成物に関する。   The present invention relates to a resin composition excellent in wear resistance and heat resistance suitable for wire coating applications.

ポリフェニレンサルファイド樹脂(以下PPS樹脂と略す)は優れた耐熱性、熱安定性、耐薬品性、電気絶縁性、耐湿熱性などエンジニアリングプラスチックとしては好適な性質を有しており、射出成形用を中心として各種電気・電子部品、機械部品および自動車部品などに使用されている。   Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has suitable properties as engineering plastics, such as excellent heat resistance, thermal stability, chemical resistance, electrical insulation, and moist heat resistance. It is used for various electric / electronic parts, machine parts and automobile parts.

自動車電線用にはポリ塩化ビニール(以下PVCと略す)が大量に使用されているが、焼却廃棄の環境影響が指摘されており、PVCを用いず、自動車用用途に耐えうる耐熱性を有する電線被覆材が求められている。PPSは高い耐熱性を有する一方、耐摩耗性、靭性が低く、そのまま電線被覆用途に使用するのは困難であり、その改良が強く望まれている。   Polyvinyl chloride (hereinafter abbreviated as PVC) is used in large amounts for automobile wires, but the environmental impact of incineration disposal has been pointed out, and PVC has no heat resistance and can withstand automotive applications. There is a need for a coating material. While PPS has high heat resistance, its wear resistance and toughness are low, and it is difficult to use as it is for wire coating applications, and its improvement is strongly desired.

例えば特許文献1には、PPS樹脂に特定芳香族化合物を配合した樹脂組成物が提案されているが、特に自動車用電線被覆用途に求められる耐摩耗性を得ることが出来ない問題があった。特許文献2には、PPS樹脂に共重合ポリアミドを配合する樹脂組成物が、特許文献3には、PPS樹脂に非晶性ポリアミドを配合する樹脂組成物が提案されているが、ともにISO6722に定められる乾熱処理後の低温巻きつけ試験で被覆が裂ける問題があった。
特開2002−363405号公報(請求項1) 特開2006−137852号公報(請求項1) 特開昭61−53356号公報(請求項1)
For example, Patent Document 1 proposes a resin composition in which a specific aromatic compound is blended with a PPS resin. However, there is a problem that it is not possible to obtain the abrasion resistance particularly required for wire coating for automobiles. Patent Document 2 proposes a resin composition in which a copolyamide is blended with a PPS resin, and Patent Document 3 proposes a resin composition in which an amorphous polyamide is blended with a PPS resin, both of which are defined in ISO 6722. There was a problem that the coating was torn in the low temperature winding test after dry heat treatment.
JP 2002-363405 A (Claim 1) JP 2006-137852 A (Claim 1) JP-A-61-53356 (Claim 1)

本発明は、PPS樹脂、ポリアミド樹脂にビスフェノールユニットとアルキレングリコールユニットを有し、かつ両端に炭素数9〜18のアシル基または炭化水素基を有する特定の芳香族化合物を特定量配合することで、耐摩耗性、耐熱性、着色性に優れる電線被覆用樹脂組成物を提供することを目的とする。   The present invention includes blending a specific amount of a specific aromatic compound having a bisphenol unit and an alkylene glycol unit in a PPS resin and a polyamide resin and having an acyl group or a hydrocarbon group having 9 to 18 carbon atoms at both ends. It aims at providing the resin composition for electric wire coating | coated which is excellent in abrasion resistance, heat resistance, and coloring property.

そこで本発明者らは上記の課題を解決すべく鋭意検討した結果、PPS樹脂、ポリアミド樹脂にビスフェノールユニットとアルキレングリコールユニットを有し、かつ両端に炭素数9〜18のアシル基または炭化水素基を有する特定の芳香族化合物を特定量配合した結果、前記目的を達成し得ることを見いだし本発明に到達した。   Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have bisphenol units and alkylene glycol units in the PPS resin and the polyamide resin, and an acyl group or hydrocarbon group having 9 to 18 carbon atoms at both ends. As a result of blending a specific amount of a specific aromatic compound having a specific amount, the inventors have found that the object can be achieved, and reached the present invention.

すなわち本発明は、
(1)(A)ポリフェニレンサルファイド樹脂100重量部に対して、(B)ポリアミド樹脂12〜100重量部、(C)下記構造式で表される芳香族化合物を6〜12重量部配合してなるポリフェニレンサルファイド樹脂組成物、
That is, the present invention
(1) (A) 12 to 100 parts by weight of a polyamide resin and (C) 6 to 12 parts by weight of an aromatic compound represented by the following structural formula are blended with 100 parts by weight of a polyphenylene sulfide resin. Polyphenylene sulfide resin composition,

Figure 2008101069
Figure 2008101069

(ここでR1、R2は炭素数1〜8の炭化水素基であり、R1とR2とは同じであっても異なっていてもよい。R3、R4は炭素数9から18のアシル基または炭化水素基であり、R3とR4とは同じであっても異なっていてもよい。R5〜R12は水素、ハロゲンまたは炭素数8以下の炭化水素基を表し、R5〜R12は同じであっても異なっていてもよい。m、nはそれぞれ1以上の整数を示し、mとnとは同じであっても異なっていてもよい。)
(2)(B)ポリアミド樹脂が、(b−1)カプロアミド単位と(b−2)ヘキサメチレンアジパミド単位の共重合体であることを特徴とする(1)記載のポリフェニレンサルファイド樹脂組成物、
(3)(B)ポリアミド樹脂が、(b−1)、(b−2)合計100重量%として、(b−1)カプロアミド単位70〜90重量%と(b−2)ヘキサメチレンアジパミド単位10〜30重量%からなる共重合体(ポリアミド6/66)であることを特徴とする(2)記載のポリフェニレンサルファイド樹脂組成物、
(4)(A)ポリフェニレンサルファイド樹脂100重量部に対して、(D)着色剤を0〜10重量部を配合してなる(1)から(3)のいずれか記載のポリフェニレンサルファイド樹脂組成物、
(5)(1)から(4)のいずれか記載のポリフェニレンサルファイド樹脂組成物からなる成形品、および
(6)成形品が電線被覆である(5)記載の成形品、
により構成される。
(Where R1 and R2 are hydrocarbon groups having 1 to 8 carbon atoms, and R1 and R2 may be the same or different. R3 and R4 are acyl groups or hydrocarbons having 9 to 18 carbon atoms. R3 and R4 may be the same or different, R5 to R12 represent hydrogen, halogen, or a hydrocarbon group having 8 or less carbon atoms, and R5 to R12 may be the same or different. M and n each represent an integer of 1 or more, and m and n may be the same or different.)
(2) The polyphenylene sulfide resin composition according to (1), wherein the (B) polyamide resin is a copolymer of (b-1) caproamide units and (b-2) hexamethylene adipamide units. ,
(3) (B) Polyamide resin is (b-1), (b-2) as a total of 100% by weight, (b-1) 70 to 90% by weight of caproamide units and (b-2) hexamethylene adipamide A polyphenylene sulfide resin composition according to (2), which is a copolymer (polyamide 6/66) comprising 10 to 30% by weight of units,
(4) (A) The polyphenylene sulfide resin composition according to any one of (1) to (3), wherein 0 to 10 parts by weight of the colorant is blended with 100 parts by weight of the polyphenylene sulfide resin.
(5) A molded article comprising the polyphenylene sulfide resin composition according to any one of (1) to (4), and (6) a molded article according to (5), wherein the molded article is a wire coating,
Consists of.

本発明の樹脂組成物は、電線被覆加工性に優れるとともに、高い耐摩耗性、耐熱性を有し、電線被覆用に好適な樹脂組成物を得ることが出来る。   The resin composition of the present invention is excellent in wire coating processability, has high wear resistance and heat resistance, and can provide a resin composition suitable for wire coating.

以下、本発明の実施形態を説明する。本発明において「重量」とは「質量」を意味する。   Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

本発明で用いられる(A)ポリフェニレンサルファイド樹脂とは、下記構造式(化2)で示される繰り返し単位を有する重合体であり、   The (A) polyphenylene sulfide resin used in the present invention is a polymer having a repeating unit represented by the following structural formula (Formula 2),

Figure 2008101069
Figure 2008101069

耐熱性の点から、好ましくは上記構造式で示される繰り返し単位含む重合体を70モル%以上、より好ましくは90モル%以上含む重合体である。またPPSはその繰り返し単位の30モル%以下程度が、下記の構造を有する繰り返し単位等で構成されていてもよい。 From the viewpoint of heat resistance, the polymer preferably contains 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula. In addition, about 30 mol% or less of the repeating units of PPS may be composed of repeating units having the following structure.

Figure 2008101069
Figure 2008101069

本発明で用いられるPPS樹脂の溶融粘度は、溶融混練が可能であれば特に制限はないが、316℃、荷重5000gの条件下で測定するメルトフローレートの測定値として10〜20,000g/10minであることが好ましく、さらには20〜10,000g/10minであることが好ましい。   The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible. However, the melt flow rate measured at 316 ° C. under a load of 5000 g is 10 to 20,000 g / 10 min. It is preferable that it is 20 to 10,000 g / 10min.

かかる特性を満たすPPSは、特公昭45−3368号公報で代表される製造方法により得られる比較的分子量の小さな重合体を得る方法、或いは特公昭52−12240号公報や特開昭61−7332号公報に記載される比較的分子量の大きな重合体を得る方法などの公知の方法によって製造できる。   PPS satisfying such properties is a method for obtaining a polymer having a relatively low molecular weight obtained by a production method represented by Japanese Patent Publication No. 45-3368, or Japanese Patent Publication No. 52-12240 and Japanese Patent Publication No. 61-7332. It can be produced by a known method such as a method for obtaining a polymer having a relatively large molecular weight described in the publication.

上記により得られたPPS樹脂は、そのまま使用してもよく、また空気中加熱による架橋/高分子量化、窒素などの不活性ガス雰囲気下或は減圧下での熱処理、また、有機溶媒、熱水、酸水溶液などによる洗浄を施した上で使用することも可能である。   The PPS resin obtained as described above may be used as it is, or it may be used for crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, organic solvent, hot water. It is also possible to use after washing with an acid aqueous solution or the like.

有機溶媒で洗浄する場合、用いる有機溶媒としてはPPSを分解する作用を有しないものであれば特に制限はなく、例えば、N−メチルピロリドン、ジメチルホルムアルデヒド、ジメチルアセトアミド、1,3−ジメチルイミダゾリジノン、ヘキサメチルホスホラスアミド、ピペラジノン類などの含窒素極性溶媒、ジメチルスルホキシド、ジメチルスルホン、スルホランなどのスルホキシド・スルホン系溶媒、アセトン、メチルエチルケトン、ジエチルケトン、アセトフェノンなどのケトン系溶媒、ジメチルエ−テル、ジプロピルエ−テル、ジオキサン、テトラヒドロフランなどのエ−テル系溶媒、クロロホルム、塩化メチレン、トリクロロエチレン、2塩化エチレン、パ−クロルエチレン、モノクロルエタン、ジクロルエタン、テトラクロルエタン、パ−クロルエタン、クロルベンゼンなどのハロゲン系溶媒、メタノ−ル、エタノ−ル、プロパノ−ル、ブタノ−ル、ペンタノ−ル、エチレングリコ−ル、プロピレングリコ−ル、フェノ−ル、クレゾ−ル、ポリエチレングリコ−ル、ポリプロピレングリコ−ルなどのアルコ−ル・フェノ−ル系溶媒、及びベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒などが挙げられる。   In the case of washing with an organic solvent, the organic solvent to be used is not particularly limited as long as it does not have an action of decomposing PPS. For example, N-methylpyrrolidone, dimethylformaldehyde, dimethylacetamide, 1,3-dimethylimidazolidinone , Nitrogen-containing polar solvents such as hexamethylphosphorus amide and piperazinones, sulfoxide and sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone, dimethyl ether and dipropyl ether -Ether solvents such as tellurium, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchloroethylene, monochloroethane, dichloroethane, tetrachloro Halogen solvents such as ethane, perchloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanole, ethylene glycol, propylene glycol, phenol, cresol And alcohol / phenol solvents such as polyethylene glycol and polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene and xylene.

洗浄温度についても特に制限はなく、通常、常温〜300℃程度が選択される。酸水溶液で洗浄する場合、用いる酸としてはPPSを分解する作用を有しないものであれば特に制限はなく、例えば、酢酸、塩酸、硫酸、リン酸、珪酸、炭酸及びプロピル酸などが挙げられる。また、酸無水物基、エポキシ基、イソシアネ−ト基などの官能基含有化合物による活性化などの種々の処理を施した上で使用することも可能である。本発明のペレットの製造方法においては、上記PPS樹脂をそのままもしくは、それと他の成分とを配合したPPS樹脂組成物が溶融押出しに供される。   There is no restriction | limiting in particular also about washing | cleaning temperature, Usually, about normal temperature-about 300 degreeC are selected. In the case of washing with an acid aqueous solution, the acid to be used is not particularly limited as long as it does not have an action of decomposing PPS, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. Moreover, it can also be used after performing various treatments such as activation with a functional group-containing compound such as an acid anhydride group, an epoxy group, or an isocyanate group. In the method for producing pellets of the present invention, the above PPS resin is used as it is or a PPS resin composition in which it is blended with other components is subjected to melt extrusion.

上記PPS樹脂との配合に供する他の成分としては特に制限はないが、本発明の効果を損なわない範囲で、シラン化合物、離型剤、結晶核剤などの通常の添加剤および少量の変性オレフィン系樹脂、あるいはその他ポリマーを添加することができる。   Although there is no restriction | limiting in particular as another component with which it mix | blends with the said PPS resin, In the range which does not impair the effect of this invention, normal additives, such as a silane compound, a mold release agent, and a crystal nucleating agent, and a small amount of modified olefins System resins or other polymers can be added.

本発明で用いられる(B)ポリアミド樹脂とは、アミノ酸、ラクタムあるいはジアミンとジカルボン酸を主たる構成成分とするポリアミドである。その主要構成成分の代表例としては、6−アミノカプロン酸、11−アミノウンデカン酸、12−アミノドデカン酸、パラアミノメチル安息香酸などのアミノ酸、ε−カプロラクタム、ω−ラウロラクタムなどのラクタム、テトラメチレンジアミン、ヘキサメチレンジアミン、1,5−ペンタンジアミン、2−メチルペンタメチレンジアミン、ノナメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、2,2,4−/2,4,4−トリメチルヘキサメチレンジアミン、5−メチルノナメチレンジアミン、メタキシレンジアミン、パラキシレンジアミン、1,3−ビス(アミノメチル)シクロヘキサン、1,4−ビス(アミノメチル)シクロヘキサン、1−アミノ−3−アミノメチル−3,5,5−トリメチルシクをロヘキサン、ビス(4−アミノシクロヘキシル)メタン、ビス(3−メチル−4−アミノシクロヘキシル)メタン、2,2−ビス(4−アミノシクロヘキシル)プロパン、ビス(アミノプロピル)ピペラジン、アミノエチルピペラジンなどの脂肪族、脂環族、芳香族のジアミン、およびアジピン酸、スペリン酸、アゼライン酸、セバシン酸、ドデカン二酸、テレフタル酸、イソフタル酸、2−クロロテレフタル酸、2−メチルテレフタル酸、5−メチルイソフタル酸、5−ナトリウムスルホイソフタル酸、2,6−ナフタレンジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸などの脂肪族、脂環族、芳香族のジカルボン酸が挙げられ、本発明においては、これらの原料から誘導されるポリアミドホモポリマーまたはコポリマーを各々単独または混合物の形で用いることができる。   The (B) polyamide resin used in the present invention is a polyamide mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, and tetramethylenediamine. , Hexamethylenediamine, 1,5-pentanediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5 5-trimethylsick Fats such as sun, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine , Cycloaliphatic, aromatic diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. Polyamide homopolymers or copolymers derived from the raw materials of Each can be used alone or in the form of mixtures.

本発明において、特に有用なポリアミド樹脂は、150℃以上の融点を有する耐熱性や強度に優れたポリアミド樹脂であり、具体的な例としてはポリカプロアミド(ポリアミド6)、ポリヘキサメチレンアジパミド(ポリアミド66)、ポリペンタメチレンアジパミド(ポリアミド56)、ポリテトラメチレンアジパミド(ポリアミド46)、ポリヘキサメチレンセバカミド(ポリアミド610)、ポリヘキサメチレンドデカミド(ポリアミド612)、ポリウンデカンアミド(ポリアミド11)、ポリドデカンアミド(ポリアミド12)、ポリカプロアミド/ポリヘキサメチレンアジパミドコポリマー(ポリアミド6/66)、ポリカプロアミド/ポリヘキサメチレンテレフタルアミドコポリマー(ポリアミド6/6T)、ポリヘキサメチレンアジパミド/ポリヘキサメチレンイソフタルアミドコポリマー(ポリアミド66/6I)、ポリヘキサメチレンテレフタルアミド/ポリヘキサメチレンイソフタルアミドコポリマー(ポリアミド6T/6I)、ポリヘキサメチレンテレフタルアミド/ポリドデカンアミドコポリマー(ポリアミド6T/12)、ポリヘキサメチレンアジパミド/ポリヘキサメチレンテレフタルアミド/ポリヘキサメチレンイソフタルアミドコポリマー(ポリアミド66/6T/6I)、ポリキシリレンアジパミド(ポリアミドXD6)、ポリヘキサメチレンテレフタルアミド/ポリ−2−メチルペンタメチレンテレフタルアミドコポリマー(ポリアミド6T/M5T)、ポリノメチレンテレフタルアミドフタルアミド単位を有する共重合体を挙げることができ、更にこれらのポリアミド樹脂を成形加工性、相溶性などの必要特性に応じて混合物として用いることも実用上好適である。耐摩耗性には、表面硬度と柔軟性のバランスが重要であり、とりわけ好ましいポリアミド樹脂は、カプロアミド単位、ヘキサメチレンアジパミド単位からなる共重合ポリアミド、ポリアミド6/66である。   In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (polyamide 6), polyhexamethylene adipamide. (Polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecane Amide (polyamide 11), polydodecanamide (polyamide 12), polycaproamide / polyhexamethylene adipamide copolymer (polyamide 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (polyamide 6 / 6T), polyhexamethy Adipamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (polyamide 6T / 12) , Polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyxylylene adipamide (polyamide XD6), polyhexamethylene terephthalamide / poly-2- Mention may be made of methylpentamethylene terephthalamide copolymers (polyamide 6T / M5T) and copolymers having polynomethylene terephthalamide phthalamide units. Can, furthermore also practically preferable to use a mixture in accordance with the required characteristics such as these polyamide resins moldability, compatibility. A balance between surface hardness and flexibility is important for wear resistance, and particularly preferred polyamide resins are copolyamides composed of caproamide units and hexamethylene adipamide units, and polyamide 6/66.

このポリアミド6/66の共重合ポリアミドの共重合重量比率は、(b−1)、(b−2)合計100重量部として、(b−1)カプロアミド単位70〜90重量%と(b−2)ヘキサメチレンアジパミド単位10〜30重量%からなることが、被覆電線の柔軟性と耐摩耗性のバランスから好ましい。より好ましくは、(b−1)カプロアミド単位75〜90重量%、(b−2)ヘキサメチレンアジパミド単位10〜25重量%の範囲である。   This polyamide 6/66 copolymerized polyamide has a copolymer weight ratio of (b-1), (b-2) total 100 parts by weight, and (b-1) 70 to 90% by weight of caproamide units (b-2). It is preferable that it consists of 10 to 30% by weight of hexamethylene adipamide units from the balance of flexibility and wear resistance of the covered electric wire. More preferably, the range is (b-1) 75 to 90% by weight of caproamide units and (b-2) 10 to 25% by weight of hexamethylene adipamide units.

これらポリアミド樹脂の重合度には特に制限がないが、サンプル濃度0.01g/mlの98%濃硫酸溶液中、25℃で測定した相対粘度で、2.0〜7.0の範囲のものが好ましく、より好ましくは2.2〜6.0、特に好ましくは2.5〜5.5範囲である。   The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 2.0 to 7.0. More preferably, it is 2.2-6.0, Most preferably, it is the range of 2.5-5.5.

本発明で用いられる(C)芳香族化合物とは、下記構造式で表される化合物である。   The (C) aromatic compound used in the present invention is a compound represented by the following structural formula.

Figure 2008101069
Figure 2008101069

ここで、R1、R2は炭素数1〜8の炭化水素基であり、具体的にはメチル基、エチル基、フェニル基、オクチル基などが例示され、中でも入手性が容易である意味でメチル基であることが特に好ましい。R1とR2とは同じであっても異なっていてもよい。R3、R4は炭素数9〜18のアシル基または炭化水素基であり、R3とR4とは同じであっても異なっていてもよい。R3、R4はアシル基である場合が好ましく、炭素数10〜15のアシル基であることが特に好ましい。R3、R4の炭素数が8以下の場合は、耐熱性の点で不十分となる。また、R3、R4の炭素数が18を越えると、相溶性が不十分となるため好ましくない。R5〜12は水素、または炭素数8以下の炭化水素基を表し、R5〜12は同じであっても異なっていてもよい。R5〜12は水素の場合が好ましい。m、nはそれぞれ1以上の整数を示し、mとnとは同じであっても異なっていてもよいが、より優れた耐熱性、耐湿熱性を有するポリアリーレンサルファイド樹脂組成物を得る意味からは、m、nがそれぞれ3以下であることが好ましく、n=m=1の場合が特に好ましい。市販されている代表例としては、花王株式会社製エキセパールBP−DLが挙げられる。 Here, R1 and R2 are hydrocarbon groups having 1 to 8 carbon atoms, and specific examples include a methyl group, an ethyl group, a phenyl group, an octyl group, and the like. It is particularly preferred that R1 and R2 may be the same or different. R3 and R4 are acyl groups or hydrocarbon groups having 9 to 18 carbon atoms, and R3 and R4 may be the same or different. R3 and R4 are preferably an acyl group, and particularly preferably an acyl group having 10 to 15 carbon atoms. When R3 and R4 have 8 or less carbon atoms, the heat resistance is insufficient. On the other hand, if R3 and R4 have more than 18 carbon atoms, the compatibility becomes insufficient, which is not preferable. R5 to 12 represent hydrogen or a hydrocarbon group having 8 or less carbon atoms, and R5 to 12 may be the same or different. R5 to 12 are preferably hydrogen. m and n each represent an integer of 1 or more, and m and n may be the same or different, but from the viewpoint of obtaining a polyarylene sulfide resin composition having better heat resistance and heat and moisture resistance. , M and n are each preferably 3 or less, particularly preferably n = m = 1. A typical example that is commercially available is Exepearl BP-DL manufactured by Kao Corporation.

本発明における(B)ポリアミド樹脂は、(A)ポリフェニレンサルファイド樹脂100重量部に対して12〜100重量部であることが必要である。12重量部以下では耐摩耗性を損ない、100重量部以上では耐熱性、柔軟性、耐火炎伝播性を損なう。好ましくは14〜90重量部、より好ましくは15〜85重量部の範囲である。   (B) Polyamide resin in this invention needs to be 12-100 weight part with respect to 100 weight part of (A) polyphenylene sulfide resin. If it is 12 parts by weight or less, the wear resistance is impaired, and if it is 100 parts by weight or more, the heat resistance, flexibility, and flame propagation property are impaired. Preferably it is 14-90 weight part, More preferably, it is the range of 15-85 weight part.

本発明において、(C)下記構造式で表される芳香族化合物は、(A)ポリフェニレンサルファイド樹脂100重量部に対して、6〜12重量部であることが必要である。6重量部以下ではISO6722で評価される耐熱性、および柔軟性を損ない、12重量部以上では安定した被覆押出が困難になるばかりか、ISO6722で評価される耐熱性の向上が認められない。好ましくは6〜10重量部の範囲である。   In the present invention, (C) the aromatic compound represented by the following structural formula needs to be 6 to 12 parts by weight with respect to 100 parts by weight of (A) polyphenylene sulfide resin. If it is 6 parts by weight or less, the heat resistance and flexibility evaluated by ISO 6722 are impaired, and if it is 12 parts by weight or more, stable coating extrusion becomes difficult, and no improvement in heat resistance evaluated by ISO 6722 is observed. Preferably it is the range of 6-10 weight part.

本発明のポリフェニレンサルファイド樹脂組成物には、さらに(D)着色剤を添加することで、自動車や家電製品など、組み立て工程にて色で部材識別が出来る電線被覆用途などに適した組成物とすることが出来るので好ましい。(D)着色剤としては、その種類に特に制限はなく、顔料、有機顔料、染料など、任意のものを使用することが出来る。耐熱性の観点から顔料がより好ましい。顔料としては、青色顔料、緑色顔料、赤色顔料、黄色顔料、紫色顔料、オレンジ顔料、ブラウン顔料、黒色顔料などが代表例として挙げられ、単独しくは複数使用することが出来る。有機顔料としては、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリンノン系、ジオキサジン系、インダンスレン系、ペリレン系などの構造のものが代表例として挙げられ、単一もしくは複数使用することが出来る。染料としては、アゾ系染料、アントラキノン系染料、フタロシアニン系染料、キノンイミン系染料、キノリン系染料、ニトロ系染料、カルボニル系染料、メチン系染料などが代表例として挙げられ、単独もしくは複数使用することが出来る。また、顔料、有機顔料、染料を同時に使用することも出来る。   The polyphenylene sulfide resin composition of the present invention is a composition suitable for wire coating applications that can identify members by color in the assembly process, such as automobiles and home appliances, by further adding a colorant (D). This is preferable. (D) There is no restriction | limiting in particular as a coloring agent, Arbitrary things, such as a pigment, an organic pigment, dye, can be used. A pigment is more preferable from the viewpoint of heat resistance. Typical examples of the pigment include blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, black pigments, and a single pigment or a plurality of pigments can be used. Representative examples of organic pigments include azo, phthalocyanine, quinacridone, benzimidazolone, isoindoline non, dioxazine, indanthrene, and perylene types. Can be used. Representative examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. I can do it. Also, pigments, organic pigments, and dyes can be used at the same time.

本発明の(D)着色剤は、(A)ポリフェニレンサルファイド樹脂100重量部に対して、0〜10重量部であることが好ましい。樹脂組成物の着色性と耐摩耗性、巻き付け試験時の柔軟性の観点から0.1〜10重量部が好ましく、さらに好ましくは0.1〜6重量部の範囲である。   The (D) colorant of the present invention is preferably 0 to 10 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. From the viewpoint of the colorability and wear resistance of the resin composition and the flexibility during the winding test, 0.1 to 10 parts by weight is preferable, and 0.1 to 6 parts by weight is more preferable.

本発明のポリフェニレンサルファイド樹脂組成物には、さらに本発明の目的を損なわない範囲で他のポリマー、銅系熱安定剤、ヒンダードフェノール系、リン系、イオウ系などの酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、離型剤、帯電防止剤、および難燃剤などの通常の添加剤を1種以上添加することができる。   The polyphenylene sulfide resin composition of the present invention further includes other polymers, copper-based heat stabilizers, hindered phenol-based, phosphorus-based, sulfur-based antioxidants and the like as long as the object of the present invention is not impaired. One or more usual additives such as ultraviolet absorbers, lubricants, mold release agents, antistatic agents, and flame retardants can be added.

本発明のポリフェニレンサルファイド樹脂組成物製造方法は特に制限はなく、例えば単軸または2軸の押出機やニーダー等の混練機を用いて280〜350℃の温度で溶融混練する方法等が挙げられる。その際、(A)ポリフェニレンサルファイド樹脂、(B)ポリアミド樹脂、(C)芳香族化合物は、ミキサーやブレンダーで事前にすべてを混合したのち溶融混練する方法や、(C)芳香族化合物と(A)ポリフェニレンサルファイド樹脂を事前に溶融混練しマスターバッチ化したのち、得られたマスターバッチと(B)ポリアミド樹脂とを溶融混練する方法、(C)芳香族化合物と(B)ポリアミド樹脂を事前に溶融混練しマスターバッチ化したのち、得られたマスターバッチと(A)ポリフェニレンサルファイド樹脂とを溶融混練する方法などが挙げられる。   The method for producing the polyphenylene sulfide resin composition of the present invention is not particularly limited, and examples thereof include a method of melt kneading at a temperature of 280 to 350 ° C. using a kneader such as a single screw or twin screw extruder or a kneader. At that time, (A) polyphenylene sulfide resin, (B) polyamide resin, and (C) aromatic compound are mixed in advance with a mixer or blender and then melt-kneaded, or (C) aromatic compound and (A ) Method of melt-kneading polyphenylene sulfide resin in advance to master batch, then melt-kneading the obtained master batch and (B) polyamide resin, (C) Melting aromatic compound and (B) polyamide resin in advance Examples of the method include a method of melt-kneading the obtained master batch and (A) polyphenylene sulfide resin after kneading and making a master batch.

本発明の樹脂組成物によって、従来では達成することのできなかった非常に高い耐摩耗性、ISO6722で定められる耐熱性を両立できるため、電線被覆用途に特に好適である。   Since the resin composition of the present invention can achieve both extremely high wear resistance that could not be achieved in the past and heat resistance defined by ISO 6722, it is particularly suitable for wire coating applications.

以下、実施例を挙げてさらに本発明を詳細に説明するが、本発明はこれらにより限定されるものではない。実施例および比較例に用いた測定方法を以下に示す。   EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited by these. Measurement methods used in Examples and Comparative Examples are shown below.

(1)耐摩耗性の評価
参考例3に従って作成した被覆電線について、ISO6722 9.3項に従って評価した。使用する針の直径は0.45mmを採用した。
(1) Evaluation of Abrasion Resistance The covered electric wire prepared according to Reference Example 3 was evaluated according to ISO 6722 9.3. The diameter of the needle used was 0.45 mm.

(2)耐熱性の評価
参考例3に従って作成した被覆電線について、ISO6722 10.1項、耐熱クラスクラスBに従い125℃で240時間乾熱処理を行い、−25℃雰囲気内で巻きつけ試験を実施した。
(2) Evaluation of heat resistance The covered electric wire prepared according to Reference Example 3 was subjected to a dry heat treatment at 125 ° C. for 240 hours in accordance with ISO 6722 10.1 and heat resistance class class B, and a winding test was performed in a −25 ° C. atmosphere. .

(3)巻き付け試験
参考例3に従って作成した被覆電線について、ISO6722 8項を参考に、常温にて巻き付け試験を実施し、柔軟性の指標とした。判断基準は以下の通りである。
◎:5回中1度も被覆裂けが発生しない。
○:5回中1回被覆裂けが発生する。
△:5回中2〜3回被覆裂けが発生する。
×:5回中4〜5回被覆裂けが発生する。
(3) Winding test The covered electric wire prepared according to Reference Example 3 was subjected to a winding test at room temperature with reference to ISO 6722, item 8, and used as an index of flexibility. Judgment criteria are as follows.
(Double-circle): A coating crack does not generate | occur | produce even once in 5 times.
○: Coating crack occurs once out of 5 times.
(Triangle | delta): Cover tearing generate | occur | produced 2 to 3 times in 5 times.
X: Cover tear occurs 4 to 5 times out of 5 times.

(4)耐火炎伝播性の評価
参考例3に従って作成した被覆電線について、ISO6722 12項に従って評価した。
(4) Evaluation of flame propagation property The covered electric wire prepared according to Reference Example 3 was evaluated according to ISO 6722, item 12.

(5)被覆加工安定性の評価
参考例3に従って作成した被覆電線10mについて、異物の有無を目視にて確認した。被覆加工安定性が悪化するとシリンダ内の滞留が起き、異物が発生する。判断基準は以下の通りである。
◎:目立った異物が見られない。
○:目立った異物が1〜2個以上見られる。
△:目立った異物が3〜910個見られる。
×:目立った異物が10個以上見られる。
(5) Evaluation of coating processing stability About the covered electric wire 10m produced according to the reference example 3, the presence or absence of the foreign material was confirmed visually. If the coating processing stability deteriorates, the cylinder stays and foreign matter is generated. Judgment criteria are as follows.
A: No noticeable foreign matter is seen.
○: One or more conspicuous foreign matters are seen.
Δ: 3 to 910 conspicuous foreign matters are seen.
X: Ten or more conspicuous foreign matters are seen.

参考例1 PPS樹脂の製造
攪拌機付きオートクレーブに硫化ナトリウム9水塩6.005kg(25モル)、酢酸ナトリウム0.205kg(2.5モル)およびNMP5kgを仕込み、窒素を通じながら徐々に205℃まで昇温し、水3.6リットルを留出した。次に反応容器を180℃に冷却後、1,4−ジクロロベンゼン3.719kg(25.3モル)ならびにNMP3.7kgを加えて、窒素下に密閉し、270℃まで昇温後、270℃で2.5時間反応した。冷却後、反応生成物を温水で5回洗浄し、次に100℃に加熱されNMP10kg中に投入して、約1時間攪拌し続けたのち、濾過し、さらに熱湯で数回洗浄した。これを90℃に加熱されたpH4の酢酸水溶液25リットル中に投入し、約1時間攪拌し続けたのち、濾過し、濾過のpHが7になるまで約90℃のイオン交換水で洗浄後、80℃で24時間減圧乾燥して、MFR600(g/10min)のポリフェニレンサルファイド樹脂を得た。なお、MFRは316℃、荷重5000gの条件でISO1133に従い測定した。
Reference Example 1 Production of PPS resin An autoclave equipped with a stirrer was charged with 6.005 kg (25 mol) of sodium sulfide nonahydrate, 0.205 kg (2.5 mol) of sodium acetate and 5 kg of NMP, and gradually heated to 205 ° C. through nitrogen. Then, 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C., 3.719 kg (25.3 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated to 270 ° C. Reacted for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water, then heated to 100 ° C., poured into 10 kg of NMP, stirred for about 1 hour, filtered, and washed several times with hot water. This was poured into 25 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and stirred for about 1 hour, filtered, washed with ion-exchanged water at about 90 ° C. until the pH of filtration became 7, It dried under reduced pressure at 80 degreeC for 24 hours, and obtained the polyphenylene sulfide resin of MFR600 (g / 10min). The MFR was measured according to ISO 1133 under the conditions of 316 ° C. and a load of 5000 g.

参考例2 共重合ポリアミド6/66樹脂の製造
実施例、ならびに比較例で用いた共重合ポリアミド樹脂は以下の方法で重合した。ヘキサメチレンジアミンとアジピン酸の当モル塩、およびεカプロラクタムをそれぞれ表に記載の重量比で投入し、投入した全量と同量の純水を加え、重合缶内をNで置換した後、攪拌しながら加熱を開始し、缶内圧力を最大20kg/cmに調整しながら最終到達温度を270℃とし反応させた。水浴中に吐出したポリマーをストランドカッターでペレタイズした。ペレットは80℃で50時間以上乾燥し、粘度数230(ml/g)の共重合ポリアミド6/66樹脂を得た。なお、粘度数は、濃度96重量%硫酸を用い、ISO307に従い測定した。
Reference Example 2 Production of Copolyamide 6/66 Resin Copolymer polyamide resin used in Examples and Comparative Examples was polymerized by the following method. Hexamethylenediamine and adipic acid equimolar salt and ε-caprolactam were added in the weight ratios shown in the table, respectively, and the same amount of pure water as the total amount added was added, and the inside of the polymerization vessel was replaced with N 2 , followed by stirring. Then, heating was started, and the final achieved temperature was set to 270 ° C. while the internal pressure of the can was adjusted to 20 kg / cm 2 at maximum. The polymer discharged into the water bath was pelletized with a strand cutter. The pellet was dried at 80 ° C. for 50 hours or more to obtain a copolymerized polyamide 6/66 resin having a viscosity number of 230 (ml / g). The viscosity number was measured in accordance with ISO 307 using 96% by weight sulfuric acid.

参考例3 ポリアミド6樹脂の製造
実施例、ならびに比較例で用いたポリアミド6樹脂は以下の方法で重合した。ε−カプロラクタム(東レ(株)製)1500g、イオン交換水375gを秤量し、重合缶に仕込み、常圧、窒素フロー下で攪拌しながら最終到達温度260℃とし反応させた。水浴中に吐出したポリマーをストランドカッターでペレタイズした。得られたペレットは95℃熱水中で20時間処理し、未反応モノマーや低重合物を抽出除去した。抽出後のペレットは80℃で50時間以上乾燥し、粘度数240(ml/g)のポリアミド6樹脂を得た。なお、粘度数は、濃度96重量%硫酸を用い、ISO307に従い測定した。
Reference Example 3 Production of polyamide 6 resin The polyamide 6 resin used in the examples and comparative examples was polymerized by the following method. 1500 g of ε-caprolactam (manufactured by Toray Industries, Inc.) and 375 g of ion-exchanged water were weighed, charged into a polymerization can, and reacted at a final reached temperature of 260 ° C. while stirring under normal pressure and nitrogen flow. The polymer discharged into the water bath was pelletized with a strand cutter. The obtained pellets were treated in hot water at 95 ° C. for 20 hours to extract and remove unreacted monomers and low polymer. The pellet after extraction was dried at 80 ° C. for 50 hours or more to obtain a polyamide 6 resin having a viscosity number of 240 (ml / g). The viscosity number was measured in accordance with ISO 307 using 96% by weight sulfuric acid.

参考例4 被覆電線の作成方法
実施例、ならびに比較例で用いた被覆電線は以下の方法で作成した。外径0.48mm、7本よりのスズめっきばん線に、聖製作所製30mmφ電線被覆装置を用い、シリンダ温度310℃、スクリュー回転数30prm、引き取り速度80m/分で実施例に示すポリフェニレンサルファイド樹脂組成物を押出成形にて被覆し、外径0.88mmの被覆電線を得た。
Reference Example 4 Method for Creating Covered Electric Wire The covered electric wires used in the examples and comparative examples were prepared by the following method. Polyphenylene sulfide resin composition shown in the examples in an outer diameter of 0.48 mm, a tin-plated wire of 7 wires, using a 30 mmφ wire coating device manufactured by Seisakusho, at a cylinder temperature of 310 ° C., a screw rotation speed of 30 prm, and a take-up speed of 80 m / min. The product was covered by extrusion to obtain a covered electric wire having an outer diameter of 0.88 mm.

実施例1
参考例1に示した重合方法で製造された(A)PPS樹脂100重量部、参考例2に示した重合方法で、カプロアミド単位80重量%、ヘキサメチレンアジパミド単位20重量%の共重合重量比にて製造された(B)ポリアミド樹脂71.4重量部、(C)芳香族化合物[花王株式会社製:商品名エキセパールBP−DL]7.1重量部を2軸押出機(東芝機械社製:TEM58)を用いてシリンダ設定温度310℃、スクリュ回転数250rpmの条件下で、すべてトップフィード(基込めフィード)し溶融混錬した後、ストランド状のガットを成形し、冷却バスで冷却後、カッターで造粒しペレットを得た。得られたペレットを参考例4に示した方法により被覆電線を作成し、前記の測定方法によって諸特性を調べた。その結果を表に示す。
Example 1
100 parts by weight of (A) PPS resin produced by the polymerization method shown in Reference Example 1 and 80% by weight of caproamide units and 20% by weight of hexamethylene adipamide units by the polymerization method shown in Reference Example 2 (B) Polyamide resin 71.4 parts by weight and (C) Aromatic compound [trade name Exepal BP-DL] 7.1 parts by weight produced by a twin screw extruder (Toshiba Machine Co., Ltd.) Manufactured by TEM58) under the conditions of a cylinder set temperature of 310 ° C. and a screw rotation speed of 250 rpm, all are top-feeded (incorporated feed), melted and kneaded, and then formed into a strand-shaped gut and cooled in a cooling bath And pelletized with a cutter. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

実施例2、3
(B)ポリアミド樹脂が表に示す重量部である以外は実施例1と同様にしてペレット、成形品を得て諸特性を調べた。その結果を表に示す。
Examples 2 and 3
(B) Pellets and molded products were obtained in the same manner as in Example 1 except that the polyamide resin was in parts by weight shown in the table, and various characteristics were examined. The results are shown in the table.

実施例4、5、6、7
(B)ポリアミド樹脂の共重合重量比が表に示す比率である以外は実施例2と同様にしてペレット、成形品を得て諸特性を調べた。その結果を表に示す。
Examples 4, 5, 6, 7
(B) Pellets and molded products were obtained in the same manner as in Example 2 except that the copolymerization weight ratio of the polyamide resin was the ratio shown in the table, and various characteristics were examined. The results are shown in the table.

実施例8
(B)ポリアミド樹脂が参考例3に示した重合方法で製造されたポリアミド6樹脂である以外は実施例2と同様にしてペレット、成形品を得て諸特性を調べた。その結果を表に示す。
Example 8
(B) Except that the polyamide resin is a polyamide 6 resin produced by the polymerization method shown in Reference Example 3, pellets and molded products were obtained in the same manner as in Example 2 and various characteristics were examined. The results are shown in the table.

実施例9、10、11、12、13、14
表に示す種類の(D)着色剤を表に示す重量部添加した以外は実施例2と同様にしてペレット、成形品を得て諸特性を調べた。その結果を表に示す。
Examples 9, 10, 11, 12, 13, 14
Pellets and molded articles were obtained in the same manner as in Example 2 except that the parts (D) of the colorant shown in the table were added in the weight parts shown in the table, and various properties were examined. The results are shown in the table.

比較例1
参考例1に示した重合方法で製造された(A)PPS樹脂100重量部、参考例2に示した重合方法で、カプロアミド単位80重量%、ヘキサメチレンアジパミド単位20重量%の共重合重量比にて製造された(B)ポリアミド樹脂42.9重量部を2軸押出機を用いて実施例1と同様にしてペレットを得た。得られたペレットを参考例4に示した方法により被覆電線を作成し、前記の測定方法によって諸特性を調べた。その結果を表に示す。
Comparative Example 1
100 parts by weight of (A) PPS resin produced by the polymerization method shown in Reference Example 1 and 80% by weight of caproamide units and 20% by weight of hexamethylene adipamide units by the polymerization method shown in Reference Example 2 Pellets were obtained in the same manner as in Example 1 by using 42.9 parts by weight of the (B) polyamide resin produced in a ratio using a twin screw extruder. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

比較例2
参考例1に示した重合方法で製造された(A)PPS樹脂100重量部を2軸押出機を用いて実施例1と同様にしてペレットを得た。得られたペレットを参考例4に示した方法により被覆電線を作成し、前記の測定方法によって諸特性を調べた。その結果を表に示す。
Comparative Example 2
Pellets were obtained in the same manner as in Example 1 using 100 parts by weight of the (A) PPS resin produced by the polymerization method shown in Reference Example 1 using a twin screw extruder. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

比較例3、4、5、6
(A)PPS樹脂、(B)ポリアミド樹脂、(C)芳香族化合物の表に示す重量部である以外は実施例1と同様にしてペレット、成形品を得て諸特性を調べた。その結果を表に示す。
Comparative Examples 3, 4, 5, 6
Except for the weight parts shown in the tables of (A) PPS resin, (B) polyamide resin, and (C) aromatic compound, pellets and molded products were obtained in the same manner as in Example 1, and various properties were examined. The results are shown in the table.

Figure 2008101069
Figure 2008101069

Figure 2008101069
Figure 2008101069

Figure 2008101069
Figure 2008101069

実施例1〜14および比較例1〜6より、PPS樹脂、ポリアミド樹脂、特定芳香族化合物を配合して得られた樹脂組成物は、優れた耐摩耗性、耐熱性を有する樹脂組成物を得られることが確認された。また、ポリアミド樹脂を共重合ポリアミド6/66樹脂とすることで、さらに柔軟性に優れる、電線被覆樹脂として特に優れる樹脂組成物を得られることが確認された。更に着色剤を配合することで、電線被覆樹脂として特に優れる樹脂組成物を得られることが確認された。   From Examples 1 to 14 and Comparative Examples 1 to 6, a resin composition obtained by blending a PPS resin, a polyamide resin, and a specific aromatic compound provides a resin composition having excellent wear resistance and heat resistance. It was confirmed that Moreover, it was confirmed that by using a polyamide resin as a copolymerized polyamide 6/66 resin, it is possible to obtain a resin composition that is further excellent in flexibility and particularly excellent as a wire coating resin. Furthermore, it was confirmed that a resin composition particularly excellent as a wire coating resin can be obtained by blending a colorant.

Claims (6)

(A)ポリフェニレンサルファイド樹脂100重量部に対して、(B)ポリアミド樹脂12〜100重量部、(C)下記構造式で表される芳香族化合物を6〜12重量部配合してなるポリフェニレンサルファイド樹脂組成物。
Figure 2008101069
(ここでR1、R2は炭素数1〜8の炭化水素基であり、R1とR2とは同じであっても異なっていてもよい。R3、R4は炭素数9から18のアシル基または炭化水素基であり、R3とR4とは同じであっても異なっていてもよい。R5〜R12は水素、ハロゲンまたは炭素数8以下の炭化水素基を表し、R5〜R12は同じであっても異なっていてもよい。m、nはそれぞれ1以上の整数を示し、mとnとは同じであっても異なっていてもよい。)
(A) Polyphenylene sulfide resin obtained by blending 12 to 100 parts by weight of polyamide resin and (C) 6 to 12 parts by weight of an aromatic compound represented by the following structural formula with respect to 100 parts by weight of polyphenylene sulfide resin Composition.
Figure 2008101069
(Where R1 and R2 are hydrocarbon groups having 1 to 8 carbon atoms, and R1 and R2 may be the same or different. R3 and R4 are acyl groups or hydrocarbons having 9 to 18 carbon atoms. R3 and R4 may be the same or different, R5 to R12 represent hydrogen, halogen, or a hydrocarbon group having 8 or less carbon atoms, and R5 to R12 may be the same or different. M and n each represent an integer of 1 or more, and m and n may be the same or different.)
(B)ポリアミド樹脂が、(b−1)カプロアミド単位と(b−2)ヘキサメチレンアジパミド単位の共重合体であることを特徴とする請求項1記載のポリフェニレンサルファイド樹脂組成物。 The polyphenylene sulfide resin composition according to claim 1, wherein the (B) polyamide resin is a copolymer of (b-1) caproamide units and (b-2) hexamethylene adipamide units. (B)ポリアミド樹脂が、(b−1)、(b−2)合計100重量%として、(b−1)カプロアミド単位70〜90重量%と(b−2)ヘキサメチレンアジパミド単位10〜30重量%からなる共重合体(ポリアミド6/66)であることを特徴とする請求項2記載のポリフェニレンサルファイド樹脂組成物。 (B) Polyamide resin is (b-1), (b-2) as a total of 100% by weight, (b-1) 70 to 90% by weight of caproamide units and (b-2) hexamethylene adipamide units 10 to 10%. The polyphenylene sulfide resin composition according to claim 2, which is a copolymer (polyamide 6/66) comprising 30% by weight. (A)ポリフェニレンサルファイド樹脂100重量部に対して、(D)着色剤を0〜10重量部を配合してなる請求項1から3のいずれか記載のポリフェニレンサルファイド樹脂組成物。 The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein 0 to 10 parts by weight of the colorant (D) is blended with 100 parts by weight of the (A) polyphenylene sulfide resin. 請求項1から4のいずれか記載のポリフェニレンサルファイド樹脂組成物からなる成形品。 A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 4. 成形品が電線被覆である請求項5記載の成形品。 The molded article according to claim 5, wherein the molded article is a wire coating.
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