JP2004193138A - Vinyl chloride based resin sheathed wire - Google Patents
Vinyl chloride based resin sheathed wire Download PDFInfo
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- JP2004193138A JP2004193138A JP2004039055A JP2004039055A JP2004193138A JP 2004193138 A JP2004193138 A JP 2004193138A JP 2004039055 A JP2004039055 A JP 2004039055A JP 2004039055 A JP2004039055 A JP 2004039055A JP 2004193138 A JP2004193138 A JP 2004193138A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
本発明は、耐熱老化性、耐油性に加えて、その他耐熱電線用途に適した諸物性を具備した塩化ビニル系樹脂組成物を用いた被覆電線に関するものである。 The present invention relates to a coated electric wire using a vinyl chloride resin composition having various properties suitable for heat-resistant electric wires in addition to heat aging resistance and oil resistance.
可塑剤により可塑化された塩化ビニル樹脂は、柔軟性や引張特性等の優れた機械的物性を有するため、電線、ホースあるいは建材等の多くの分野で利用されている。しかしながら、従来の、汎用の可塑剤により可塑化された塩化ビニル樹脂は、高温下に曝されることにより可塑剤が揮発し、その結果柔軟性や伸びが容易に損なわれるという難点がある。また、塩化ビニル樹脂の熱劣化によっても同様な機械的物性の低下が起こる。
この耐熱老化性を高めるための手段として、トリメリット酸エステル系あるいはピロメリット酸エステル系の可塑剤を用いる方法が検討されているが、従来の可塑剤では得られる耐熱老化性は十分とは言えなかった。また、上述のトリメリット酸エステル系可塑剤あるいはピロメリット酸エステル系可塑剤を用いると、耐油性が劣るという問題も生じる。
また、電線用途、なかでも自動車電線用途では、耐熱性付与の手段として、通常、架橋技術が採用されているが、これにより必要な装置、工数等が増えるという問題がある。そのため架橋技術以外の方法での電線加工方法が注目されている。そこで、上述の耐熱老化性を得るための、上述のトリメリット酸エステルあるいはピロメリット酸エステル系可塑剤を用いる方法が検討されているが、自動車電線等に要求される耐油性、耐寒性、耐摩耗性、硬度等の諸物性を総合的に満足させる塩化ビニル系樹脂組成物は見出されなかった。
A vinyl chloride resin plasticized by a plasticizer has excellent mechanical properties such as flexibility and tensile properties, and is therefore used in many fields such as electric wires, hoses, and building materials. However, a conventional vinyl chloride resin plasticized with a general-purpose plasticizer has a drawback that the plasticizer volatilizes when exposed to a high temperature, and as a result, flexibility and elongation are easily impaired. Further, similar mechanical deterioration of mechanical properties occurs due to thermal deterioration of the vinyl chloride resin.
As a means for increasing the heat aging resistance, a method using a trimellitic acid ester-based or pyromellitic acid ester-based plasticizer has been studied, but it can be said that the heat aging resistance obtained with a conventional plasticizer is sufficient. Did not. Further, when the above-mentioned trimellitic acid ester plasticizer or pyromellitic acid ester plasticizer is used, there is a problem that oil resistance is poor.
Further, in electric wire applications, especially in automotive electric wire applications, as a means for imparting heat resistance, a cross-linking technique is usually employed. However, there is a problem in that the required equipment and man-hours are increased. Therefore, an electric wire processing method other than the cross-linking technique has attracted attention. Therefore, in order to obtain the above-mentioned heat aging resistance, a method using the above-mentioned trimellitic acid ester or pyromellitic acid ester-based plasticizer has been studied, but the oil resistance, cold resistance, and oil resistance required for automobile electric wires and the like are being studied. No vinyl chloride-based resin composition satisfying various physical properties such as abrasion and hardness has been found.
一方、鉛系安定剤を用いて、耐熱老化性を高める技術について数多く知られている。特に鉛系安定剤として珪酸鉛系化合物を使用する事により耐熱老化性が顕著に向上することは公知の事実となっている（例えば、特許文献１参照）。しかし、近年、経済協力開発機構（Ｏｒｇａｎｉｓａｔｉｏｎ ｆｏｒ Ｅｃｏｎｏｍｉｃ Ｃｏ−ｏｐｅｒａｔｉｏｎ ａｎｄ Ｄｅｖｅｌｏｐｍｅｎｔ：ＯＥＣＤ）による世界中の鉛撤廃の検討、厚生省よりＪＩＳ上下水道管の鉛溶出基準の見直しによる鉛系安定剤の使用禁止、通産省による２０００年末までに自動車のリサイクル率を９０％にするガイドラインが提出され、自動車メーカーでは新型車の鉛使用量の半減等の非鉛系の方向付けが進みつつある。これらの中で塩化ビニル系樹脂における鉛系安定剤の使用は、今後益々厳しく制限され、非鉛系安定剤への切替えが必要となってくる。
本発明は、上記の従来の問題点を解決し、耐熱老化性、耐油性に加えて耐寒性、適度の硬度等の諸特性を有する耐熱電線用途に適した塩化ビニル系樹脂組成物を用いた被覆電線を提供することを目的とする。 The present invention solves the above-mentioned conventional problems, and uses a vinyl chloride-based resin composition suitable for heat-resistant electric wire applications having various properties such as cold aging resistance, moderate hardness in addition to heat aging resistance and oil resistance. It is intended to provide a covered electric wire.
本発明者らは、かかる問題点を解決するために鋭意検討を行った結果、特定の直鎖率のトリメリット酸エステル系もしくはピロメリット酸エステル系の可塑剤をポリエステル系可塑剤と組合わせた特定の塩化ビニル系樹脂組成物が非鉛系安定剤を用いた場合においても、鉛系安定剤を用いた場合と同等の物性を維持できること、さらにはその場合に、全可塑剤中のトリメリット酸エステルの重量比などをさらに限定したとき、もしくは特定のピロメリット酸エステルを用い、ポリエステル系可塑剤を特定の比率にしたときに諸物性が向上し、耐熱電線用途として適した塩化ビニル系樹脂組成物およびそれを用いた被覆電線が得られることを見い出し、この知見に基づき本発明をなすに至った。 The present inventors have conducted intensive studies to solve such problems, and as a result, combined a trimellitate or pyromellitic ester plasticizer with a specific linearity with a polyester plasticizer. Even when a specific vinyl chloride-based resin composition uses a lead-free stabilizer, it can maintain the same physical properties as when a lead-based stabilizer is used. When the weight ratio of the acid ester is further limited, or when a specific pyromellitic acid ester is used and the polyester plasticizer is used in a specific ratio, various physical properties are improved, and a vinyl chloride resin suitable for heat-resistant electric wire applications. The present inventors have found that a composition and a coated electric wire using the same can be obtained, and have accomplished the present invention based on this finding.
すなわち、本発明は、
（１）塩化ビニル系樹脂１００重量部に対し、炭素数が４〜１２で直鎖率が５０〜１００％の飽和脂肪族アルコールを原料として得られるトリメリット酸エステルおよびピロメリット酸エステルからなる群から選ばれる少なくとも１種の多価カルボン酸エステル系可塑剤３０〜６０重量部、２５℃での粘度が１０００ｃｐｓ以上のポリエステル系可塑剤３〜２０重量部、ハイドロタルサイト化合物５〜４０重量部および亜鉛系金属石鹸０．０５〜５重量部から成り、この可塑剤の合計添加量が３５〜７０重量部であり、かつ全可塑剤中のトリメリット酸エステルの割合が重量比で０．５以下、全可塑剤中のポリエステル系可塑剤の割合が重量比で０．４以下である塩化ビニル系樹脂組成物を被覆材に用いた被覆電線、および
（２）多価カルボン酸エステル系可塑剤として炭素数８〜１０で直鎖率が９０％以上の飽和脂肪族アルコールを原料とするピロメリット酸エステルを用い、かつ全可塑剤中のポリエステル系可塑剤の割合が重量比で０．１〜０．４の範囲で用いたことを特徴とする（１）項記載の被覆電線
を提供するものである。
上記（１）又は（２）項に記載の発明を以下の説明において第１又は第２発明と、それぞれいう。
本発明において、直鎖率とは、多価カルボン酸エステル化合物のエステル部のアルキル基の炭素の結合形態に係るパラメータであり、直鎖アルキル基および分岐アルキル基の合計数に対する直鎖アルキル基数の割合（％）をいい、この直鎖率は、多価カルボン酸のエステル化に用いる飽和脂肪族アルコール中の直鎖アルコール組成（モル比）に相当するので、本明細書では、この飽和脂肪族アルコールの組成の直鎖率で説明する。なお、前記のエステル化合物は直鎖アルキル基と分岐アルキル基とが１つのエステル化合物中に併存する場合や、エステル部が全て直鎖アルキル基の化合物と、全て分岐アルキル基の化合物との混合物の場合、またはこれらが混在する場合など、その態様は制限はない。
That is, the present invention
(1) A group consisting of trimellitic acid esters and pyromellitic acid esters obtained from a saturated aliphatic alcohol having 4 to 12 carbon atoms and a linear ratio of 50 to 100% based on 100 parts by weight of a vinyl chloride resin. 30 to 60 parts by weight of at least one polycarboxylic acid ester-based plasticizer selected from the group consisting of 3 to 20 parts by weight of a polyester-based plasticizer having a viscosity at 25 ° C. of 1000 cps or more, 5 to 40 parts by weight of a hydrotalcite compound, and The zinc-based metal soap is composed of 0.05 to 5 parts by weight, the total amount of the plasticizer is 35 to 70 parts by weight, and the proportion of trimellitate in all the plasticizers is 0.5 or less by weight. A coated wire using a vinyl chloride resin composition having a weight ratio of a polyester plasticizer of 0.4 or less in all plasticizers as a coating material, and (2) a polyvalent carboxy resin. A pyromellitic acid ester containing a saturated aliphatic alcohol having 8 to 10 carbon atoms and a linear ratio of 90% or more as a raw material is used as the acid ester plasticizer, and the ratio of the polyester plasticizer in all the plasticizers is a weight ratio. The coated electric wire according to the above (1) is used in the range of 0.1 to 0.4.
The invention described in the above (1) or (2) will be referred to as the first or second invention in the following description, respectively.
In the present invention, the linearity ratio is a parameter relating to the bonding form of carbon of the alkyl group in the ester portion of the polycarboxylic acid ester compound, and is defined as the number of linear alkyl groups relative to the total number of linear alkyl groups and branched alkyl groups. It means a ratio (%), and this linear ratio corresponds to the linear alcohol composition (molar ratio) in the saturated aliphatic alcohol used for the esterification of polyvalent carboxylic acid. The linear ratio of the alcohol composition will be described. In addition, the said ester compound is a case where a straight-chain alkyl group and a branched alkyl group coexist in one ester compound, or a mixture of a compound in which all the ester portions are straight-chain alkyl groups and a compound in which all the branched alkyl groups are present. There is no limitation on the mode, for example, or when these are mixed.
本発明によれば耐熱老化性、耐油性、耐寒性、適度の硬度等の諸特性を有し、耐熱性に優れる塩化ビニル系樹脂組成物を用いた被覆電線を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it has various characteristics, such as heat aging resistance, oil resistance, cold resistance, and moderate hardness, and can provide the covered electric wire using the vinyl chloride resin composition excellent in heat resistance.
本発明で用いられる塩化ビニル系樹脂とは、塩化ビニル単独重合体および塩化ビニル系共重合体であり、その製造方法は従来公知の重合方法で行われ、例えば、懸濁重合等が挙げられる。これらの塩化ビニル系樹脂の重合度は、通常７００〜５０００程度であり、好ましくは１０００〜３５００、さらに好ましくは１５００〜３０００である。この重合度が低すぎると耐熱性等が低下し、高すぎると成形加工性が低下する。
塩化ビニル単独重合体は、市販品を用いることができ、例えば、大洋塩ビ（株）社製のＴＨ−１０００、ＴＨ−１３００、ＴＨ−１４００、ＴＨ−１７００、ＴＨ−２０００、ＴＨ−２５００、ＴＨ−２８００、ＴＨ−３０００、ＴＨ−３８００（いずれも商品名）等を用いることができ、重合度はそれぞれ１０００、１３００、１４００、１７００、２０００、２５００、２８００、３０００、３８００である。
The vinyl chloride resin used in the present invention is a vinyl chloride homopolymer or a vinyl chloride copolymer, and the production thereof is carried out by a conventionally known polymerization method, such as suspension polymerization. The polymerization degree of these vinyl chloride resins is generally about 700 to 5000, preferably 1000 to 3500, and more preferably 1500 to 3000. If the degree of polymerization is too low, heat resistance and the like are reduced, and if it is too high, moldability is reduced.
As the vinyl chloride homopolymer, commercially available products can be used. For example, TH-1000, TH-1300, TH-1400, TH-1700, TH-2000, TH-2500, and TH-2500 manufactured by Taiyo Vinyl Co., Ltd. -2800, TH-3000, TH-3800 (all of which are trade names), and the degree of polymerization is 1000, 1300, 1400, 1700, 2000, 2500, 2,800, 3000, and 3800, respectively.
塩化ビニル系共重合体の場合、例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン等の炭素数２〜３０のα−オレフィン類、アクリル酸およびそのエステル類、メタクリル酸およびそのエステル類、マレイン酸およびそのエステル類、酢酸ビニル、プロピオン酸ビニル、アルキルビニルエーテル等のビニル化合物、ジアリルフタレート等の多官能性モノマーおよびこれらの混合物と塩化ビニルモノマーとの共重合体、エチレン−アクリル酸エチル共重合体等のエチレン−アクリル酸エステル共重合体、エチレン−メタクリル酸メチル共重合体、エチレン−メタクリル酸エステル共重合体、エチレン−酢酸ビニル共重合体（ＥＶＡ）、塩素化ポリエチレン、ブチルゴム、架橋アクリルゴム、ポリウレタン、ブタジエン−スチレン−メチルメタクリレート共重合体（ＭＢＳ）、ブタジエン−アクリロニトリル−（α−メチル）スチレン共重合体（ＡＢＳ）、スチレン−ブタジエン共重合体、ポリエチレン、ポリメチルメタクリレートおよびこれらの混合物へ塩化ビニルモノマーをグラフトしたグラフト共重合体等が挙げられる。これらの内、例えば、塩化ビニル−酢酸ビニル共重合体、ＥＶＡ−塩化ビニル共重合体は、市販品として入手可能であり、各々の大洋塩ビ（株）社製のＴＶ−８００とＴＧ−１１０、ＴＧ−１２０（いずれも商品名）等がある。 In the case of a vinyl chloride copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene Α-olefins having 2 to 30 carbon atoms, such as 1-tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl Vinyl compounds such as vinyl ethers, polyfunctional monomers such as diallyl phthalate, copolymers of these mixtures with vinyl chloride monomers, ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymer, ethylene-methacrylic Acid methyl copolymer, ethylene-methacrylic acid ester copolymer, Tylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer ( ABS), a styrene-butadiene copolymer, polyethylene, polymethyl methacrylate, and a graft copolymer obtained by grafting a vinyl chloride monomer to a mixture thereof. Among these, for example, vinyl chloride-vinyl acetate copolymer and EVA-vinyl chloride copolymer are available as commercial products, and each of TV-800 and TG-110, manufactured by Taiyo PVC Co., Ltd. TG-120 (all are trade names).
本発明で用いられる可塑剤は、炭素数が４〜１２であり、好ましくは８〜１０であり、さらに、直鎖率が５０〜１００％であり、好ましくは９０％以上である飽和脂肪族アルコールを原料として得られるトリメリット酸エステルおよびピロメリット酸エステルの多価カルボン酸エステル系可塑剤を必須成分として用いる。これら多価カルボン酸エステル系可塑剤は、上述の炭素数が４〜１２で直鎖率が５０〜１００％の飽和脂肪族アルコールとトリメリット酸あるいはピロメリット酸との通常のエステル化法によりエステル化して得られるものである。トリメリット酸エステル系可塑剤としては、例えば、トリオクチルトリメリテート、トリ（２−エチルヘキシル）トリメリテート、トリイソデシルトリメリテート等がある。ピロメリット酸エステル系可塑剤としては、テトラオクチルピロメリテート等がある。
この可塑剤の原料として用いるアルコールの炭素数が４未満では、得られる耐熱老化性は不十分になり、炭素数が１２を越えると、塩化ビニル系樹脂に対する親和性が極端に劣るため加工時のゲル化不良を引き起こす。また、直鎖率が５０％未満では、得られる耐熱老化性は不十分になる。
The plasticizer used in the present invention has 4 to 12 carbon atoms, preferably 8 to 10 carbon atoms, and further has a linear chain ratio of 50 to 100%, preferably 90% or more. As an essential component, a polycarboxylic acid ester-based plasticizer of trimellitic acid ester and pyromellitic acid ester obtained by using as a raw material is used. These polycarboxylic acid ester-based plasticizers are prepared by the usual esterification method of the above-mentioned saturated aliphatic alcohol having 4 to 12 carbon atoms and a linear ratio of 50 to 100% with trimellitic acid or pyromellitic acid. It is obtained by conversion. Examples of the trimellitate plasticizer include trioctyl trimellitate, tri (2-ethylhexyl) trimellitate, and triisodecyl trimellitate. Examples of the pyromellitic ester plasticizer include tetraoctyl pyromellitate.
If the carbon number of the alcohol used as a raw material of the plasticizer is less than 4, the heat aging resistance obtained is insufficient, and if the carbon number exceeds 12, the affinity for the vinyl chloride resin is extremely poor, so that the processing time during processing is extremely low. Causes poor gelation. If the linear chain ratio is less than 50%, the obtained heat aging resistance becomes insufficient.
特に炭素数８〜１０、直鎖率が９０％以上の飽和脂肪族アルコールを原料とする多価カルボン酸エステルが耐熱老化性の点で好適であり、中でもピロメリット酸エステルが最適である。
上記多価カルボン酸エステル系可塑剤の添加量は、塩化ビニル系樹脂１００重量部に対し、３０〜６０重量部とされるが、３５〜５０重量部が最も好ましい。添加量が３０重量部未満では、得られる組成物の柔軟性が乏しく、被覆電線特性としての伸び特性が劣り、耐熱性および耐寒性も不十分となる。添加量が６０重量部を越えると、被覆電線の諸物性において硬度が不十分となる。
In particular, a polycarboxylic acid ester made of a saturated aliphatic alcohol having 8 to 10 carbon atoms and a linear ratio of 90% or more is suitable from the viewpoint of heat aging resistance, and among them, pyromellitic acid ester is most preferable.
The amount of the polycarboxylic acid ester-based plasticizer to be added is 30 to 60 parts by weight, preferably 35 to 50 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 30 parts by weight, the resulting composition has poor flexibility, poor elongation properties as coated wire properties, and insufficient heat resistance and cold resistance. If the addition amount exceeds 60 parts by weight, the hardness of the coated electric wire becomes insufficient in various physical properties.
上記の可塑剤は、市販品として入手可能であり、例えば、旭電化工業（株）社製のＣ−８８０、Ｃ−８１０、ＵＬ−８０、ＵＬ−１００（いずれも商品名）等が挙げられる。
本発明で用いられるポリエステル系の可塑剤は、二塩基酸と多価アルコールを含むアルコールの組み合わせの反応により得られるものである。例えば、二塩基酸としてはアジピン酸、セバシン酸、アゼライン酸、フタル酸等がある。アルコールとしては、ブチルアルコール、ヘキサノール、オクタノール、２−エチルヘキサノール、ノンアルコール、デカノール等の１価アルコール、エチレンジオール、プロピレンジオール、１−２−プロパンジオール、１−３−ブタンジオール等の２価アルコール、グリセリン等の３価アルコールが挙げられる。
ポリエステル系可塑剤は、これらの各々の二塩基酸と多価アルコールを含むアルコールを通常のエステル化法によりエステル化して得られ、例えばアジピン酸と１，３−ブタンジオールおよび２−エチルヘキサノールの混合アルコールを通常のエステル化法によりエステル化して得られるものがある。多価アルコールについては、アルキル基が直鎖または分岐およびこれらの混合物も含まれる。このポリエステル系可塑剤は、２５℃での粘度が１０００ｃｐｓ以上のものが好ましく、２０００ｃｐｓ以上であれば更に好ましい。２５℃での粘度が１０００ｃｐｓ未満では満足な耐油性が得られない。
The above-mentioned plasticizer is available as a commercial product, for example, C-880, C-810, UL-80, UL-100 (all trade names) manufactured by Asahi Denka Kogyo KK, and the like. .
The polyester plasticizer used in the present invention is obtained by a reaction of a combination of a dibasic acid and an alcohol containing a polyhydric alcohol. For example, dibasic acids include adipic acid, sebacic acid, azelaic acid, phthalic acid and the like. Examples of the alcohol include monohydric alcohols such as butyl alcohol, hexanol, octanol, 2-ethylhexanol, non-alcohol, and decanol; and dihydric alcohols such as ethylene diol, propylene diol, 1-2-propane diol, and 1-3-butane diol. And trihydric alcohols such as glycerin.
The polyester plasticizer is obtained by esterifying each of these dibasic acids and alcohols containing polyhydric alcohols by a usual esterification method. For example, a mixture of adipic acid with 1,3-butanediol and 2-ethylhexanol is obtained. Some are obtained by esterifying an alcohol by a usual esterification method. For polyhydric alcohols, the alkyl groups include straight or branched ones and mixtures thereof. The polyester plasticizer preferably has a viscosity at 25 ° C. of 1000 cps or more, more preferably 2000 cps or more. If the viscosity at 25 ° C. is less than 1000 cps, satisfactory oil resistance cannot be obtained.
このようなポリエステル系可塑剤の添加量は、塩化ビニル系樹脂１００重量部に対し、３〜２０重量部である。１重量部未満では耐油性の改善効果が不十分であり、１００重量部を越えるとブリード或いは加工時のゲル化不良を引き起こす。
このようなポリエステル系可塑剤は、市販品として入手可能であり、例えば、旭電化工業（株）社製のＰＮ−１０３０、ＰＮ−１４３０、ＨＰＮ−３１３０（いずれも商品名）等が挙げられる。
本発明では、特に、耐熱性および耐油性の向上を達成するためには、前記にあるトリメリット酸エステルおよび／またはピロメリット酸エステルから成る多価カルボン酸エステル系可塑剤とポリエステル系可塑剤の併用は重要である。
The addition amount of such a polyester plasticizer is 3 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 1 part by weight, the effect of improving oil resistance is insufficient, and if it exceeds 100 parts by weight, bleeding or poor gelation during processing is caused.
Such a polyester plasticizer is available as a commercial product, and examples thereof include PN-1030, PN-1430, and HPN-3130 (all trade names) manufactured by Asahi Denka Kogyo KK.
In the present invention, in particular, in order to achieve an improvement in heat resistance and oil resistance, the polyvalent carboxylic acid ester-based plasticizer comprising the trimellitic acid ester and / or pyromellitic acid ester and the polyester-based plasticizer are used. Combination is important.
ＪＩＳ Ｃ ３４０６やＪＡＳＯ Ｄ ６１１の規格に合格する一般耐熱電線用途では、１２０℃で１２０時間加熱し、屈曲後、１０００Ｖに１分間耐える電線としての耐熱性が要求される（後述するシートでの試験で加熱後伸び残率７０％以上に相当）ほか、所定の耐油性、耐寒性、適度の硬度等が要求される。そのために必要な多価カルボン酸エステル系可塑剤の添加量は、塩化ビニル系樹脂１００重量部に対して、炭素数が４〜１２で直鎖率が５０〜１００％の飽和脂肪族アルコールを原料として得られるトリメリット酸エステルおよび／またはピロメリット酸エステルの多価カルボン酸エステル系可塑剤３０〜６０重量部、２５℃での粘度が１０００ｃｐｓ以上のポリエステル系可塑剤３〜２０重量部、ハイドロタルサイト化合物５〜４０重量部および亜鉛系金属石鹸０．０５〜５重量部から成り、かつ前記可塑剤の合計添加重量部数が３５〜７０重量部であり、かつ全可塑剤中のトリメリット酸エステルの割合が重量比で０．５以下、全可塑剤中のポリエステル系可塑剤の割合が重量比で０．４以下である必要がある。
また、上述の配合組成は一般耐熱電線用途の規格に対するものであるが、後述した高耐熱性自動車電線用途に対しても十分満足する配合組成範囲も含有している。
For general heat-resistant electric wire applications that pass JIS C 3406 and JASO D 611 standards, heat resistance is required as an electric wire that can be heated at 120 ° C. for 120 hours, bent and withstands 1000 V for 1 minute (test on a sheet described later). In addition, the residual elongation after heating is equivalent to 70% or more), and predetermined oil resistance, cold resistance, appropriate hardness and the like are required. The amount of the polyvalent carboxylic acid ester-based plasticizer required for this is such that a saturated aliphatic alcohol having 4 to 12 carbon atoms and a linear ratio of 50 to 100% is used as a raw material relative to 100 parts by weight of the vinyl chloride resin. 30 to 60 parts by weight of a polyvalent carboxylic acid ester plasticizer of trimellitic acid ester and / or pyromellitic acid ester obtained as above, 3 to 20 parts by weight of a polyester plasticizer having a viscosity at 25 ° C. of 1000 cps or more, hydrotal 5 to 40 parts by weight of the site compound and 0.05 to 5 parts by weight of the zinc-based metal soap, and 35 to 70 parts by weight of the plasticizer in total, and trimellitic acid ester in all the plasticizers Is required to be 0.5 or less by weight, and the ratio of the polyester-based plasticizer in all the plasticizers is required to be 0.4 or less by weight.
In addition, the above-mentioned composition is in accordance with the standard for general heat-resistant electric wire applications, but also includes a composition range that is sufficiently satisfied for high heat-resistant automotive electric wire applications described later.
ここで、上述の多価カルボン酸エステルの添加部数が３０重量部未満では耐熱老化性が不足し、６０重量部を越えると硬度に影響を及ぼす。また、ポリエステル系可塑剤の添加量が３重量部未満では耐油性が劣り、２０重量部以上では耐熱性が劣る。また、可塑剤の合計添加量が３５重量部以下では耐寒性が劣り、７０重量部以上では硬度が低下し、電線として用いることができない。さらに、使用する全可塑剤量に対するトリメリット酸エステルの割合は重量比で０．５以下が好ましく、零でもよいが、トリメリット酸エステルの全可塑剤量に占める割合が重量比で０．５を越えると、耐熱老化性が不十分となる。また、ポリエステル系可塑剤の全可塑剤量に占める割合は重量比で０．４以下が好ましく、重量比が０．４を越えると耐熱老化性がやはり不十分となる。その下限はより好ましくは０．０５である。
特にＪＡＳＯ Ｄ ６０８の規格に合格する高耐熱性自動車電線用途では、１２０℃で１６８時間加熱し屈曲後１０００Ｖに１分間耐える電線としての高度の耐熱性が要求される（後述するシートでの試験で加熱後伸び残率８０％以上に相当）ほか、所定の耐油性、耐摩耗性、耐寒性、適度の硬度等が要求される。そのために、塩化ビニル系樹脂１００重量部に対して、前記多価カルボン酸エステルとして、炭素数が８〜１０で直鎖率が９０％以上の飽和脂肪族アルコールを原料として得られるピロメリット酸エステルを３０〜６０重量部配合する。このピロメリット酸エステルの添加量が３０重量部未満では耐熱老化性が不足し、６０重量部を越えると硬度に影響を及ぼす。また、ピロメリット酸エステルとポリエステル系可塑剤の合計量が３５重量部以下では耐寒性が劣り、７０重量部以上では硬度が低下し、電線として用いることができない。このときの全可塑剤に対する前記のポリエステル系可塑剤の割合は重量比で０．１〜０．４である。
Here, when the number of the added polyvalent carboxylic acid ester is less than 30 parts by weight, the heat aging resistance is insufficient, and when it exceeds 60 parts by weight, the hardness is affected. When the amount of the polyester plasticizer is less than 3 parts by weight, the oil resistance is poor, and when it is 20 parts by weight or more, the heat resistance is poor. When the total amount of the plasticizer is 35 parts by weight or less, the cold resistance is inferior, and when the total amount is 70 parts by weight or more, the hardness decreases, and the plasticizer cannot be used as an electric wire. Further, the ratio of trimellitate to the total amount of plasticizer used is preferably 0.5 or less by weight, and may be zero, but the ratio of trimellitate to the total amount of plasticizer is 0.5% by weight. If it exceeds, the heat aging resistance becomes insufficient. Further, the ratio of the polyester-based plasticizer to the total amount of the plasticizer is preferably 0.4 or less by weight ratio, and when the weight ratio exceeds 0.4, the heat aging resistance also becomes insufficient. The lower limit is more preferably 0.05.
In particular, for high heat-resistant automotive electric wire applications that pass the standard of JASO D 608, high heat resistance as an electric wire that is heated at 120 ° C. for 168 hours and withstands 1000 V for 1 minute after bending is required (in a sheet test described later). In addition, it is required to have predetermined oil resistance, abrasion resistance, cold resistance, appropriate hardness and the like. Therefore, a pyromellitic acid ester obtained from a saturated aliphatic alcohol having 8 to 10 carbon atoms and a linear ratio of 90% or more as the polycarboxylic acid ester with respect to 100 parts by weight of a vinyl chloride resin is used. In an amount of 30 to 60 parts by weight. When the amount of the pyromellitic acid ester is less than 30 parts by weight, the heat aging resistance is insufficient, and when it exceeds 60 parts by weight, the hardness is affected. When the total amount of the pyromellitic acid ester and the polyester-based plasticizer is 35 parts by weight or less, the cold resistance is inferior. When the total amount is 70 parts by weight or more, the hardness is reduced, and the resin cannot be used as an electric wire. At this time, the ratio of the polyester plasticizer to all the plasticizers is 0.1 to 0.4 by weight.
上記に規定される塩化ビニル系樹脂組成物を用いることにより、電線用途として合格するためのシート試験による合格基準である１６０℃で２００時間加熱後の伸び残率７０％以上（一般耐熱用途）もしくは８０％以上（耐熱自動車用途）、浸油後の伸び残率７０％以上（一般耐熱用途）もしくは８０％以上（耐熱自動車用途）、耐寒性−２０℃以下、硬度８８〜９８を達成することができる。
本発明で用いられるハイドロタルサイト化合物は、無毒安定剤として熱安定性、透明性、電気特性等の特性を有しており、特に毒性のある鉛系安定剤の代替として用いている。このハイドロタルサイト化合物は、主にＭｇxＺｎyＡｌ2(ＯＨ)2(x+y)+4ＣＯ3・ｎＨ2Ｏ（式中、x 、ｙは各々、２≦ｘ≦６、０≦ｙ≦２、４≦（ｘ＋ｙ）≦６の数を示し、ｎは、０≦ｎ≦１０の結晶水の数を示す。）の構造を持ち、天然物あるいは合成物のどちらでも良く、不純物が少量であることからも、合成物が望ましい。このハイドロタルサイト化合物としては、Ｍｇ6Ａｌ2(ＯＨ)16ＣＯ3・ｎＨ2Ｏ、Ｍｇ4Ａｌ2(ＯＨ)12ＣＯ3・ｎＨ2Ｏ、Ｍｇ3ＺｎＡｌ2(ＯＨ)12ＣＯ3・ｎＨ2Ｏ（但し、ｎは、０≦ｎ≦１０の結晶水の数を示す。）等が挙げられ、市販品として入手可能であり、例えば、協和化学工業（株）社製の合成ハイドロタルサイトとして、アルカマイザー１、アルカマイザー２、アルカマイザー４（いずれも商品名）等がある。このハイドロタルサイト化合物は、そのままでも、あるいは長鎖脂肪酸等で処理したものでも良く、用いる際は、単独使用あるいは２種類以上を公知の方法により混合して用いても構わない。
By using the vinyl chloride resin composition specified above, the elongation residual after heating at 160 ° C. for 200 hours, which is a passing criterion by a sheet test for passing as an electric wire application, is 70% or more (general heat resistance application) or 80% or more (for heat-resistant vehicles), 70% or more of residual elongation after oil immersion (for general heat-resistant applications) or 80% or more (for heat-resistant vehicles), cold resistance of -20 ° C or less, and hardness of 88-98. it can.
The hydrotalcite compound used in the present invention has properties such as thermal stability, transparency, and electrical properties as a non-toxic stabilizer, and is used as a substitute for a particularly toxic lead-based stabilizer. This hydrotalcite compound is mainly composed of Mg x Zn y Al 2 (OH) 2 (x + y) +4 CO 3 .nH 2 O (where x and y are respectively 2 ≦ x ≦ 6, 0 ≦ y≤2, 4≤ (x + y) ≤6, and n represents the number of crystal waters satisfying 0≤n≤10), which may be either a natural product or a synthetic product. Synthetic products are also desirable because of their small quantities. Examples of the hydrotalcite compounds include Mg 6 Al 2 (OH) 16 CO 3 .nH 2 O, Mg 4 Al 2 (OH) 12 CO 3 .nH 2 O, and Mg 3 ZnAl 2 (OH) 12 CO 3 .nH 2 O (where n represents the number of crystal waters satisfying 0 ≦ n ≦ 10) and the like, which is available as a commercial product, for example, synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd. There are Alkamizer 1, Alkamizer 2, and Alkamizer 4 (all are trade names). The hydrotalcite compound may be used as it is, or may be treated with a long-chain fatty acid or the like. When used, it may be used alone or as a mixture of two or more kinds.
このハイドロタルサイト化合物の添加量は、塩化ビニル系樹脂１００重量部に対し、５〜４０重量部であり、好ましくは７〜３０重量部であり、さらに好ましくは９〜２０重量部である。添加量が５重量部未満では、得られる耐熱性老化性は不充分であり、また、４０重量部を越えると、溶融成形時において着色や発泡等の問題が出てくる。
本発明で用いられる亜鉛系金属石鹸は、耐熱性の向上に加えて色相改善並びに初期着色防止効果が大きく、特に、前述のハイドロタルサイト化合物類の添加系においては効果を発揮する。亜鉛系金属石鹸としては、例えば、ステアリン酸亜鉛、オクチル酸亜鉛、ラウリン酸亜鉛等が挙げられる。この亜鉛系金属石鹸の添加量は、塩化ビニル系樹脂１００重量部に対し、０．０５〜５量部であり、好ましくは０．２〜３重量部であり、さらに好ましくは０．５〜２重量部である。この添加量が０．０５重量部未満では、耐熱性の向上、色相改善および初期着色防止性向上の効果が不十分になり、５重量部を越えると、亜鉛焼け現象を起こし着色が顕著に現れ、耐熱性が低下する。この亜鉛系金属石鹸は、市販品を用いることができ、例えば、ステアリン酸亜鉛では、キクチカラー（株）社製のＺＳ−１００等が挙げられる。
The amount of the hydrotalcite compound to be added is 5 to 40 parts by weight, preferably 7 to 30 parts by weight, and more preferably 9 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the added amount is less than 5 parts by weight, the obtained heat-resistant aging property is insufficient, and if it exceeds 40 parts by weight, problems such as coloring and foaming during melt molding arise.
The zinc-based metal soap used in the present invention has a large effect of improving the hue and preventing the initial coloring in addition to the improvement of the heat resistance, and exhibits an effect particularly in the above-mentioned hydrotalcite compound-added system. Examples of the zinc-based metal soap include zinc stearate, zinc octylate, zinc laurate and the like. The amount of the zinc-based metal soap is 0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Parts by weight. If the amount is less than 0.05 parts by weight, the effects of improving heat resistance, hue and initial coloration will be insufficient, and if it exceeds 5 parts by weight, zinc burning will occur and coloring will appear significantly. , Heat resistance decreases. As the zinc-based metal soap, a commercially available product can be used. For example, as zinc stearate, ZS-100 manufactured by Kikuchi Color Co., Ltd. can be used.
本発明において、ハイドロタルサイト化合物と亜鉛系金属石鹸を併用することで色相並びに加工時の初期着色防止性を向上させているが、それは、塩化ビニル樹脂の加工温度ではハイドロタルサイト化合物は滑性効果が無いため、比較的融点が低く塩化ビニル樹脂内での分散性の良い亜鉛系金属石鹸を添加することで、滑性を向上させハイドロタルサイト化合物単独使用の場合に生じる塩化ビニル系樹脂内での局所的な分解を抑制できるためであると考える。
なお、本発明における塩化ビニル系樹脂組成物は必要に応じ、上記以外の安定剤、滑剤、紫外線吸収剤、酸化防止剤、帯電防止剤、難燃剤、充填剤、顔料、加工助剤等の通常塩化ビニル系樹脂に対して用いられている添加剤を、本発明における効果を損なわない範囲で適宜配合して用いても良い。例えば、電線の絶縁材料やシース材料などの被覆材に用いる場合、塩化ビニル系樹脂１００重量部に対して、難燃剤として三酸化アンチモン等を１〜２０重量部程度配合して難燃化を図ることができる。
In the present invention, by using a hydrotalcite compound and a zinc-based metal soap in combination, the hue and the initial coloring prevention property at the time of processing are improved, but at the processing temperature of the vinyl chloride resin, the hydrotalcite compound has lubricity. Since there is no effect, by adding a zinc-based metal soap having a relatively low melting point and a good dispersibility in the vinyl chloride resin, the lubricity is improved and the inside of the vinyl chloride-based resin generated when using the hydrotalcite compound alone is improved. It is considered that this is because local decomposition at the point can be suppressed.
In addition, the vinyl chloride resin composition in the present invention may be, if necessary, a stabilizer, a lubricant, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, a filler, a pigment, a processing aid, etc. The additives used for the vinyl chloride resin may be appropriately blended and used as long as the effects of the present invention are not impaired. For example, when used as a covering material such as an insulating material or a sheath material of an electric wire, 1 to 20 parts by weight of antimony trioxide or the like is blended as a flame retardant with respect to 100 parts by weight of a vinyl chloride resin to achieve flame retardancy. be able to.
また、本発明における塩化ビニル系樹脂組成物によれば、所期の目的である耐熱老化性向上が達成されるが、さらなる耐熱性向上等の物性を改善する目的で従来公知の架橋技術を併用することもできる。
本発明における塩化ビニル系樹脂組成物は、塩化ビニル系樹脂に対して、上述の炭素数が４〜１２で直鎖率が５０〜１００％の飽和脂肪族アルコールを原料として得られるトリメリット酸エステルおよび／またはピロメリット酸エステルから成る多価カルボン酸エステル系可塑剤、２５℃での粘度が１０００ｃｐｓ以上のポリエステル系可塑剤、ハイドロタルサイト化合物および、亜鉛系金属石鹸を、例えば、ヘンシェルミキサー、バンバリーミキサー、リボンブレンダー等の攪拌機により攪拌混合を行い、得られた塩化ビニル系樹脂組成物を配合粉として、例えば、コニカル二軸押出機、パラレル二軸押出機、単軸押出機、コニーダー型混練機、ロール混練機等の混練機により溶融成形してペレットとして得ることができる。
In addition, according to the vinyl chloride resin composition of the present invention, the intended improvement in heat aging resistance is achieved, but a conventionally known crosslinking technique is used in combination with the purpose of further improving physical properties such as further improvement in heat resistance. You can also.
The vinyl chloride resin composition according to the present invention is a trimellitic acid ester obtained from a saturated aliphatic alcohol having a carbon number of 4 to 12 and a linear ratio of 50 to 100% based on the vinyl chloride resin. And / or a polycarboxylic acid ester plasticizer comprising pyromellitic acid ester, a polyester plasticizer having a viscosity at 25 ° C. of 1000 cps or more, a hydrotalcite compound, and a zinc metal soap, for example, a Henschel mixer, a Banbury Stir-mixing is performed by a stirrer such as a mixer and a ribbon blender, and the obtained vinyl chloride-based resin composition is used as a compounding powder. It can be obtained as pellets by melt molding with a kneader such as a roll kneader.
これらの塩化ビニル系樹脂組成物である配合粉あるいはペレットを用いて、コニカル二軸押出機、パラレル二軸押出機、単軸押出機等の押出機により溶融成形加工することにより、被覆電線を得ることができる。本発明における塩化ビニル系樹脂組成物を導体上に被覆して電線とするには、従来公知の押出機を備えた押出被覆装置を用いればよく、例えば、押出機本体１７０〜１９５℃、クロスヘッド部１８０℃の設定温度で、線速３５０〜４５０ｍ／分程度の被覆電線の製造が可能である。 Using the blended powder or pellets of these vinyl chloride resin compositions, melt-molding is performed by an extruder such as a conical twin-screw extruder, a parallel twin-screw extruder, or a single-screw extruder to obtain a covered electric wire. be able to. In order to cover the conductor with the vinyl chloride resin composition of the present invention to form an electric wire, an extrusion coating apparatus equipped with a conventionally known extruder may be used. For example, an extruder main body at 170 to 195 ° C, a crosshead At a set temperature of 180 ° C., a coated electric wire having a linear speed of about 350 to 450 m / min can be manufactured.
以下、実施例により本発明を更に具体的に説明する。
尚、実施例における測定方法は以下の通りである。
表１および２に示す塩化ビニル系樹脂組成物を三井三池加工機（株）社製５００Ｌスーパーヘンシェルミキサーにて１２０℃になるまで混合して配合粉を得た。ここで得られた塩化ビニル系樹脂組成物である配合粉を、池貝鉄工（株）社製の二軸同方向押出機ＧＴ−１１０を用いて溶融成形して、塩化ビニル系樹脂組成物をペレットとして得た。以下の塩化ビニル系樹脂組成物の物性および被覆電線における評価については、ここで得られたペレットを用いて行った。
上述で得られたペレットを用いて、（株）安田精機製作所製のテスト・ミキシング・ロール・マシン １９１−ＷＭ ｔｙｐｅロールにて、ロール温度１８０℃で１５分間混練した後、（株）神藤金属工業所製のＡＳＦＡ１５０型式圧縮成形機にてプレス温度１８０℃、圧力５０ｋｇ／ｃｍ２で４分間プレス加工を行い、厚み１ｍｍのシートを得た。得られたシートを用いて、以下の物性について評価した。
Hereinafter, the present invention will be described more specifically with reference to examples.
In addition, the measuring method in an Example is as follows.
The vinyl chloride-based resin compositions shown in Tables 1 and 2 were mixed with a 500 L Super Henschel mixer manufactured by Mitsui Miike Koki Co., Ltd. until the temperature reached 120 ° C. to obtain a compounded powder. The compounded powder, which is a vinyl chloride resin composition obtained here, is melt-formed using a twin screw co-extruder GT-110 manufactured by Ikegai Iron Works Co., Ltd. to pelletize the vinyl chloride resin composition. As obtained. The following physical properties of the vinyl chloride resin composition and evaluation of the coated electric wire were performed using the pellets obtained here.
After kneading the pellets obtained above with a test mixing roll machine 191-WM type roll manufactured by Yasuda Seiki Seisakusho Co., Ltd. at a roll temperature of 180 ° C. for 15 minutes, Koto Metal Co., Ltd. Pressing was performed at a press temperature of 180 ° C. and a pressure of 50 kg / cm 2 for 4 minutes using an in-house ASFA150 type compression molding machine to obtain a sheet having a thickness of 1 mm. The following physical properties were evaluated using the obtained sheet.
加熱後伸び残率については、シートの加熱前と１５８℃のギヤオーブンで１６８時間加熱後の引張伸び率をＪＩＳ−Ｋ７１１３に準ずる引張試験法にて測定し、加熱後の引張伸び率を加熱前の引張伸び率にて除して算出した。
浸油後伸び残率については、シートの加熱浸油前と７０℃に加熱したＪＩＳ−Ｋ６３０１に規定されるＮｏ．１油に４時間浸した後、引張伸び率をＪＩＳ−Ｋ７１１３に準ずる引張試験法にて測定し、加熱後の引張伸び率を加熱前の引張伸び率にて除して算出した。
さらに、被覆電線用としての塩化ビニル系樹脂組成物の物性について以下の通り評価を行った。試験用サンプルは、上記のプレス加工により、厚み０．５ｍｍ、１ｍｍ、２ｍｍ、１２ｍｍシートを用いて行った。
耐寒性については、厚み２ｍｍのシートを用いて、ＪＩＳ−Ｋ６７２３に準ずる耐寒性試験法にて媒体はエタノールを用いて測定を行った。
硬度については、厚み１２ｍｍのシートを用いて、ＪＩＳ−Ｋ６３０１に準ずる定荷重式硬さ試験法により測定を行った。
Regarding the residual elongation after heating, the tensile elongation before heating the sheet and after heating for 168 hours in a gear oven at 158 ° C. was measured by a tensile test method according to JIS-K7113, and the tensile elongation after heating was measured before heating. Calculated by dividing by the tensile elongation.
Regarding the elongation residual ratio after oil immersion, No. stipulated in JIS-K6301 before heating oil immersion and heating at 70 ° C. After soaking in one oil for 4 hours, the tensile elongation was measured by a tensile test method according to JIS-K7113, and the tensile elongation after heating was calculated by dividing the tensile elongation before heating.
Further, the physical properties of the vinyl chloride resin composition for covered electric wires were evaluated as follows. The test samples were formed by the above-mentioned press working using 0.5 mm, 1 mm, 2 mm, and 12 mm sheets.
With respect to cold resistance, a medium having a thickness of 2 mm was measured by a cold resistance test method according to JIS-K6723 using ethanol as a medium.
The hardness was measured using a sheet having a thickness of 12 mm by a constant load type hardness test method according to JIS-K6301.
次に、一般耐熱被覆電線用途に適した塩化ビニル系樹脂組成物について、より具体的に説明する。
一般耐熱被覆電線では、加熱後伸び残率７０％以上の耐熱老化性、浸油後伸び残率７０％以上の耐油性、−２０℃以下の耐寒性、８８〜９８の範囲の硬度を必要とする。
Next, the vinyl chloride resin composition suitable for general heat-resistant coated electric wire applications will be described more specifically.
General heat-resistant coated wires require heat aging resistance of 70% or more after heating, oil resistance of 70% or more after oil immersion, cold resistance of -20 ° C or less, and hardness in the range of 88 to 98. I do.
参考例１
平均重合度が２０００も塩化ビニル系樹脂単独重合体１００重量部、多価カルボン酸エステル系可塑剤として原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテート４０重量部に、原料アルコールの直鎖率が９５％であるトリオクチルトリメリテート５重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を５重量部用いることにより、全可塑剤に対するトリオクチルトリメリテートの割合が重量比で０．１、さらに２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を全可塑剤に対して重量比で０．１となるように用いた他は、表１に示す組成で前述の物性の測定で述べたようにしてシートを得て物性を測定した。結果を表１に示す。
Reference Example 1
An average degree of polymerization of 2,000 was also added to 100 parts by weight of a vinyl chloride resin homopolymer, 40 parts by weight of tetraoctyl pyromellitate having a linear ratio of 95% as a polyvalent carboxylic acid ester plasticizer, By using 5 parts by weight of trioctyl trimellitate having a linear ratio of 95% and 5 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., the ratio of trioctyl trimellitate to all plasticizers is increased by weight. The above-mentioned physical properties were obtained using the composition shown in Table 1, except that a polyester-based plasticizer having a viscosity of 3000 cps at 25 ° C. and a weight ratio of 0.1 to the total plasticizer was used. The sheet was obtained and the physical properties were measured as described above. Table 1 shows the results.
参考例２
多価カルボン酸エステル系可塑剤として原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテート２５重量部に、原料アルコールの直鎖率が９５％であるトリオクチルトリメリテート２５重量部、２５℃での粘度が３０００ｃｐｓ以上のポリエステル系可塑剤を１０重量部用いることにより、全可塑剤に対するトリオクチルトリメリテートの割合が重量比で０．５、さらに２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を全可塑剤に対する重量比で０．１７となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。結果を表１に示す。
Reference Example 2
25 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol is 95%, 25 parts by weight of trioctyl trimellitate in which the linear ratio of the raw material alcohol is 95%, By using 10 parts by weight of a polyester plasticizer having a viscosity of 3000 cps or more at 25 ° C., the ratio of trioctyl trimellitate to all plasticizers is 0.5 by weight, and the viscosity of the polyester at 25 ° C. is 3000 cps. A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1, except that the weight ratio of the system plasticizer to the total plasticizer was 0.17. Table 1 shows the results.
参考例３
多価カルボン酸エステル系可塑剤として原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテート３２．５重量部に、原料アルコールの直鎖率が９５％であるトリオクチルトリメリテート５重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を１２．５重量部用いることにより、全可塑剤に対するトリオクチルトリメリテートの比率が重量比で０．１、さらに２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を全可塑剤中に対する重量比で０．２５となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。結果を表１に示す。
Reference Example 3
As a polycarboxylic acid ester-based plasticizer, 32.5 parts by weight of tetraoctyl pyromellitate in which the raw material alcohol has a linear ratio of 95%, and 5 parts by weight of trioctyl trimellitate in which the raw material alcohol has a linear ratio of 95% 12.5 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., the ratio of trioctyl trimellitate to all plasticizers is 0.1 by weight, and the viscosity at 25 ° C. A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1, except that a polyester-based plasticizer of 3000 cps was used in a weight ratio of 0.25 to all the plasticizers. Table 1 shows the results.
参考例４
多価カルボン酸エステル系可塑剤として原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテート２０重量部に、原料アルコールの直鎖率が９５％であるトリオクチルトリメリテート１０重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を２０重量部用いることにより、全可塑剤に対するトリオクチルトリメリテートの比率が重量比で０．２、さらに２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を全可塑剤中の割合が０．４となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。結果を表１に示す。
Reference example 4
20 parts by weight of tetraoctyl pyromellitate having a raw alcohol ratio of 95% as a polyvalent carboxylic acid ester-based plasticizer, 10 parts by weight of trioctyl trimellitate having a raw alcohol ratio of 95%, By using 20 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., a ratio of trioctyl trimellitate to all the plasticizers is 0.2 by weight, and further a polyester plastic having a viscosity at 25 ° C. of 3000 cps is used. A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1 except that the plasticizer was used so that the ratio in the total plasticizer was 0.4. Table 1 shows the results.
次に、自動車用耐熱被覆電線用途に適した塩化ビニル系樹脂組成物について、より具体的に説明する。
この自動車用被覆耐熱電線では、加熱後伸び残率８０％以上の耐熱老化性、浸油後伸び残率８０％以上の耐油性、−２０℃以下の耐寒性、８８〜９８の範囲の硬度を示し、これらの諸特性はＪＡＳＯ Ｄ ６０８規格を満足するものである。
Next, the vinyl chloride resin composition suitable for heat-resistant coated electric wires for automobiles will be described more specifically.
In this coated heat-resistant electric wire for automobiles, the heat aging resistance after elongation after heating is 80% or more, the oil resistance after elongation after oil immersion is 80% or more, the cold resistance at -20 ° C or less, and the hardness in the range of 88 to 98. As shown, these characteristics satisfy the JASO D608 standard.
参考例５
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを３５重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を１０重量部、さらに直鎖率９５％であるテトラオクチルトリメリテートの割合が重量比で０．２２となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。結果を表２に示す。
Reference example 5
35 parts by weight of tetraoctyl pyromellitate having a linear ratio of 95% of the raw material alcohol, 10 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., and tetraoctyl trimellitate having a linear ratio of 95% A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1, except that the proportion of tate was 0.22 by weight. Table 2 shows the results.
参考例６
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを４０重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を５重量部、さらに直鎖率９５％であるテトラオクチルトリメリテートの割合が重量比で０．１１となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。結果を表２に示す。
Reference Example 6
40 parts by weight of tetraoctyl pyromellitate having a linear ratio of the raw material alcohol of 95%, 5 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., and tetraoctyl trimellitate having a linear ratio of 95% A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1, except that the proportion of tate was 0.11 by weight. Table 2 shows the results.
参考例７
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを４０重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を１５重量部、さらに直鎖率９５％であるテトラオクチルトリメリテートの割合が重量比で０．２７となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。結果を表２に示す。
Reference Example 7
40 parts by weight of tetraoctyl pyromellitate having a linear ratio of the raw material alcohol of 95%, 15 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., and tetraoctyl trimellitate having a linear ratio of 95% A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1, except that the proportion of tate was 0.27 by weight. Table 2 shows the results.
参考例８
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを５０重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を１０重量部、さらに直鎖率９５％であるテトラオクチルトリメリテートの割合が重量比で０．１７となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。結果を表２に示す。
Reference Example 8
50 parts by weight of tetraoctyl pyromellitate having a linear ratio of 95% of the starting alcohol, 10 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., and tetraoctyl trimellitate having a linear ratio of 95% A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1, except that the weight ratio of the tate was 0.17. Table 2 shows the results.
比較例１
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを２０重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を１５重量部、さらにポリエステル系可塑剤の割合が重量比で０．４３となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。
全可塑剤中のポリエステル系可塑剤の割合がを０．４３と多いため、加熱後の伸び残率は７３％と低く、耐寒性は−１５℃と高く、硬度は９９と高く、自動車用高耐熱電線用途で必要とされる諸物性が得られなかった。結果を表２に示す。
Comparative Example 1
20 parts by weight of tetraoctyl pyromellitate having a linear ratio of the raw material alcohol of 95%, 15 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., and a ratio of the polyester plasticizer of 0% by weight. A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1, except that it was used so as to be 0.43.
Since the ratio of the polyester plasticizer in all the plasticizers is as large as 0.43, the residual elongation after heating is as low as 73%, the cold resistance is as high as −15 ° C., the hardness is as high as 99, and the height for automobiles is high. Various physical properties required for heat-resistant electric wire applications could not be obtained. Table 2 shows the results.
比較例２
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを５５重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を２０重量部、さらにポリエステル系可塑剤の割合が重量比で０．２７となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。
全可塑剤の使用量が７５重量部と多いため、硬度が８６と低く、自動車用高耐熱電線用途で必要とされる硬度が得られなかった。結果を表２に示す。
Comparative Example 2
55 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol is 95%, 20 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., and the ratio of the polyester plasticizer is 0 by weight. A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1 except that the sheet was used so as to obtain .27.
Since the total amount of the plasticizer used was as large as 75 parts by weight, the hardness was as low as 86, and the hardness required for the use of high heat resistant electric wires for automobiles could not be obtained. Table 2 shows the results.
比較例３
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを５０重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤を用いない他は参考例１と同様にしてシートを得て物性を測定した。
ポリエステル系可塑剤を用いないため、油浸漬後の伸び残率が７６％と低く、自動車用高耐熱電線用途で必要とされる油浸漬後伸び残率値が得られなかった。結果を表２に示す。
Comparative Example 3
A sheet was obtained in the same manner as in Reference Example 1 except that 50 parts by weight of tetraoctyl pyromellitate having a linear ratio of the raw material alcohol of 95% and a polyester plasticizer having a viscosity of 3000 cps at 25 ° C. were not used. Was measured.
Since no polyester plasticizer was used, the residual elongation after oil immersion was as low as 76%, and the residual elongation after oil immersion required for automotive high heat resistant wire applications could not be obtained. Table 2 shows the results.
比較例４
原料アルコールの直鎖率が９５％であるテトラオクチルピロメリテートを６０重量部、２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤５重量部、さらにポリエステル系可塑剤の割合が重量比で０．０８となるように用いた他は参考例１と同様にしてシートを得て物性を測定した。
ポリエステル系可塑剤の割合が重量比で０．０８と低いため、油浸漬後の伸び残率が７８％と低く、自動車用高耐熱電線用途で必要とされる油浸漬後伸び残率値が得られなかった。結果を表２に示す。
Comparative Example 4
60 parts by weight of tetraoctyl pyromellitate in which the linear ratio of the raw material alcohol is 95%, 5 parts by weight of a polyester plasticizer having a viscosity of 3000 cps at 25 ° C., and a ratio of the polyester plasticizer of 0.1% by weight. A sheet was obtained and the physical properties were measured in the same manner as in Reference Example 1 except that the value was set to 08.
Since the weight ratio of the polyester plasticizer is as low as 0.08, the residual elongation after oil immersion is as low as 78%, and the residual elongation after oil immersion required for high heat resistant electric wire for automobiles is obtained. I couldn't. Table 2 shows the results.
実施例１
参考例２および参考例５の塩化ビニル系樹脂組成物を用いて、６０ｍｍφ、Ｌ／Ｄ＝２５の押出機により、設定温度を材料投入側から順次、シリンダー部１７０℃、１９０℃、１９０℃、クロスヘッド部１８５℃とし、線速３００ｍ／分で導体上に所定厚の絶縁層を押出成形して被覆電線を得て、被覆電線としての諸物性を評価した。評価方法は、ＪＡＳＯ Ｄ ６１１（＝ＪＩＳ Ｃ３４０６）規格およびＪＡＳＯ Ｄ ６０８規格に準拠した。評価結果を表３にまとめて示す。
表３の結果から分かるように、本発明において被覆電線用途に適しているとして提供される塩化ビニル系樹脂組成物を用いた第１および第２発明に該当する被覆電線は、電線規格で定められた耐熱性をはじめとする諸物性に全て合格することが確かめられた。
Example 1
Using the vinyl chloride resin composition of Reference Example 2 and Reference Example 5, the cylinder temperature was set to 170 ° C., 190 ° C., 190 ° C. in the order from the material input side by an extruder of 60 mmφ and L / D = 25. At a crosshead temperature of 185 ° C., an insulating layer having a predetermined thickness was extruded on a conductor at a linear speed of 300 m / min to obtain a coated electric wire, and various physical properties as the coated electric wire were evaluated. The evaluation method was based on JASO D 611 (= JIS C3406) standard and JASO D 608 standard. The evaluation results are shown in Table 3.
As can be seen from the results in Table 3, the coated electric wires corresponding to the first and second inventions using the vinyl chloride resin composition provided as being suitable for the coated electric wire application in the present invention are defined by electric wire standards. It was confirmed that all properties including heat resistance were passed.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004039055A JP2004193138A (en) | 1997-09-08 | 2004-02-16 | Vinyl chloride based resin sheathed wire |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24287197 | 1997-09-08 | ||
| JP2004039055A JP2004193138A (en) | 1997-09-08 | 2004-02-16 | Vinyl chloride based resin sheathed wire |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10158199A Division JPH11140263A (en) | 1997-09-08 | 1998-06-05 | Vinyl chloride-based resin composition and coated electric wire using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004193138A true JP2004193138A (en) | 2004-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004039055A Pending JP2004193138A (en) | 1997-09-08 | 2004-02-16 | Vinyl chloride based resin sheathed wire |
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| JP (1) | JP2004193138A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406514C (en) * | 2006-09-19 | 2008-07-30 | 上海电缆研究所 | Semi-horniness flame-proof PVC sheath material for high-voltage cable |
| WO2010041378A1 (en) * | 2008-10-09 | 2010-04-15 | 株式会社Adeka | Vinyl chloride resin composition for transparent product, and transparent molded product produced by molding the composition |
| JP2012102309A (en) * | 2010-10-13 | 2012-05-31 | Mitsubishi Chemicals Corp | Polyvinyl chloride resin composition and electric wire |
| CN103680716A (en) * | 2012-09-21 | 2014-03-26 | 北京斯普乐电线电缆有限公司 | High temperature-resistant cable for thermoplastic type car |
| CN103724878A (en) * | 2013-12-31 | 2014-04-16 | 上海长顺电梯电缆有限公司 | Elevator traveling cable according with CSA standard |
| CN103730198A (en) * | 2013-12-31 | 2014-04-16 | 上海长顺电梯电缆有限公司 | Lift shaft cable meeting CSA standards |
| WO2014077280A1 (en) * | 2012-11-13 | 2014-05-22 | 矢崎総業株式会社 | Polyvinyl chloride resin composition for automobile electric wires and ultrathin low-voltage electric wire for automobiles |
| JP2017075335A (en) * | 2017-01-20 | 2017-04-20 | 日立金属株式会社 | Polyvinyl chloride resin composition and insulated wire prepared therewith, and method for producing insulated wire |
| KR20170127559A (en) | 2015-03-13 | 2017-11-21 | 가부시키가이샤 아데카 | Trimellitic acid triester plasticizer and a vinyl chloride resin composition containing the same |
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|---|---|---|---|---|
| CN100406514C (en) * | 2006-09-19 | 2008-07-30 | 上海电缆研究所 | Semi-horniness flame-proof PVC sheath material for high-voltage cable |
| JP5580742B2 (en) * | 2008-10-09 | 2014-08-27 | 株式会社Ａｄｅｋａ | Vinyl chloride resin composition for hard transparent product and hard transparent molded product formed by molding the composition |
| WO2010041378A1 (en) * | 2008-10-09 | 2010-04-15 | 株式会社Adeka | Vinyl chloride resin composition for transparent product, and transparent molded product produced by molding the composition |
| US8598259B2 (en) | 2008-10-09 | 2013-12-03 | Adeka Corporation | Vinyl chloride resin composition for transparent product, and transparent molded product produced by molding the composition |
| JP2012102309A (en) * | 2010-10-13 | 2012-05-31 | Mitsubishi Chemicals Corp | Polyvinyl chloride resin composition and electric wire |
| CN103680716B (en) * | 2012-09-21 | 2015-09-02 | 北京斯普乐电线电缆有限公司 | High temperature-resistancable cable for thermoplastic type car |
| CN103680716A (en) * | 2012-09-21 | 2014-03-26 | 北京斯普乐电线电缆有限公司 | High temperature-resistant cable for thermoplastic type car |
| WO2014077280A1 (en) * | 2012-11-13 | 2014-05-22 | 矢崎総業株式会社 | Polyvinyl chloride resin composition for automobile electric wires and ultrathin low-voltage electric wire for automobiles |
| US9976044B2 (en) | 2012-11-13 | 2018-05-22 | Yazaki Corporation | Polyvinyl chloride resin composition for automotive electric wire, and ultrathin-wall low-voltage electric wire for automobile |
| CN103730198A (en) * | 2013-12-31 | 2014-04-16 | 上海长顺电梯电缆有限公司 | Lift shaft cable meeting CSA standards |
| CN103724878A (en) * | 2013-12-31 | 2014-04-16 | 上海长顺电梯电缆有限公司 | Elevator traveling cable according with CSA standard |
| KR20170127559A (en) | 2015-03-13 | 2017-11-21 | 가부시키가이샤 아데카 | Trimellitic acid triester plasticizer and a vinyl chloride resin composition containing the same |
| JP2017075335A (en) * | 2017-01-20 | 2017-04-20 | 日立金属株式会社 | Polyvinyl chloride resin composition and insulated wire prepared therewith, and method for producing insulated wire |
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