JP2004158465A - Vinyl chloride based resin sheathed wire - Google Patents
Vinyl chloride based resin sheathed wire Download PDFInfo
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本発明は、耐熱老化性、耐油性、その他耐熱電線用途に適した諸特性を有する塩化ビニル系樹脂組成物を用いた被覆電線に関する。 The present invention relates to a coated electric wire using a vinyl chloride resin composition having heat aging resistance, oil resistance, and other characteristics suitable for heat-resistant electric wire applications.
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などの優れた機械的物性を有するため、電線、ホース或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、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、柔軟性や伸びが容易に損なわれる。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おこる。
このような高度な耐熱老化性を得るための手段として、トリメリット酸エステル系或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知られているが、原料に直鎖率の低いアルコールを用いた可塑剤では得られる耐熱老化性は十分とは言えない。
A vinyl chloride resin plasticized with 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, the vinyl chloride resin plasticized by a general-purpose plasticizer volatilizes when exposed to a high temperature, and easily loses flexibility and elongation. In addition, the same mechanical deterioration in mechanical properties occurs due to thermal deterioration of the vinyl chloride resin.
As a means for obtaining such high heat aging resistance, a method using a trimellitic acid ester-based or pyromellitic acid ester-based plasticizer is known, but an alcohol having a low linear ratio is used as a raw material. The heat aging resistance obtained with a plasticizer is not sufficient.
また、熱安定剤として珪酸鉛系化合物を使用することにより耐熱老化性が向上する（例えば、特許文献１参照）ことが知られているが、珪酸鉛系化合物の単独使用では色相や加工時の初期着色防止性が劣る。
さらに、上記のような耐熱性可塑剤を用いた場合、耐油性が劣るという問題も生じる。
また、電線用途特に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、そのための装置や工数増の問題があり、架橋以外の方法としてトリメリット酸エステル系或いはピロメリット酸エステル系可塑剤の使用が検討されているが、耐油性、耐寒性、耐摩耗性、硬度など自動車電線に要求されるその他の特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ていない。
Further, when the above-mentioned heat-resistant plasticizer is used, there is a problem that oil resistance is poor.
In addition, in electric wire applications, particularly in automotive electric wire applications, a crosslinking technique is usually employed as a means of imparting heat resistance. However, there is a problem of an increase in equipment and man-hours for such a purpose. Although the use of acid ester plasticizers is being studied, a vinyl chloride resin composition that comprehensively satisfies other properties required for automotive electric wires, such as oil resistance, cold resistance, abrasion resistance, and hardness, has been found. It has not been.
従って、本発明は、耐熱老化性、耐油性に優れかつ電線用途に適した耐摩耗性、耐寒性、適度の硬度等の諸特性を有する耐熱電線用途に好適な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。 Therefore, the present invention uses a vinyl chloride resin composition which is excellent in heat aging resistance, oil resistance and has various properties such as abrasion resistance, cold resistance and moderate hardness suitable for electric wire applications and which is suitable for heat resistant electric wire applications. It is an object to provide a covered electric wire.
本発明者らは、上記目的を達成するために鋭意検討を行った結果、本発明を完成させるに至ったものである。
すなわち、本発明は、
（１）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ピロメリット酸エステルの群から選ばれた少なくとも一種からなる多価カルボン酸エステル系可塑剤３０〜５０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、塩基性珪酸鉛０．１〜２０重量部および金属石鹸０．１〜１０重量部が配合されてなり、かつ前記可塑剤の合計量が３５〜６０重量部であり、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０．３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ことを特徴とする被覆電線、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０．１〜０．４の範囲で用いたことを特徴とする（１）記載の被覆電線
を提供するものである。
The present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention.
That is, the present invention
(1) A group 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 50 parts by weight of a polycarboxylic acid ester-based plasticizer composed of at least one 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, and 0.1 to 20 basic lead silicate. Parts by weight and 0.1 to 10 parts by weight of metal soap, the total amount of the plasticizer is 35 to 60 parts by weight, and the proportion of trimellitate in the total plasticizer is 0 by weight. (3) a coated electric wire, wherein a vinyl chloride resin composition having a weight ratio of polyester plasticizer in all plasticizers of not more than 0.4 is used as a coating material; As the carboxylic acid ester-based plasticizer, 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, and the weight ratio of the polyester-based plasticizer to the total plasticizer is used. The coated wire according to (1) is used in the range of 0.1 to 0.4.
請求項１および請求項２の発明によれば、耐熱電線用途に適した耐熱性、耐油性をはじめ耐寒性、耐摩耗性、適度の硬度等の諸特性を満足する塩化ビニル系樹脂組成物を被覆材に用いているため、ＪＡＳＯ Ｄ ６１１（＝ＪＩＳＣ ３４０６）規格ないしはＪＡＳＯ Ｄ ６０８規格に合格する耐熱被覆電線を提供することができ、工業的価値は極めて大きい。 According to the first and second aspects of the present invention, there is provided a vinyl chloride resin composition which satisfies various properties such as heat resistance, oil resistance, cold resistance, abrasion resistance, and appropriate hardness suitable for heat-resistant electric wire applications. Since it is used as a covering material, it is possible to provide a heat-resistant covered electric wire that meets the JASO D 611 (= JISC 3406) standard or the JASO D 608 standard, and has an extremely large industrial value.
本発明に使用される塩化ビニル系樹脂とは、塩化ビニル単独重合体及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、例えば懸濁重合法等が挙げられる。
ここで塩化ビニル系共重合体の例としては、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、ポリブタジエン−スチレン−メチルメタクリレート（ＭＢＳ）、ポリブタジエン−アクリロニトリル−（α−メチル）スチレン（ＡＢＳ）、スチレンブタジエン共重合体、ポリスチレン、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。
The vinyl chloride-based resin used in the present invention is a vinyl chloride homopolymer and a vinyl chloride-based copolymer, and its production method is a conventionally known polymerization method, such as a suspension polymerization method. Can be
Here, examples of the vinyl chloride copolymer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, Α-olefins having 2 to 30 carbon atoms, such as dodecene, 1-tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate and vinyl propionate A vinyl compound such as an alkyl vinyl ether; a polyfunctional monomer such as diallyl phthalate; a copolymer of a mixture thereof with a vinyl chloride monomer; an ethylene-acrylate copolymer such as an ethylene-ethyl acrylate copolymer; -Methyl methacrylate copolymer, ethylene-methacrylate copolymer , Ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, polybutadiene-styrene-methyl methacrylate (MBS), polybutadiene-acrylonitrile- (α-methyl) styrene (ABS), styrene butadiene Examples include copolymers, polystyrene, polymethyl methacrylate, and graft copolymers obtained by grafting a vinyl chloride monomer onto a mixture thereof.
本発明では、塩化ビニル系樹脂の可塑剤として、炭素数が４〜１２、好ましくは８〜１０で、直鎖率が５０％〜１００％、好ましくは９０％以上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の群から選ばれる少なくとも一種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未満であると、得られる耐熱老化性は不十分になり、１２より大きい場合には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。又、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。
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。
In the present invention, a saturated aliphatic alcohol having 4 to 12 carbon atoms, preferably 8 to 10 carbon atoms, and a linear ratio of 50% to 100%, preferably 90% or more is used as a plasticizer for the vinyl chloride resin. At least one polyvalent carboxylic acid ester-based plasticizer selected from the group consisting of trimellitic acid ester and pyromellitic acid ester is used as an essential component. When the carbon number of the alcohol used as the raw material of the plasticizer is less than 4, the heat aging resistance obtained is insufficient, and when it is larger than 12, the affinity for the vinyl chloride resin is extremely poor, so Causes poor gelation. On the other hand, when the linear chain ratio is less than 50%, the obtained heat aging resistance becomes insufficient.
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.
上記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或いはピロメリット酸と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である。 The polycarboxylic acid ester-based plasticizer is obtained by esterifying the above-mentioned saturated aliphatic alcohol having 4 to 12 carbon atoms and having a linear ratio of 50 to 100% with trimellitic acid or pyromellitic acid by an ordinary esterification method. It is obtained by conversion.
その添加量は、塩化ビニル系樹脂１００重量部に対し、３０〜５０重量部であり、３０〜４５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、被覆材として伸び特性に劣り、耐熱老化性、耐寒性も不十分である。５０重量部より多い場合は硬度、耐摩耗性が不十分となる傾向にある。
本発明で用いられる塩基性珪酸鉛は、例えばＰｂＯとＳｉＯ２の混合物を溶融し、冷却後粉砕した物であり、その混合比はＰｂＯ／ＳｉＯ２＝９０／１０〜６０／４０（重量比）の範囲が望ましい。また、その添加量は、塩化ビニル系樹脂１００重量部に対し、０．１〜２０重量部である。添加量が０．１重量部未満では得られる耐熱老化性が不十分になり、２０重量部を越えると伸び等の機械的物性が損なわれるため好ましくない。
The addition amount is 30 to 50 parts by weight, and most preferably 30 to 45 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 will have poor flexibility, poor elongation properties as a coating material, and insufficient heat aging resistance and cold resistance. If the amount is more than 50 parts by weight, hardness and abrasion resistance tend to be insufficient.
The basic lead silicate used in the present invention is, for example, a mixture of PbO and SiO 2 melted, cooled and pulverized, and the mixing ratio is PbO / SiO 2 = 90/10 to 60/40 (weight ratio). Is desirable. The amount of addition is 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the addition amount is less than 0.1 part by weight, the obtained heat aging resistance becomes insufficient, and if it exceeds 20 parts by weight, mechanical properties such as elongation are impaired, which is not preferable.
本発明で用いられる金属石鹸としては、例えば、バリウム、マグネシウム、鉛、カルシウム、亜鉛、カドミウム、アルミニウム、ナトリウム、錫等の金属のラウリン酸塩、パルミチン酸塩、ステアリン酸塩、オレイン酸塩、フタル酸塩、安息香酸塩、アジピン酸塩、マレイン酸塩等を挙げることができるが、これらは塩基性塩であっても構わない。さらにこれらの中でもステアリン酸カルシウム、ステアリン酸バリウム、ステアリン酸鉛、二塩基性ステアリン酸鉛が好ましく用いられ、これらは単独もしくは二種以上を組み合わせて併用しても良く、必要に応じて多数種を組み合わせることにより、色相改善並びに初期着色防止性向上の効果は大きい。
また、これら金属石鹸の添加量は、塩化ビニル系樹脂１００重量部に対し、０．１〜１０重量部である。０．１重量部未満では色相改善及び初期着色防止性向上の効果が不十分になり、１０重量部を越えると加工成形時のゲル化不良を引き起こす。
Examples of the metal soap used in the present invention include laurate, palmitate, stearate, oleate, and phthalate of metals such as barium, magnesium, lead, calcium, zinc, cadmium, aluminum, sodium, and tin. Examples thereof include acid salts, benzoates, adipates, and maleates, and these may be basic salts. Further among these, calcium stearate, barium stearate, lead stearate, dibasic lead stearate are preferably used, and these may be used alone or in combination of two or more kinds, and a plurality of kinds may be combined as necessary. As a result, the effect of improving the hue and the effect of preventing the initial coloring are great.
The addition amount of these metal soaps is 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.1 part by weight, the effect of improving the hue and the effect of preventing the initial coloring are insufficient. If the amount exceeds 10 parts by weight, poor gelation at the time of working and molding is caused.
本発明において、塩基性珪酸鉛と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塩基性珪酸鉛が溶融せず分散性が悪いため、比較的融点が低く塩化ビニル樹脂内での分散性の良い金属石鹸を添加することで、塩基性珪酸鉛単独使用の場合に生じる塩化ビニル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。
本発明の目的である耐油性向上には、上述の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なる多価カルボン酸エステル系可塑剤に加えポリエステル系の可塑剤を添加することが重要である。
ここでポリエステル系の可塑剤としては、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を通常のエステル化法によりエステル化して得られる物で、２５℃での粘度が１０００ｃｐｓ以上の物が好ましく、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。
In the present invention, the use of basic lead silicate and metal soap improves the hue as well as the ability to prevent initial coloring during processing.However, this is because the basic lead silicate does not melt and disperse at the processing temperature of the vinyl chloride resin. Addition of a metal soap with a relatively low melting point and good dispersibility in vinyl chloride resin due to poor properties suppresses local decomposition in vinyl chloride resin that occurs when using basic lead silicate alone I think it is possible.
In order to improve the oil resistance, which is an object of the present invention, it is important to add a polyester-based plasticizer in addition to the above-mentioned polyvalent carboxylate-based plasticizer composed of trimellitic acid ester and / or pyromellitic acid ester. .
Here, as the polyester plasticizer, for example, a product obtained by esterifying adipic acid with 1,3-butanediol and 2-ethylhexanol by a normal esterification method, and having a viscosity at 25 ° C. of 1000 cps or more. Is preferable, and 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、好ましくは１〜１００重量部であり、更に好ましくは３〜５０重量部であり、最も好ましくは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になり、又、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。 The addition amount of such a polyester plasticizer is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, and most preferably 3 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. Department. If the amount is less than 1 part by weight, the effect of improving oil resistance becomes insufficient, and if it exceeds 100 parts by weight, bleeding or poor gelation during processing is caused.
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、耐摩耗性、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配合量は塩化ビニル系樹脂１００重量部に対して３０〜５０重量部である。３０重量部未満では耐熱老化性が不足し、５０重量部を越えると耐磨耗性に劣る。また、ポリエステル系可塑剤が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、可塑剤の合計量が３５重量部以下では耐寒性が劣り、６０重量部以上では硬度が低下し、電線として使用できない。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０．３以下が好ましく、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０．３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。 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, a predetermined oil resistance, abrasion resistance, cold resistance, appropriate hardness, etc. are required. The amount of the polycarboxylic acid ester-based plasticizer required for that purpose is 30 to 50 parts by weight based on 100 parts by weight of the vinyl chloride resin. If it is less than 30 parts by weight, the heat aging resistance is insufficient, and if it exceeds 50 parts by weight, the abrasion resistance is poor. When the amount of the polyester plasticizer is less than 3 parts by weight, the oil resistance is poor, and when the amount 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. When the total amount is 60 parts by weight or more, the hardness is reduced and the plasticizer cannot be used as an electric wire. Furthermore, the ratio of trimellitate to the total amount of plasticizer used is preferably 0.3 or less by weight, and when the ratio of trimellitate to the total amount of plasticizer exceeds 0.3 by weight, heat resistance is increased. Aging property 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.
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、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塩化ビニル系樹脂１００重量部に対して３０〜５０重量部配合する。３０重量部未満では耐熱老化性が不足し、５０重量部を越えると耐磨耗性に劣る。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、６０重量部以上では硬度が低下し、電線として使用できない。 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, as a polyvalent carboxylic acid ester, 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 a raw material is added to 30 parts by weight of the vinyl chloride resin based on 100 parts by weight. ５０50 parts by weight. If it is less than 30 parts by weight, the heat aging resistance is insufficient, and if it exceeds 50 parts by weight, the abrasion resistance is poor. If the total amount of the pyromellitic acid ester and the polyester-based plasticizer is 35 parts by weight or less, the cold resistance is poor. If the total amount is 60 parts by weight or more, the hardness is reduced, and it cannot be used as an electric wire.
上記の配合条件を満たす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８５％以上、耐寒性−２０℃以下、耐磨耗性４０回以上、硬度８８〜９８を達成することができる。
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、上記以外の可塑剤、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ときには、難燃剤として三酸化アンチモンなどを、塩化ビニル系樹脂１００重量部に対して１〜２０重量部程度配合して難燃化を図るとよい。
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。
By using a composition that satisfies the above compounding conditions, the elongation residual after heating at 160 ° C. for 200 hours is 70% or more (general heat resistance application) or 80% or more, which is a passing criterion by a sheet test for passing as an electric wire application. (Use for heat-resistant automobiles), residual elongation after oil immersion of 85% or more, cold resistance of -20 ° C or less, abrasion resistance of 40 times or more, and hardness of 88 to 98 can be achieved.
In addition, the vinyl chloride resin composition in the present invention is, if necessary, a plasticizer, a stabilizer, a lubricant, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, a filler, a pigment, a processing aid other than those described above. Such additives as those commonly used for vinyl chloride resins 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 electric wires, antimony trioxide or the like is blended as a flame retardant in an amount of about 1 to 20 parts by weight with respect to 100 parts by weight of a vinyl chloride resin to achieve flame retardancy. Good.
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.
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、上述の炭素数が４〜１２で直鎖率が５０〜１００％の飽和の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なる多価カルボン酸エステル系可塑剤と塩基性珪酸鉛および金属石鹸、もしくはさらに２５℃での粘度が１０００ｃｐｓ以上のポリエステル系可塑剤を、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・配合された配合粉として、或いはその配合粉を、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造粒したペレットとして得ることができる。
また、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１７０〜１９５℃、クロスヘッド部１８０℃の設定温度で、線速３５０〜４５０ｍ／分程度の電線製造が可能である。
The vinyl chloride resin composition of the present invention is obtained by adding a trimellitic acid ester obtained by using, as a raw material, the above-mentioned saturated alcohol having 4 to 12 carbon atoms and a linear ratio of 50 to 100% to the vinyl chloride resin. A polycarboxylic acid ester plasticizer composed of pyromellitic acid ester and a basic lead silicate and metal soap, or a polyester plasticizer having a viscosity at 25 ° C. of 1000 cps or more, for example, Henschel mixer, Banbury mixer, ribbon blender As a compound powder stirred and compounded by a stirrer or the like, or by using a compounder such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a kneader-type kneader, or a roll kneader It can be obtained as granulated pellets.
In addition, in order to cover the conductor with the vinyl chloride resin composition of the present invention to form an electric wire, a conventionally known extrusion coating apparatus equipped with an extruder may be used. At the set temperature of the head section of 180 ° C., it is possible to manufacture electric wires at a linear speed of about 350 to 450 m / min.
以下、実施例により本発明を具体的に説明するがこれらは本発明の範囲をなんら制限するものではない。尚、実施例により得られたプレスシートの色相の評価と、加熱後伸び残率の測定は下記に示す方法による。
・色相：シートを目視により評価したものである。
・加熱後伸び残率：シートの加熱前と１６０℃のギヤオーブンで２００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：シートの加熱浸油前と１２０℃に加熱したＪＩＳ−Ｋ６３０１に規定されるＮｏ．１油に８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。
Hereinafter, the present invention will be described specifically with reference to Examples, but these do not limit the scope of the present invention. The evaluation of the hue of the press sheet obtained in the examples and the measurement of the residual elongation after heating are performed by the following methods.
Hue: The sheet was visually evaluated.
-Residual elongation after heating: The tensile elongation before heating the sheet and after heating for 200 hours in a gear oven at 160 ° C was measured by a tensile test method according to JIS-K7113, and the tensile elongation after heating was measured before heating. It was calculated by dividing by the tensile elongation.
-Elongation residual ratio after oil immersion: No. stipulated in JIS-K6301 before heating oil immersion of the sheet and heated to 120 ° C. After soaking in one oil for 8 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.
さらに、電線として使用する条件としての耐寒性、耐摩耗性、硬度についての評価はプレスシートを用い下記に示す方法による。
・耐寒性：ＪＩＳ−Ｋ６７２３に準ずる耐寒性試験法にて媒体はエタノールを使用して測定を行った。
・耐磨耗性：ＪＡＳＯ Ｄ ６１１−８６に準じブレード往復法試験にて、ブレード荷重を１５００ｇとし、ブレードとアングル型試験台とがサンプルを挟み通電するに至るまでの往復回数を磨耗回数として測定することにより評価した。
・硬度：ＪＩＳ−Ｋ６３０１に準ずる定荷重式硬さ試験法にて測定を行った。
Furthermore, evaluation of cold resistance, wear resistance, and hardness as conditions for use as an electric wire is performed using a press sheet and the method described below.
-Cold resistance: Measurement was performed using ethanol as a medium in a cold resistance test method according to JIS-K6723.
Abrasion resistance: In a blade reciprocation test according to JASO D 611-86, the blade load was set to 1500 g, and the number of reciprocations until the blade and the angle type test table sandwiched the sample and turned on electricity was measured as the number of abrasions. Was evaluated.
Hardness: Measured by a constant load hardness test method according to JIS-K6301.
特に電線用途に適した塩化ビニル系樹脂組成物を用いた電線を提供するための請求項１および請求項２の発明について、より具体的に説明する。 In particular, the invention of claims 1 and 2 for providing an electric wire using a vinyl chloride resin composition suitable for electric wire applications will be described more specifically.
参考例１〜５
表１に示した配合割合にしたがって、平均重合度が２０００の塩化ビニル単独重合体に、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に加え、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を、全可塑剤中のトリオクチルトリメリテートの割合が重量比で０．３以下となるよう、さらに２５℃での粘度が３０００ｃｐｓのポリエステル系可塑剤をポリエステル系可塑剤を全可塑剤中の割合が０．４以下となるようにそれぞれ配合し、この配合物を１８０℃のロール混練機にて１５分間混練した後、１８０℃のプレス成形機にて５０ｋｇ／ｃｍ２の圧力で４分間プレス成形して、厚さ０．５ｍｍ、１ｍｍ、２ｍｍ、１２ｍｍのシートを得た。１ｍｍ厚のシートを用いて、成形時及び加熱時（１６０℃のギヤオーブンで２００時間加熱）の色相評価および加熱後伸び残率と浸油後伸び残率の測定を、また、２ｍｍ厚のシートを用いて耐寒性、０．５ｍｍのシートを用いて耐摩耗性、１２ｍｍ厚のシートを用いて硬度をそれぞれ測定した。結果を表１に示す。
Reference Examples 1 to 5
According to the compounding ratio shown in Table 1, a vinyl chloride homopolymer having an average degree of polymerization of 2,000 was added to tetraoctyl pyromellitate having a linear ratio of raw material alcohol of 95% as a polycarboxylic acid ester-based plasticizer. The trioctyl trimellitate having a raw material alcohol having a linear ratio of 95% is further added with a viscosity at 25 ° C. so that the weight ratio of trioctyl trimellitate in all plasticizers is 0.3 or less. A 3000 cps polyester plasticizer is blended with each other so that the ratio of the polyester plasticizer to the total plasticizer is 0.4 or less, and the blend is kneaded with a roll kneader at 180 ° C. for 15 minutes. The sheet was press-formed at a pressure of 50 kg / cm 2 for 4 minutes using a press forming machine at a temperature of 0.5 ° C. to obtain sheets having thicknesses of 0.5 mm, 1 mm, 2 mm and 12 mm. Using a 1 mm thick sheet, the hue evaluation at the time of molding and heating (heating in a 160 ° C. gear oven for 200 hours) and measurement of the residual elongation after heating and the residual elongation after oil immersion were performed. , The wear resistance was measured using a 0.5 mm sheet, and the hardness was measured using a 12 mm thick sheet. Table 1 shows the results.
比較例１、２
表１に示した配合割合にしたがって、参考例１〜５と同様の方法で各厚さのシートを得て物性を測定した。結果を表１に示す。
Comparative Examples 1 and 2
According to the compounding ratios shown in Table 1, sheets of each thickness were obtained in the same manner as in Reference Examples 1 to 5, and the physical properties were measured. Table 1 shows the results.
表１の結果から、参考例１〜５の組成物はいずれも、加熱後伸び残率７０％以上の耐熱老化性、浸油後伸び残率８５％以上の耐油性、−２０℃以下の耐寒性、摩耗回数４０回以上の耐摩耗性、８８〜９８の範囲の硬度を示し、一般耐熱電線用途で必要とする諸特性を満足するものであることがわかる。また、参考例１のように、トリメリット酸エステル量、ポリエステル系可塑剤量を少な目に調整することにより、自動車用耐熱架橋電線の規格を満足する高度の耐熱性も実現できることがわかる。
一方、比較例１の組成物はポリエステル系可塑剤の全可塑剤中の割合が０．５と多いため加熱後の伸び残率が６５％と低く、また、比較例２の組成物もトリオクチルトリメリテートの全可塑剤中の割合が０．５と多いため加熱後の伸び残率が６０％と低くなっており、一般耐熱電線用途で必要とされる耐熱老化性が得られないことがわかる。
From the results in Table 1, all of the compositions of Reference Examples 1 to 5 have heat aging resistance of elongation residual after heating of 70% or more, oil resistance of elongation residual after oil immersion of 85% or more, and cold resistance of -20 ° C or less. It shows abrasion resistance, abrasion resistance of 40 times or more, and hardness in the range of 88 to 98, and it can be seen that it satisfies various characteristics required for general heat-resistant electric wire applications. Also, as in Reference Example 1, by adjusting the amount of trimellitic acid ester and the amount of the polyester-based plasticizer to a small amount, it can be seen that a high degree of heat resistance that satisfies the standard for heat-resistant crosslinked electric wires for automobiles can be realized.
On the other hand, the composition of Comparative Example 1 has a low residual elongation after heating of 65% because the ratio of the polyester-based plasticizer in the total plasticizer is as large as 0.5, and the composition of Comparative Example 2 is also trioctyl. Since the proportion of trimellitate in the total plasticizer is as large as 0.5, the residual elongation after heating is as low as 60%, and the heat aging resistance required for general heat-resistant electric wire applications cannot be obtained. Understand.
参考例６〜１３、比較例３〜９
表２および表３に示した組成割合にしたがって、多価カルボン酸エステル系可塑剤として、原料アルコーの直鎖率が９５％であるテトラオクチルピロメリテートのみを用いた他は、参考例１〜５と同様にして厚さ０．５ｍｍ、１ｍｍ、２ｍｍ、１２ｍｍのシートを得た。
得られたシートを用いて、参考例１と同様、成形時の色相評価をし、加熱後伸び残率、浸油後伸び残率、耐寒性、耐摩耗性および硬度をそれぞれ測定した。参考例の結果を表２に、比較例の結果を表３にそれぞれ示す。
Reference Examples 6 to 13 and Comparative Examples 3 to 9
According to the composition ratios shown in Tables 2 and 3, as reference examples except that only tetraoctyl pyromellitate in which the raw material alcohol had a linear ratio of 95% was used as a polycarboxylic acid ester-based plasticizer. In the same manner as in Example 5, sheets having thicknesses of 0.5 mm, 1 mm, 2 mm, and 12 mm were obtained.
Using the obtained sheet, the hue at the time of molding was evaluated in the same manner as in Reference Example 1, and the residual elongation after heating, the residual elongation after oil immersion, cold resistance, abrasion resistance and hardness were measured. Table 2 shows the results of the reference example, and Table 3 shows the results of the comparative example.
表２の結果から、参考例６〜１３の組成物はいずれも、加熱後伸び残率８０％以上の耐熱老化性、浸油後伸び残率８５％以上の耐油性、−２０℃以下の耐寒性、摩耗回数４０回以上の耐摩耗性、８８〜９８の範囲の硬度を示し、自動車用耐熱電線用途で必要とする諸特性（ＪＡＳＯ Ｄ ６０８）を満足するものであることがわかる。一方、表３の結果から、比較例３、７の組成物のように全可塑剤中に占めるポリエステル系可塑剤の配合割合が多過ぎると加熱後伸び残率（耐熱老化性）が不十分となり、比較例８、９の組成物のように少な過ぎると浸油後伸び残率（耐油性）が不十分となることがわかる。また、比較例４、５、６の組成物のようにポリエステル系可塑剤の配合割合を適量としても全可塑剤量が多すぎると、耐摩耗性、硬度が不足し電線用途としての必要特性を満足しないことがわかる。 From the results in Table 2, all of the compositions of Reference Examples 6 to 13 have heat aging resistance of 80% or more of residual elongation after heating, oil resistance of 85% or more of residual elongation after immersion, and cold resistance of -20 ° C or less. It shows abrasion resistance, abrasion resistance of 40 times or more, and hardness in the range of 88 to 98, and it can be seen that it satisfies various characteristics (JASO D 608) required for heat-resistant electric wires for automobiles. On the other hand, from the results in Table 3, when the blending ratio of the polyester-based plasticizer in the total plasticizer is too large as in the compositions of Comparative Examples 3 and 7, the residual elongation after heating (heat aging resistance) becomes insufficient. It can be seen that if the composition is too small as in the compositions of Comparative Examples 8 and 9, the residual elongation after oil immersion (oil resistance) becomes insufficient. Also, even if the mixing ratio of the polyester-based plasticizer is set to an appropriate amount as in the compositions of Comparative Examples 4, 5, and 6, when the total amount of the plasticizer is too large, the abrasion resistance and the hardness are insufficient, and the necessary properties for electric wire applications are reduced. It turns out that they are not satisfied.
実施例１
参考例２および参考例６の組成物を用いて、６０ｍｍφ、Ｌ／Ｄ２５の押出機により、設定温度を材料投入側から順次１７５℃、１９０℃、１９３℃、クロスヘッド部１８０℃とし、線速４００ｍ／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諸特性を評価した。評価項目、方法は、ＪＡＳＯ Ｄ ６１１（＝ＪＩＳ Ｃ ３４０６）規格およびＪＡＳＯ Ｄ ６０８規格に準拠した。評価結果を表４にまとめて示す。
Example 1
Using the compositions of Reference Examples 2 and 6, the set temperatures were sequentially set to 175 ° C., 190 ° C., 193 ° C. and 180 ° C. in the crosshead section from the material input side by an extruder having a diameter of 60 mm and an L / D of 25. An insulating layer having a predetermined thickness was extruded on the conductor at 400 m / min to obtain a coated electric wire, and various characteristics were evaluated. Evaluation items and methods were based on JASO D 611 (= JIS C 3406) standard and JASO D 608 standard. The evaluation results are shown in Table 4.
表４の結果から分かるように、本発明において電線用途に適しているとして提供される組成物を用いた請求項１および請求項２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特性にすべて合格することが確かめられた。 As can be seen from the results in Table 4, the coated electric wire corresponding to Claims 1 and 2 using the composition provided as being suitable for electric wire use in the present invention has the heat resistance specified by the electric wire standard. It was confirmed that all the properties including the above were passed.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004039077A JP2004158465A (en) | 1995-09-05 | 2004-02-16 | Vinyl chloride based resin sheathed wire |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22767195 | 1995-09-05 | ||
| JP22767095 | 1995-09-05 | ||
| JP2004039077A JP2004158465A (en) | 1995-09-05 | 2004-02-16 | Vinyl chloride based resin sheathed wire |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23454396A Division JP3706208B2 (en) | 1995-09-05 | 1996-09-04 | Vinyl chloride resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004158465A true JP2004158465A (en) | 2004-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004039077A Pending JP2004158465A (en) | 1995-09-05 | 2004-02-16 | Vinyl chloride based resin sheathed wire |
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| JP (1) | JP2004158465A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105225749A (en) * | 2015-08-18 | 2016-01-06 | 合肥市再德高分子材料有限公司 | A kind of heat-resisting oil resistant cable |
| US10811165B2 (en) | 2014-12-05 | 2020-10-20 | Kuraray Co., Ltd. | Insulation material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01182351A (en) * | 1988-01-12 | 1989-07-20 | Mitsubishi Kasei Vinyl Co | Electron radiation crosslinkable vinyl chloride resin composition |
| JPH0753818A (en) * | 1993-08-11 | 1995-02-28 | Asahi Denka Kogyo Kk | Vinyl chloride-based resin composition |
-
2004
- 2004-02-16 JP JP2004039077A patent/JP2004158465A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01182351A (en) * | 1988-01-12 | 1989-07-20 | Mitsubishi Kasei Vinyl Co | Electron radiation crosslinkable vinyl chloride resin composition |
| JPH0753818A (en) * | 1993-08-11 | 1995-02-28 | Asahi Denka Kogyo Kk | Vinyl chloride-based resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10811165B2 (en) | 2014-12-05 | 2020-10-20 | Kuraray Co., Ltd. | Insulation material |
| CN105225749A (en) * | 2015-08-18 | 2016-01-06 | 合肥市再德高分子材料有限公司 | A kind of heat-resisting oil resistant cable |
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