JP2017019943A - Polyvinyl chloride resin composition, and wire and cable prepared therewith - Google Patents
Polyvinyl chloride resin composition, and wire and cable prepared therewith Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
- H01B7/0208—Cables with several layers of insulating material
- H01B7/0216—Two layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Abstract
Description
本発明は、塩化ビニル樹脂組成物並びにこれを用いた電線及びケーブルに関するものである。 The present invention relates to a vinyl chloride resin composition and electric wires and cables using the same.
塩化ビニル樹脂（ＰＶＣ）は、低コストで難燃性を有する材料であり、柔軟性付与のため可塑剤を添加することで電線被覆材として使用される。 Vinyl chloride resin (PVC) is a low-cost and flame-retardant material, and is used as a wire coating material by adding a plasticizer to impart flexibility.
可塑剤としては、安価でＰＶＣとの相溶性が高いジ−２−エチルヘキシルフタレート（ＤＯＰ）が主に使われるが（例えば特許文献１参照）、近年、ＲＥＡＣＨ規則に加え、ＲｏＨＳ指令の使用禁止物質に指定される恐れもあり、今後の使用が危ぶまれている。 As a plasticizer, di-2-ethylhexyl phthalate (DOP), which is inexpensive and highly compatible with PVC, is mainly used (see, for example, Patent Document 1). In recent years, in addition to the REACH regulations, substances prohibited to use in the RoHS directive are used. In the future, there is a risk that it will be designated, and its future use is in danger.
ＤＯＰの代替候補としては、ＤＯＰに次いで電線被覆材として使用実績のあるジイソノニルフタレート（ＤＩＮＰ）が挙げられるが（例えば特許文献２参照）、ＤＩＮＰはゴム用途にも使用され、供給逼迫を起す可能性があるため、その他の可塑剤の実用化が望まれている。 DOP alternative candidates include diisononyl phthalate (DINP), which has been used as a wire covering material after DOP (see, for example, Patent Document 2). Therefore, practical application of other plasticizers is desired.
その他の可塑剤としては、ＤＯＰ、ＤＩＮＰと同等のＰＶＣとの相溶性を有するテレフタル酸エステル構造の可塑剤がある（例えば特許文献３〜４参照）。 As another plasticizer, there is a plasticizer having a terephthalic acid ester structure having compatibility with PVC equivalent to DOP and DINP (for example, see Patent Documents 3 to 4).
しかしながら、下記一般式（１）で表されるテレフタル酸エステルは下記一般式（２）で表されるフタル酸エステルと比較して耐候性に劣るため、電線用途で屋外使用するには問題がある（各式中のＲはアルキル鎖炭素数を示す）。
また、添加剤の中には、ＰＶＣやテレフタル酸エステルと相溶しづらく、組成物表面にブリードし、ベタつきを生じる問題が発生するものがある。 Further, some additives are difficult to be compatible with PVC and terephthalic acid ester, and bleed on the surface of the composition and cause stickiness.
そこで、本発明は、可塑剤としてテレフタル酸エステルを使用しても耐候性及び耐ブリード性が良好な塩化ビニル樹脂組成物並びにこれを用いた電線及びケーブルを提供することを目的とする。 Therefore, an object of the present invention is to provide a vinyl chloride resin composition having good weather resistance and bleed resistance even when terephthalic acid ester is used as a plasticizer, and an electric wire and cable using the same.
上記目的を達成するため、本発明によれば、以下の塩化ビニル樹脂組成物並びにこれを用いた電線及びケーブルが提供される。 In order to achieve the above object, according to the present invention, the following vinyl chloride resin composition, and electric wires and cables using the same are provided.
［１］可塑剤としてテレフタル酸エステルを含有する塩化ビニル樹脂組成物であって、
塩化ビニル樹脂１００質量部に対して、前記テレフタル酸エステルを１００質量部以下、シリコーンゴムを０．１質量部以上含有する塩化ビニル樹脂組成物。
［２］塩化ビニル樹脂１００質量部に対して、前記テレフタル酸エステルを１０〜１００質量部含有する前記［１］に記載の塩化ビニル樹脂組成物。
［３］塩化ビニル樹脂１００質量部に対して、前記シリコーンゴムを０．１〜５質量部含有する前記［１］又は前記［２］に記載の塩化ビニル樹脂組成物。
［４］前記テレフタル酸エステルは、１本当たりのアルキル鎖の炭素数が８〜１０であるテレフタル酸エステルである前記［１］〜［３］のいずれか１つに記載の塩化ビニル樹脂組成物。
［５］可塑剤としてテレフタル酸エステルを含有する塩化ビニル樹脂組成物であって、塩化ビニル樹脂１００質量部に対して、前記テレフタル酸エステルを１００質量部以下、シリコーンゴムを０．１質量部以上含有する塩化ビニル樹脂組成物からなる絶縁層を備えた電線。
［６］可塑剤としてテレフタル酸エステルを含有する塩化ビニル樹脂組成物であって、塩化ビニル樹脂１００質量部に対して、前記テレフタル酸エステルを１００質量部以下、シリコーンゴムを０．１質量部以上含有する塩化ビニル樹脂組成物からなるシースを備えたケーブル。
［７］前記［５］に記載の電線を備えた前記［６］に記載のケーブル。
[1] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer,
A vinyl chloride resin composition containing 100 parts by mass or less of the terephthalic acid ester and 0.1 parts by mass or more of silicone rubber with respect to 100 parts by mass of the vinyl chloride resin.
[2] The vinyl chloride resin composition according to the above [1], containing 10 to 100 parts by mass of the terephthalic acid ester with respect to 100 parts by mass of the vinyl chloride resin.
[3] The vinyl chloride resin composition according to [1] or [2] above, containing 0.1 to 5 parts by mass of the silicone rubber with respect to 100 parts by mass of the vinyl chloride resin.
[4] The vinyl chloride resin composition according to any one of [1] to [3], wherein the terephthalic acid ester is a terephthalic acid ester having 8 to 10 carbon atoms per alkyl chain. .
[5] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein the terephthalic acid ester is 100 parts by mass or less and the silicone rubber is 0.1 part by mass or more with respect to 100 parts by mass of the vinyl chloride resin. An electric wire provided with an insulating layer made of a vinyl chloride resin composition.
[6] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein the terephthalic acid ester is 100 parts by mass or less and the silicone rubber is 0.1 part by mass or more with respect to 100 parts by mass of the vinyl chloride resin. A cable including a sheath made of a vinyl chloride resin composition.
[7] The cable according to [6], including the electric wire according to [5].
本発明によれば、可塑剤としてテレフタル酸エステルを使用しても耐候性及び耐ブリード性が良好な塩化ビニル樹脂組成物並びにこれを用いた電線及びケーブルが提供される。 ADVANTAGE OF THE INVENTION According to this invention, even if it uses a terephthalic acid ester as a plasticizer, a weather resistance and bleeding resistance are favorable, and an electric wire and a cable using the same are provided.
〔塩化ビニル樹脂組成物〕
本発明の実施形態に係る塩化ビニル樹脂組成物は、可塑剤としてテレフタル酸エステルを含有する塩化ビニル樹脂組成物であって、塩化ビニル樹脂１００質量部に対して、前記テレフタル酸エステルを１００質量部以下、シリコーンゴムを０．１質量部以上含有する。
[Vinyl chloride resin composition]
A vinyl chloride resin composition according to an embodiment of the present invention is a vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, and 100 parts by mass of the terephthalic acid ester with respect to 100 parts by mass of the vinyl chloride resin. Hereinafter, 0.1 mass part or more of silicone rubber is contained.
本発明者は、テレフタル酸エステルが耐候性に劣る理由は、テレフタル酸エステルはエステルのカルボキシル基が開いた構造のため、外部から侵入する水の接触が容易となり加水分解性が高いためと考えた。 The present inventor considered that the reason that terephthalic acid ester is inferior in weather resistance is that terephthalic acid ester has a structure in which the carboxyl group of the ester is open, so that it can easily contact water entering from the outside and has high hydrolyzability .
そこで、テレフタル酸エステル使用時の耐候性劣化を抑制するために、種々の添加剤について添加検討を行った結果、撥水性に優れるシリコーンゴムを添加することで耐候性が改善できることを見出した。 Then, in order to suppress the weather resistance deterioration at the time of terephthalic acid ester use, as a result of examining addition about various additives, it discovered that a weather resistance could be improved by adding the silicone rubber excellent in water repellency.
一方、液状のシリコーンオイルでは、耐候性は改善するものの、ＰＶＣやテレフタル酸エステルと相溶しづらく、組成物表面にブリードし、ベタつきが生じる問題が発生した。 On the other hand, although the weather resistance is improved in the liquid silicone oil, it is difficult to be compatible with PVC or terephthalic acid ester, and it bleeds on the surface of the composition and causes stickiness.
そのため、耐候性と共に耐ブリード性も考慮して検討した結果、固形状のシリコーンゴムがこれらを両立できることを見出し、本発明の塩化ビニル樹脂組成物を開発するに至った。 Therefore, as a result of considering the weather resistance as well as the bleed resistance, it was found that a solid silicone rubber can achieve both of these, and the vinyl chloride resin composition of the present invention has been developed.
（テレフタル酸エステル）
本発明の実施形態に係る塩化ビニル樹脂組成物で可塑剤として使用されるテレフタル酸エステルとしては、１本当たりのアルキル鎖の炭素数が８〜１０（Ｃ８〜Ｃ１０）であるテレフタル酸エステルが好適である。Ｃ８未満では必要な耐熱性が得られにくい。アルキル鎖炭素数が少ない程、即ち分子量が低い程、加熱による可塑剤の揮発が促進され、塩化ビニル樹脂組成物が硬化するためである。一方、Ｃ１１以上であると、可塑剤のエステル合成に必要なアルコール入手が困難であり、コストが高くなるため実用性が低く、Ｃ１０以下であるほうが好ましい。
(Terephthalic acid ester)
The terephthalic acid ester used as a plasticizer in the vinyl chloride resin composition according to the embodiment of the present invention is preferably a terephthalic acid ester having 8 to 10 (C8 to C10) carbon atoms per alkyl chain. It is. If it is less than C8, it is difficult to obtain necessary heat resistance. This is because the smaller the number of alkyl chain carbon atoms, that is, the lower the molecular weight, the more the volatilization of the plasticizer by heating is promoted and the vinyl chloride resin composition is cured. On the other hand, when it is C11 or more, it is difficult to obtain an alcohol necessary for ester synthesis of the plasticizer, and the cost becomes high, so the practicality is low, and C10 or less is preferable.
テレフタル酸エステルのアルキル鎖は、直鎖構造であっても分岐鎖構造であってもよいが、分岐鎖構造であることが好ましい。具体的には、Ｃ８のものとしてジ−２−エチルヘキシルテレフタレート（ＤＯＴＰ）、Ｃ９のものとしてジイソノニルテレフタレート（ＤＩＮＴＰ）、Ｃ１０のものとしてジイソデシルテレフタレート（ＤＩＤＴＰ）が挙げられるが、これらに限られない。 The alkyl chain of the terephthalic acid ester may have a straight chain structure or a branched chain structure, but is preferably a branched chain structure. Specific examples include di-2-ethylhexyl terephthalate (DOTP) as C8, diisononyl terephthalate (DINTP) as C9, and diisodecyl terephthalate (DIDTP) as C10.
本発明の実施の形態において、上記テレフタル酸エステルの添加量は、塩化ビニル樹脂１００質量部に対して、１００質量部以下とする。１０質量部以上、添加することが好ましい。シリコーンゴムを添加することにより、テレフタル酸エステル添加に対し効果を発揮するが、テレフタル酸エステルの添加量が１００質量部を超えると、可塑剤自体がブリードし、表面にベタつきが発生する。 In embodiment of this invention, the addition amount of the said terephthalic acid ester shall be 100 mass parts or less with respect to 100 mass parts of vinyl chloride resins. It is preferable to add 10 parts by mass or more. By adding silicone rubber, an effect is exhibited with respect to the addition of terephthalic acid ester. However, when the addition amount of terephthalic acid ester exceeds 100 parts by mass, the plasticizer itself bleeds and stickiness occurs on the surface.
（シリコーンゴム）
本発明の実施形態に係る塩化ビニル樹脂組成物で使用されるシリコーンゴムとしては、例えば、ジメチルシリコーンゴム、メチルフェニルシリコーンゴム、ビニルフェニルシリコーンゴム、メチルビニルフェニルシリコーンゴムが好適である。
(silicone rubber)
As the silicone rubber used in the vinyl chloride resin composition according to the embodiment of the present invention, for example, dimethyl silicone rubber, methyl phenyl silicone rubber, vinyl phenyl silicone rubber, and methyl vinyl phenyl silicone rubber are suitable.
本発明の実施の形態において、上記シリコーンゴムの添加量は、塩化ビニル樹脂１００質量部に対して、０．１質量部以上必要である。添加量０．１質量部未満では必要な耐候性が得られない。また、添加量は、５質量部以下であることが好ましい。５質量部を超えると、加工性に問題が生じやすい。 In the embodiment of the present invention, the amount of the silicone rubber added is required to be 0.1 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. If the amount added is less than 0.1 parts by mass, the required weather resistance cannot be obtained. Moreover, it is preferable that the addition amount is 5 parts by mass or less. If it exceeds 5 parts by mass, a problem is likely to occur in workability.
（塩化ビニル樹脂）
塩化ビニル樹脂としては、塩化ビニルの単独重合体（すなわちポリ塩化ビニル）のほか、塩化ビニルと他の共重合可能なモノマーとの共重合体、及びこれらの混合物が挙げられる。塩化ビニルと共重合可能なモノマーとしては、酢酸ビニル、塩化ビニリデン、（メタ）アクリル酸、アクリロニトリル等が挙げられる。
(Vinyl chloride resin)
Examples of the vinyl chloride resin include vinyl chloride homopolymers (that is, polyvinyl chloride), copolymers of vinyl chloride and other copolymerizable monomers, and mixtures thereof. Examples of the monomer copolymerizable with vinyl chloride include vinyl acetate, vinylidene chloride, (meth) acrylic acid, acrylonitrile and the like.
塩化ビニル樹脂は、平均重合度１０００〜２５００のものを用いることが好ましい。平均重合度１０００〜２０００のものが耐熱性、耐寒性、成形性の面からより好ましい。重合度が低くなると成形性は向上するが耐熱性、耐寒性が低下する。逆に重合度が高くなると耐熱性、耐寒性は向上するが、成形性が悪くなる。 It is preferable to use a vinyl chloride resin having an average degree of polymerization of 1000 to 2500. Those having an average degree of polymerization of 1000 to 2000 are more preferred in terms of heat resistance, cold resistance and moldability. When the degree of polymerization is lowered, moldability is improved, but heat resistance and cold resistance are lowered. Conversely, when the degree of polymerization is increased, heat resistance and cold resistance are improved, but moldability is deteriorated.
塩化ビニル樹脂は、必要に応じて、重合度の異なるものを２種以上ブレンドして用いても良い。 If necessary, two or more types of vinyl chloride resins having different degrees of polymerization may be blended and used.
（その他の成分）
本発明の実施の形態においては、本発明の効果を奏する限り、上記成分以外に、ＰＶＣ以外のポリマ、無機充填剤、安定剤、酸化防止剤、可塑剤、滑剤、着色剤、紫外線吸収剤、光安定剤、架橋剤、架橋助剤等の添加剤を種々配合することが可能である。
(Other ingredients)
In the embodiment of the present invention, as long as the effects of the present invention are exhibited, in addition to the above components, polymers other than PVC, inorganic fillers, stabilizers, antioxidants, plasticizers, lubricants, colorants, UV absorbers, Various additives such as a light stabilizer, a crosslinking agent, and a crosslinking aid can be blended.
例えば、耐熱性・耐寒性・絶縁性などを向上させたい場合は、必要に応じてフタル酸エステル、イソフタル酸エステル、トリメリット酸エステル、ピロメリット酸エステル、エポキシ化大豆油などの他の可塑剤をブレンドして使用しても良い。 For example, if you want to improve heat resistance, cold resistance, insulation, etc., other plasticizers such as phthalic acid ester, isophthalic acid ester, trimellitic acid ester, pyromellitic acid ester, epoxidized soybean oil as needed May be used in a blend.
〔電線〕
本発明の実施形態に係る電線は、導体と、導体の外周に被覆された、本発明の実施形態に係る上記塩化ビニル樹脂組成物からなる絶縁層とを備えたことを特徴とする。
〔Electrical wire〕
The electric wire which concerns on embodiment of this invention was equipped with the conductor and the insulating layer which consists of the said vinyl chloride resin composition concerning embodiment of this invention coat | covered on the outer periphery of the conductor, It is characterized by the above-mentioned.
図１は、本発明の実施の形態に係る電線の一例を模式的に示す横断面図である。
図１に示すように、本実施の形態に係る電線１０は、導体１と、導体１の外周に被覆された絶縁層２とを備える。被覆される導体１としては、例えば外径０．１５〜７ｍｍφ程度の導体を使用することができる。錫メッキ軟銅線を撚り合わせた導体などを好適に使用することができるが、これに限定されるものではない。導体１は、図１のように１本である場合に限られず、複数本であってもよい。
FIG. 1 is a cross-sectional view schematically showing an example of an electric wire according to an embodiment of the present invention.
As shown in FIG. 1, the
絶縁層２は、本発明の実施の形態に係る上記の塩化ビニル樹脂組成物から構成されている。押出被覆等の成形手段により絶縁層として被覆することで電線１０を得ることができる。必要に応じて、電子線照射等の方法により架橋処理を施してもよい。
The insulating
本実施の形態においては、絶縁層を、図１のように単層で構成したが、多層構造とすることもできる。この場合、少なくとも最外層は、上記塩化ビニル樹脂組成物を用いて形成する。 In the present embodiment, the insulating layer is constituted by a single layer as shown in FIG. 1, but it may be a multilayer structure. In this case, at least the outermost layer is formed using the vinyl chloride resin composition.
〔ケーブル〕
本発明の実施形態に係るケーブルは、本発明の実施形態に係る上記塩化ビニル樹脂組成物を被覆材料（シースないし絶縁層及びシース）として使用したことを特徴とする。
〔cable〕
A cable according to an embodiment of the present invention is characterized by using the above-described vinyl chloride resin composition according to an embodiment of the present invention as a coating material (sheath or insulating layer and sheath).
図２は、本発明の実施の形態に係るケーブルの一例を模式的に示す横断面図である。
図２に示すように、本実施の形態に係るケーブル２０は、導体１に絶縁層２を被覆した上記の本発明の実施の形態に係る電線１０、３本を紙等の介在３と共に撚り合わせた三芯撚り線と、その外周に巻き付けられた押えテープ４と、その外周に押出被覆されたシース５とを備える。三芯撚り線に限らず、電線１本（単芯）でもよく、三芯以外の多芯撚り線であってもよい。押えテープ４は省略することもできるし、編組に替えてもよい。
FIG. 2 is a cross-sectional view schematically showing an example of the cable according to the embodiment of the present invention.
As shown in FIG. 2, the cable 20 according to the present embodiment is obtained by twisting together three
シース５は、本発明の実施の形態に係る上記の塩化ビニル樹脂組成物から構成されている。本実施の形態においては、絶縁層２も上記の塩化ビニル樹脂組成物から構成したが、これに限られるものではなく、その他の絶縁層用樹脂組成物（ノンハロゲン難燃性樹脂組成物であることが好ましい）から構成されていてもよい。シース５は、必要に応じて、電子線照射等の方法により架橋処理を施されてもよい。
The sheath 5 is comprised from said vinyl chloride resin composition which concerns on embodiment of this invention. In the present embodiment, the insulating
本実施の形態においては、シースを、図２のように単層で構成したが、多層構造とすることもできる。この場合、少なくとも最外層は、上記塩化ビニル樹脂組成物を用いて形成する。 In the present embodiment, the sheath is composed of a single layer as shown in FIG. 2, but it may be a multilayer structure. In this case, at least the outermost layer is formed using the vinyl chloride resin composition.
以下に、本発明を実施例によりさらに具体的に説明する。なお、本発明は、以下の実施例によって、いかなる制限を受けるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. Note that the present invention is not limited in any way by the following examples.
表１〜２に実施例、表３に従来例及び比較例を示す。 Tables 1 and 2 show examples, and Table 3 shows conventional examples and comparative examples.
＜試験片（シート）の作製方法＞
平均重合度１３００のＰＶＣ１００質量部に対して、表１〜３に示した割合で可塑剤、シリコーンゴム、シリコーンオイル、安定剤としてカルシウム−亜鉛系非鉛安定剤、充填剤として炭酸カルシウムを混合した。その後、混練（ロール温度１６０℃, ５分）とプレス（プレス温度１８０℃, 予熱３分, 加圧１０ＭＰａで２分）により厚さ１ｍｍのシートを成形した。なお、可塑剤はロール混練可能な量として４０質量部以上の添加が必要であるため、テレフタル酸エステル添加量１０質量部の例においてはＤＩＮＰ（ジイソノニルフタレート）３０質量部をブレンドして作製した。
<Method for producing test piece (sheet)>
A plasticizer, silicone rubber, silicone oil, calcium-zinc non-lead stabilizer as a stabilizer, and calcium carbonate as a filler were mixed at a ratio shown in Tables 1 to 3 with respect to 100 parts by mass of PVC having an average degree of polymerization of 1300. . Thereafter, a sheet having a thickness of 1 mm was formed by kneading (roll temperature 160 ° C., 5 minutes) and pressing (press temperature 180 ° C., preheating 3 minutes,
表１〜３中の材料は、以下のものを使用した。
（１）塩化ビニル樹脂（信越化学工業（株）製，商品名：TK-1300）
（２）可塑剤
・テレフタル酸エステル
ＤＯＴＰ（ジ−２−エチルヘキシルテレフタレート）
ＤＩＮＴＰ（ジイソノニルテレフタレート）
ＤＩＤＴＰ（ジイソデシルテレフタレート）
・フタル酸エステル
ＤＩＮＰ（ジイソノニルフタレート）
ＤＯＰ（ジ−２−エチルヘキシルフタレート）
（３）シリコーンゴム（信越シリコーン製，商品名：KE-76）
（４）シリコーンオイル（信越シリコーン製，商品名：KF-96-100cs）
（５）安定剤：Ca-Zn系非鉛安定剤
（６）充填剤：炭酸カルシウム（（株）丸東製，商品名：ソフトン1500）
The following materials were used in Tables 1-3.
(1) Vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: TK-1300)
(2) Plasticizer / terephthalic acid ester DOTP (di-2-ethylhexyl terephthalate)
DINTP (Diisononyl terephthalate)
DIDTP (Diisodecyl terephthalate)
・ Phthalic acid ester DINP (diisononyl phthalate)
DOP (di-2-ethylhexyl phthalate)
(3) Silicone rubber (made by Shin-Etsu Silicone, trade name: KE-76)
(4) Silicone oil (made by Shin-Etsu Silicone, trade name: KF-96-100cs)
(5) Stabilizer: Ca-Zn lead-free stabilizer (6) Filler: Calcium carbonate (Maruto Co., Ltd., trade name: Softon 1500)
＜試験方法＞
耐候性は、スガ試験機製メタルハライドランプ耐候促進試験機Ｍ６Ｔにより評価した。試料面放射照度１．５ｋｗ／ｍ２、温度６０℃、湿度５０％、光源−試料間距離３５０ｍｍ、照射時間７２時間（３分水噴霧＋１１７分照射の１２０分サイクル×３６回）の条件で照射し、照射後／照射前の引張試験の伸び残率と照射後の外観を評価した。引張試験はJISK6723に準拠して行なった。伸び残率の評価判定は、６０％以上を合格（○）、６０％未満を不合格（×）とした。また、外観の評価判定は、照射後の試料表面にクラック（ひび割れ）がない場合を合格（○）、ある場合を不合格（×）とした。耐候性判定は、伸び残率○かつ外観○の場合を合格（○）とし、何れかが×の場合は不合格（×）とした。結果を表１〜３に示す。
<Test method>
The weather resistance was evaluated with a metal halide lamp weather resistance acceleration tester M6T manufactured by Suga Test Instruments. Irradiation under conditions of sample surface irradiance 1.5 kw / m 2 , temperature 60 ° C., humidity 50%, light source-sample distance 350 mm, irradiation time 72 hours (3 minutes water spray +117 minutes irradiation 120 minutes cycle × 36 times) Then, the elongation residual ratio of the tensile test after irradiation / before irradiation and the appearance after irradiation were evaluated. The tensile test was performed according to JISK6723. In the evaluation of the residual elongation rate, 60% or more was accepted (◯), and less than 60% was rejected (x). Moreover, the evaluation evaluation of an external appearance made the pass ((circle)) the case where there is no crack (crack) on the sample surface after irradiation, and made the disqualification (x) the case where there exists. In the weather resistance determination, the case of the residual elongation rate ○ and the appearance ○ was determined to be acceptable (◯), and if any of the results was ×, it was determined to be unacceptable (×). The results are shown in Tables 1-3.
耐ブリード性は、温度７０℃×湿度９０％の恒温恒湿槽で評価した。７２時間放置し、取り出し後、表面べたつきがない場合を合格（○）とし、ある場合を不合格（×）とした。結果を表１〜３に示す。 Bleed resistance was evaluated in a constant temperature and humidity chamber having a temperature of 70 ° C. and a humidity of 90%. After leaving for 72 hours and taking out, the case where there was no stickiness on the surface was regarded as acceptable (◯), and the case where it was present was regarded as unacceptable (x). The results are shown in Tables 1-3.
参考として行なった、ＤＯＰ又はＤＩＮＰを用いた従来例１，２では、耐候性・耐ブリード性ともに合格であった。 In the conventional examples 1 and 2 using DOP or DINP performed as a reference, both weather resistance and bleed resistance were acceptable.
実施例１及び比較例１はＤＯＴＰを１０質量部添加した場合であるが、シリコーンゴムを０．１質量部添加した実施例１では耐候性・耐ブリード性ともに合格であったが、シリコーンゴムを添加しなかった比較例１では耐候試験後にクラックが発生し、外観が不合格であるため耐候性の判定は不合格であった。 In Example 1 and Comparative Example 1, 10 parts by weight of DOTP was added. In Example 1 in which 0.1 part by weight of silicone rubber was added, both weather resistance and bleed resistance were acceptable. In Comparative Example 1 which was not added, cracks occurred after the weather resistance test, and the appearance was unacceptable, so the weather resistance was not acceptable.
また、実施例２，３及び比較例２，３はＤＯＴＰの添加量が４０，１００質量部の場合であるが、シリコーンゴムを０．１質量部添加した実施例２，３は実施例１と同様に合格である一方で、シリコーンゴムを添加しなかった比較例２，３は比較例１の場合と同様に外観が不合格であるほか、伸び残率も不合格であったため耐候性の判定は不合格であった。 Examples 2 and 3 and Comparative Examples 2 and 3 are cases in which the amount of DOTP added is 40,100 parts by mass. Examples 2 and 3 in which 0.1 part by mass of silicone rubber is added are the same as Example 1. Similarly, in Comparative Examples 2 and 3 in which silicone rubber was not added, the appearance was rejected in the same manner as in Comparative Example 1, and the residual elongation was also rejected, so that the weather resistance was judged. Was rejected.
以上より、シリコーンゴム０．１質量部以上が耐候性と耐ブリード性の両立に必要であることが示された。 From the above, it was shown that 0.1 part by mass or more of silicone rubber is necessary for achieving both weather resistance and bleed resistance.
実施例６，１１，１３及び比較例７〜９より、ＤＯＴＰは１００質量部を超えるとＤＯＴＰ自身がブリードしてしまったことから、ＤＯＴＰの添加量は１００質量部が限界であることが分かる。 From Examples 6, 11, 13 and Comparative Examples 7 to 9, it can be seen that DOTP is limited to 100 parts by mass because DOTP itself bleeds when it exceeds 100 parts by mass.
実施例４〜９より、シリコーンゴムを２．５〜５質量部添加しても耐候性と耐ブリード性の両立が出来ることが分かる。 From Examples 4 to 9, it can be seen that both weather resistance and bleed resistance can be achieved even when 2.5 to 5 parts by mass of silicone rubber is added.
実施例４〜６及び比較例４〜６より、シリコーンゴムでは耐候性と耐ブリード性の両立ができたが、シリコーンオイルでは耐候性は改善されたものの、組成物表面にブリードし、べたつきが発生した。 From Examples 4 to 6 and Comparative Examples 4 to 6, the silicone rubber was able to achieve both weather resistance and bleed resistance, but the silicone oil improved weather resistance, but bleeds on the surface of the composition and causes stickiness. did.
実施例４，６，１０〜１３より、テレフタル酸エステルのアルキル鎖炭素数Ｃ８〜Ｃ１０で同傾向であることが示された。 From Examples 4, 6, and 10 to 13, it was shown that the terephthalic acid ester had the same tendency with an alkyl chain carbon number of C8 to C10.
なお、本発明は、上記実施の形態及び実施例に限定されず種々に変形実施が可能である。 In addition, this invention is not limited to the said embodiment and Example, A various deformation | transformation implementation is possible.
１：導体、２：絶縁層、３：介在、４：押えテープ、５：シース
１０：電線、２０：ケーブル
1: Conductor, 2: Insulating layer, 3: Intervening, 4: Pressing tape, 5: Sheath 10: Electric wire, 20: Cable
Claims (7)
塩化ビニル樹脂１００質量部に対して、前記テレフタル酸エステルを１００質量部以下、シリコーンゴムを０．１質量部以上含有する塩化ビニル樹脂組成物。 A vinyl chloride resin composition containing terephthalic acid ester as a plasticizer,
A vinyl chloride resin composition containing 100 parts by mass or less of the terephthalic acid ester and 0.1 parts by mass or more of silicone rubber with respect to 100 parts by mass of the vinyl chloride resin.
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| CN102993602B (en) * | 2012-11-27 | 2014-08-06 | 宁波一舟塑胶有限公司 | CMP-grade flame-retardant smoke-inhibiting polyvinyl chloride cable sheath material and preparation method thereof |
| JP6028613B2 (en) | 2013-02-19 | 2016-11-16 | 日立金属株式会社 | Insulated wire and cable using flame retardant vinyl chloride resin composition |
| CN103509295B (en) * | 2013-10-12 | 2016-03-02 | 绿宝电缆（集团）有限公司 | A kind of environment-friendly heatproof composite elastic cable material for wires and cables |
| CN103509293B (en) * | 2013-10-12 | 2016-04-13 | 绿宝电缆（集团）有限公司 | A kind of Environment-friendlycold-resistant cold-resistant polyvinyl chloride cable |
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| JP6512003B2 (en) | 2019-05-15 |
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