JP5184454B2 - Rubber composition with excellent low-temperature shrinkability - Google Patents
Rubber composition with excellent low-temperature shrinkability Download PDFInfo
- Publication number
- JP5184454B2 JP5184454B2 JP2009163046A JP2009163046A JP5184454B2 JP 5184454 B2 JP5184454 B2 JP 5184454B2 JP 2009163046 A JP2009163046 A JP 2009163046A JP 2009163046 A JP2009163046 A JP 2009163046A JP 5184454 B2 JP5184454 B2 JP 5184454B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- mass
- oil
- rubber composition
- elongation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はゴム組成物に関し、詳しくは、電線、ケーブルの接続部用部品の常温収縮チューブ成形用として好適な、絶縁性で、低温収縮性に優れるゴム組成物に関する。 The present invention relates to a rubber composition, and more particularly, to a rubber composition that is suitable for forming a normal temperature shrinkable tube for connecting parts of electric wires and cables, and is excellent in insulation and low temperature shrinkage.
電線、ケーブルの接続部用の部品として、従来、常温収縮チューブが用いられてきている。常温収縮チューブは、その内径がケーブル接続部の被装着部分の外径よりも小さい寸法で製造した絶縁性チューブを予め拡径し、チューブの内径が被装着部分の外径よりも大きく保持させたものである。拡径状態の保持方法としては、通常、螺旋状に切れ目の入ったプラスチック製筒状保持材に保持したチューブを被装着部に差込み、筒状保持材を抜き取ることにより、チューブを収縮させ、被装着部と密着させることにより、接続部の電気的保護、気密性、水密性、を保持させる。そのため、挿入が容易で作業性がよく、現地で火気を使用せず、また作業に特別な工具を必要としない。 Conventionally, a normal temperature shrinkable tube has been used as a component for connecting portions of electric wires and cables. The normal temperature shrinkable tube is pre-expanded insulative tube with an inner diameter smaller than the outer diameter of the attached part of the cable connection part, and the inner diameter of the tube is kept larger than the outer diameter of the attached part. Is. As a holding method in the expanded diameter state, a tube held by a plastic cylindrical holding material that is spirally cut is usually inserted into an attachment portion, and the tube is contracted by removing the cylindrical holding material. By closely contacting the mounting portion, the electrical protection, airtightness, and watertightness of the connecting portion are maintained. Therefore, insertion is easy and workability is good, no fire is used on site, and no special tools are required for the work.
常温収縮チューブとは、チューブを高温に加熱することで収縮を起こさせる熱収縮チューブに対し、上記のように常温の状態で加熱することなくチューブを収縮させることができるものを指す。この常温収縮チューブに最も要求される特性の一つは、拡径保持した状態から元の寸法に近い状態に復元することである。この特性は、ゴムの永久伸び特性に相当する。接続部を一定期間拡径状態で保管した後、ケーブルを通して収縮した際、収縮が不十分であると、ケーブルとの十分な密着力が得られず、絶縁破壊強さが低下するなどの問題が生じてしまう。
また、拡径する際、チューブが切断されないよう高い伸び特性が必要となる。さらに、電線、ケーブルの接続部に使用するためには高い電気絶縁特性が必要となる。これらの要求特性に見合う材料として、従来は、主にシリコーンゴム、エチレン・プロピレンゴムが用いられている。
A normal temperature shrinkable tube refers to a tube that can be shrunk without being heated at room temperature as described above with respect to a heat shrinkable tube that is shrunk by heating the tube to a high temperature. One of the most required characteristics of this cold shrinkable tube is to restore it from a state where the diameter has been expanded to a state close to the original dimension. This characteristic corresponds to the permanent elongation characteristic of rubber. When the connection part is stored in a diameter-expanded state for a certain period and then contracted through the cable, if the contraction is insufficient, sufficient adhesion to the cable cannot be obtained, resulting in a decrease in dielectric breakdown strength. It will occur.
Further, when expanding the diameter, high elongation characteristics are required so that the tube is not cut. Furthermore, in order to use for the connection part of an electric wire and a cable, a high electrical insulation characteristic is required. Conventionally, silicone rubber and ethylene / propylene rubber are mainly used as materials that meet these required characteristics.
しかしながら、従来の常温収縮チューブに用いられる材料のうち、シリコーンゴムは諸特性に優れるものの、エチレン・プロピレンゴムなどと比べると材料単価が高く、シリコーンゴムを用いた常温収縮チューブは製品コストが高価になる欠点がある。また、エチレン・プロピレンゴムを用いた常温収縮チューブは、常温での伸びおよび永久伸びが優れて、経済的にも優れているものである（特許文献１〜４参照）。しかし、例えば、０℃以下のような低温環境で作業を行う際に、永久伸び（収縮性）が不十分な場合があり、チューブに用いられるゴム組成物の低温収縮性について、さらなる検討が必要であった。一方、従来の低温環境での永久伸びが良好な組成物では、上記のチューブに用いた場合、チューブの拡径作業時に問題となる伸びおよび引張り応力について必ずしも要求特性を満足できるものではなかった。 However, among the materials used for conventional cold shrinkable tubes, silicone rubber is superior in various properties, but the material unit price is higher than ethylene / propylene rubber, etc., and cold shrinkable tubes using silicone rubber are expensive. There are disadvantages. Moreover, the normal temperature shrinkable tube using ethylene-propylene rubber has excellent elongation at room temperature and permanent elongation, and is economically superior (see Patent Documents 1 to 4). However, for example, when working in a low temperature environment such as 0 ° C. or lower, permanent elongation (shrinkability) may be insufficient, and further investigation is necessary regarding the low temperature shrinkage of the rubber composition used for the tube. Met. On the other hand, in the case of a conventional composition having a good permanent elongation in a low temperature environment, when used in the above-mentioned tube, the required properties for the elongation and tensile stress which are problematic during the diameter expansion operation of the tube cannot always be satisfied.
本発明は、上記の従来の技術が有する問題点を解決し、電線、ケーブルの接続部用部品の常温収縮チューブ成形用として好適な、高い絶縁性を有し、常温における永久伸び特性および伸び特性に優れ、かつ、低温収縮性に優れたゴム組成物を提供することを目的とする。 The present invention solves the above-mentioned problems of the prior art, has a high insulation property suitable for forming a normal temperature shrinkable tube for connecting parts of electric wires and cables, and has a permanent elongation characteristic and an elongation characteristic at normal temperature. An object of the present invention is to provide a rubber composition excellent in low temperature shrinkage.
前記の目的を達成するために、本発明者らは鋭意検討した結果、特定の配合の油展および非油展のエチレン・プロピレン・ジエン共重合体（以下、「ＥＰＤＭ」という）、有機過酸化物、焼成クレー、カーボンブラック、およびプロセスオイルを含有するゴム組成物が低温収縮性に優れ、かつ常温の作業性に優れたものとし得ることを見出し、本発明をなすに至ったものである。 In order to achieve the above object, the present inventors have intensively studied, and as a result, oil-extended and non-oil-extended ethylene / propylene / diene copolymer (hereinafter referred to as “EPDM”), organic peroxidation of a specific formulation. It has been found that a rubber composition containing a product, calcined clay, carbon black, and process oil has excellent low-temperature shrinkability and excellent workability at room temperature, and has led to the present invention.
すなわち、本発明は、
（１）非油展ＥＰＤＭ（Ａ）と油展ＥＰＤＭ（Ｂ）をＡ：Ｂが質量比３：７〜５：５で混合されたＥＰＤＭの混合物１００質量部に対して、有機過酸化物を４．５〜５．５質量部、焼成クレーを３０〜７０質量部、カーボンブラックを１〜２０質量部、およびプロセスオイルを１５〜２５質量部を含有することを特徴とするゴム組成物、
（２）前記ＥＰＤＭの混合物１００質量部に対して、前記焼成クレーを５０〜７０質量部含有することを特徴とする（１）項記載のゴム組成物、
（３）前記ＥＰＤＭの混合物１００質量部に対して、前記焼成クレーを３０〜５０質量部、およびシリカを２０質量部以下含有することを特徴とする（１）項記載のゴム組成物、および
（４）前記焼成クレーがシランカップリング剤で表面処理された焼成クレーであることを特徴とする（１）〜（３）のいずれか１項に記載のゴム組成物、
を提供するものである。
That is, the present invention
(1) An organic peroxide is added to 100 parts by mass of a mixture of non-oil-extended EPDM (A) and oil-extended EPDM (B) in which A: B is mixed at a mass ratio of 3: 7 to 5: 5. A rubber composition comprising 4.5 to 5.5 parts by mass, 30 to 70 parts by mass of calcined clay, 1 to 20 parts by mass of carbon black, and 15 to 25 parts by mass of process oil,
(2) The rubber composition as described in the item (1), which contains 50 to 70 parts by mass of the calcined clay with respect to 100 parts by mass of the EPDM mixture,
(3) 30 to 50 parts by mass of the calcined clay and 20 parts by mass or less of silica with respect to 100 parts by mass of the EPDM mixture, 4) The rubber composition according to any one of (1) to (3), wherein the calcined clay is a calcined clay surface-treated with a silane coupling agent.
Is to provide.
本発明は、常温、低温（０℃以下）ともに、伸び特性及び永久伸び特性を満足した常温収縮チューブ用の組成物を得ることができる。 INDUSTRIAL APPLICABILITY The present invention can provide a composition for a normal temperature shrinkable tube that satisfies both elongation characteristics and permanent elongation characteristics at both normal temperature and low temperature (0 ° C. or less).
本発明のゴム組成物は、非油展ＥＰＤＭ（Ａ）と油展ＥＰＤＭ（Ｂ）をＡ：Ｂが質量比３：７〜５：５で混合されたＥＰＤＭの混合物１００質量部に対して、有機過酸化物を４．５〜５．５質量部、焼成クレーを３０〜７０質量部、カーボンブラックを１〜２０質量部、およびプロセスオイルを１５〜２５質量部を含有するものである。本発明のゴム組成物は、例えば、伸びが６００％以上、０℃環境での永久伸びが２０％以下というような、常温、低温ともに、伸び特性及び永久伸び特性に優れた絶縁ゴム組成物を可能とすることができる。 The rubber composition of the present invention is a non-oil-extended EPDM (A) and an oil-extended EPDM (B) with respect to 100 parts by mass of a mixture of EPDM in which A: B is mixed at a mass ratio of 3: 7 to 5: 5. It contains 4.5 to 5.5 parts by mass of organic peroxide, 30 to 70 parts by mass of calcined clay, 1 to 20 parts by mass of carbon black, and 15 to 25 parts by mass of process oil. The rubber composition of the present invention is, for example, an insulating rubber composition excellent in elongation characteristics and permanent elongation characteristics at both normal temperature and low temperature, such as elongation of 600% or more and permanent elongation at 0 ° C. of 20% or less. Can be possible.
本発明に用いられる非油展ＥＰＤＭとしては、公知のものを使用でき、エチレン、プロピレンと、エチリデンノルボーネン、１，４ヘキサジエン、ジシクロペンタジエン等のジエン系モノマーとの共重合体があげられる。本発明においては、１２５℃におけるムーニー粘度（ＭＬ１＋４）が好ましくは７０〜９０、さらに好ましくは８０〜９０以上のＥＰＤＭが使用される。ＥＰＤＭのムーニー粘度は、その分子量の指標になり、分子量が高いほど粘度は大きく、逆に分子量が低くなれば粘度も低くなる。 As the non-oil-extended EPDM used in the present invention, known ones can be used, and examples thereof include copolymers of ethylene, propylene and diene monomers such as ethylidene norbornene, 1,4 hexadiene, dicyclopentadiene. In the present invention, EPDM having a Mooney viscosity (ML 1 + 4 ) at 125 ° C. of preferably 70 to 90, more preferably 80 to 90 or more is used. The Mooney viscosity of EPDM is an index of its molecular weight. The higher the molecular weight, the larger the viscosity, and conversely, the lower the molecular weight, the lower the viscosity.
本発明に用いられる油展ＥＰＤＭとしては、上記の非油展ＥＰＤＭと同様のＥＰＤＭに伸展油を含有させたものである。伸展油としてはパラフィン系のオイル等が挙げられる。油展ＥＰＤＭにおける伸展油の含有量は、油展されるＥＰＤＭ１００質量部に対し、伸展油７０〜１２０質量部が好ましい。本発明においては、１２５℃におけるムーニー粘度（ＭＬ１＋４）が好ましくは７０以下、さらに好ましくは６０以下のＥＰＤＭが使用される。 The oil-extended EPDM used in the present invention is an EPDM similar to the above-mentioned non-oil-extended EPDM containing an extended oil. Examples of the extending oil include paraffinic oil. The content of the extending oil in the oil-extended EPDM is preferably 70 to 120 parts by mass of the extending oil with respect to 100 parts by mass of the oil-extended EPDM. In the present invention, EPDM having a Mooney viscosity (ML 1 + 4 ) at 125 ° C. of preferably 70 or less, more preferably 60 or less is used.
本発明において、１２５℃におけるムーニー粘度（ＭＬ１＋４）は、ＪＩＳ Ｋ ６３００の未加硫ゴム−物理特性−ムーニー粘度計による粘度及びスコーチタイムの求め方に準拠し、ムーニー粘度計を１２５℃に予熱しておき、未加硫ゴムをセットして１分間静置し、その後ローターを回転させてから４分後の値を求めたものである。
本発明においては、ムーニー粘度が高い高分子量のＥＰＤＭと油展にすることによりムーニー粘度が低くなったＥＰＤＭとの混合物を用いることが好ましい。
In the present invention, Mooney viscosity (ML 1 + 4 ) at 125 ° C. is based on JIS K 6300 unvulcanized rubber—physical properties—how to obtain viscosity and scorch time using Mooney viscometer, and Mooney viscometer is preheated to 125 ° C. The unvulcanized rubber was set and allowed to stand for 1 minute, and then the value obtained 4 minutes after the rotor was rotated.
In the present invention, it is preferable to use a mixture of a high molecular weight EPDM having a high Mooney viscosity and an EPDM having a Mooney viscosity lowered by oil-extended.
本発明におけるＥＰＤＭの混合物は、非油展ＥＰＤＭ（Ａ）と油展ＥＰＤＭ（Ｂ）の混合比率（質量比）がＡ：Ｂで、３：７〜５：５、好ましくは３．５：６．５〜４．５：５．５である。非油展ＥＰＤＭの割合が多すぎると伸びが不足し、非油展ＥＰＤＭの割合が少なすぎると永久伸びが悪くなる。
なお、本発明において、非油展ＥＰＤＭと油展ＥＰＤＭの混合比率算出における油展ＥＰＤＭの質量には、伸展油の質量が含まれる。
In the EPDM mixture in the present invention, the mixing ratio (mass ratio) of non-oil-extended EPDM (A) and oil-extended EPDM (B) is A: B, 3: 7 to 5: 5, preferably 3.5: 6. 5-4.5: 5.5. If the ratio of the non-oil-extended EPDM is too large, the elongation is insufficient, and if the ratio of the non-oil-extended EPDM is too small, the permanent elongation becomes worse.
In the present invention, the mass of the oil-extended EPDM in the calculation of the mixing ratio of the non-oil-extended EPDM and the oil-extended EPDM includes the mass of the extended oil.
本発明において、有機過酸化物は架橋剤（加硫剤）として作用する。その代表例としてはジクミルパーオキサイドを挙げることができるが、その他の公知の有機過酸化物も用いることができる。有機過酸化物の含有量は、架橋後の製品の状態において、非油展ＥＰＤＭと油展ＥＰＤＭの混合物１００質量部に対し、４．５〜５．５質量部であり、４．５〜５質量部が好ましい。有機過酸化物の含有量が少なすぎると永久伸びが大きくなりチューブの収縮が不安定となる傾向にあり、有機過酸化物の含有量が多すぎると引張り伸びが低くなり、３００％モジュラスが上昇し、拡径に悪影響を及ぼす恐れがある。 In the present invention, the organic peroxide acts as a crosslinking agent (vulcanizing agent). A typical example is dicumyl peroxide, but other known organic peroxides can also be used. The content of the organic peroxide is 4.5 to 5.5 parts by mass with respect to 100 parts by mass of the mixture of non-oil-extended EPDM and oil-extended EPDM in the state of the product after crosslinking, and 4.5 to 5 Part by mass is preferred. If the content of the organic peroxide is too small, the permanent elongation tends to increase and the shrinkage of the tube tends to become unstable. If the content of the organic peroxide is too large, the tensile elongation decreases and the 300% modulus increases. In addition, there is a possibility of adversely affecting the diameter expansion.
本発明において焼成クレーは、通常電力ケーブル用の絶縁樹脂組成物に添加されるものであれば、問題なく使用でき、例えば、けい酸アルミニウムを主体とする鉱物系充填剤を使用できる。焼成クレーの含有量は、非油展ＥＰＤＭと油展ＥＰＤＭの混合物１００質量部に対して３０〜７０質量部であり、５０〜７０質量部が好ましく、５０〜６０質量部がさらに好ましい。焼成クレーの含有量が少なすぎると永久伸びが大きくなり、焼成クレーの含有量が多すぎると３００％モジュラスが上昇する傾向にある。
焼成クレーの表面処理の有無は特に問わないが、シラン処理されている方が補強効果が高いため好ましい。
In the present invention, the fired clay can be used without any problem as long as it is usually added to an insulating resin composition for power cables. For example, a mineral filler mainly composed of aluminum silicate can be used. The content of the calcined clay is 30 to 70 parts by weight, preferably 50 to 70 parts by weight, and more preferably 50 to 60 parts by weight with respect to 100 parts by weight of the mixture of non-oil-extended EPDM and oil-extended EPDM. If the content of the calcined clay is too small, the permanent elongation increases, and if the content of the calcined clay is too large, the 300% modulus tends to increase.
The presence or absence of surface treatment of the fired clay is not particularly limited, but silane treatment is preferable because of its high reinforcing effect.
本発明におけるカーボンブラックは、通常電力ケーブル用の絶縁樹脂組成物に添加されるものであれば、問題なく使用できる。非油展ＥＰＤＭと油展ＥＰＤＭの混合物１００質量部に対して、１〜２０質量部であり、１０〜２０質量部が好ましい。カーボンブラックの含有量が多すぎると引張応力が大きくなり、伸びは小さくなり電力ケーブルの接続部材として使用した場合、拡径作業性が低下する傾向にある。またカーボンブラックの持つ導電性により電気絶縁特性が低下する。また、カーボンブラックの含有量が少なすぎると加工性に悪影響を与える可能性がある。 The carbon black in the present invention can be used without any problem as long as it is usually added to an insulating resin composition for power cables. It is 1-20 mass parts with respect to 100 mass parts of mixtures of non-oil extended EPDM and oil extended EPDM, and 10-20 mass parts is preferable. When the content of carbon black is too large, the tensile stress increases, the elongation decreases, and when used as a power cable connecting member, the diameter expansion workability tends to decrease. In addition, the electrical insulation properties of the carbon black deteriorate due to the conductivity of the carbon black. Moreover, when there is too little content of carbon black, there exists a possibility of having a bad influence on workability.
プロセスオイルは、硬度を低下させ引張り伸び率を向上させる作用をするが、高粘度のパラフィン系、ナフテン系、アロマ系いずれも使用できる。本発明におけるプロセスオイルは非油展ＥＰＤＭと油展ＥＰＤＭの混合物１００質量部に対して１５〜２５質量部が好ましい。プロセスオイル１５質量部未満ではゴム組成物の混練り時の加工性が悪く、硬度が硬く引張り伸びが不足し、チューブの拡径が容易でなくなる。２５質量部を超えると加工性の悪さに加えて永久伸びが大きくなる傾向にある。 The process oil acts to lower the hardness and improve the tensile elongation, but any high viscosity paraffin, naphthene or aroma can be used. The process oil in the present invention is preferably 15 to 25 parts by mass with respect to 100 parts by mass of a mixture of non-oil extended EPDM and oil extended EPDM. If the amount of the process oil is less than 15 parts by mass, the processability at the time of kneading the rubber composition is poor, the hardness is hard and the tensile elongation is insufficient, and the tube diameter is not easily expanded. When the amount exceeds 25 parts by mass, permanent elongation tends to increase in addition to poor workability.
本発明のゴム組成物には、伸びを小さくせず、永久伸びを悪くさせない範囲で他の充填剤、加工助剤、加硫助剤、老化防止剤等を適宜添加することができる。他の充填剤としては、当該充填剤を加えることによりカーボンブラックを多量配合しても、伸張時の引張り応力特性と低温時の永久伸び特性に優れたゴム組成物にすることができる充填剤が好ましい。この追加した充填剤の含有量が多くなると、吸水量が大きくなることがあるため、非油展ＥＰＤＭと油展ＥＰＤＭの混合物１００質量部に対して、この充填剤の含有量は２０質量部以下であることが好ましく、１０〜２０質量部であることがさらに好ましい。この充填剤としては、具体的にはシリカなどを挙げることができる。また、シリカを含む場合には、上記の焼成クレーは非油展ＥＰＤＭと油展ＥＰＤＭの混合物１００質量部に対して、３０〜５０質量部であることが好ましい。 In the rubber composition of the present invention, other fillers, processing aids, vulcanization aids, anti-aging agents, and the like can be appropriately added as long as the elongation is not reduced and the permanent elongation is not deteriorated. As other fillers, there is a filler that can be made into a rubber composition excellent in tensile stress characteristics at elongation and permanent elongation characteristics at low temperature even if a large amount of carbon black is blended by adding the filler. preferable. If the added filler content increases, the amount of water absorption may increase. Therefore, the filler content is 20 parts by mass or less with respect to 100 parts by mass of the non-oil-extended EPDM and oil-extended EPDM mixture. It is preferable that it is 10-20 mass parts. Specific examples of the filler include silica. Moreover, when silica is included, the calcined clay is preferably 30 to 50 parts by mass with respect to 100 parts by mass of the mixture of non-oil-extended EPDM and oil-extended EPDM.
以下、本発明を実施例および比較例に基づいてさらに詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to this.
実施例１〜９および比較例１〜８
表１および表２の組成の欄に示す加硫剤を除く各成分を表１および表２に示す量で、バンバリーミキサーにて１５０℃で混練し、混練後、６０℃前後のオープンロールに移して加硫剤を投入し、シート状に成形した。このシートを１６０℃の温度で３０分プレス加硫し、実施例および比較例のゴム組成物からなる絶縁シートを作製した。
Examples 1-9 and Comparative Examples 1-8
Each component except the vulcanizing agent shown in the column of composition in Table 1 and Table 2 is kneaded at 150 ° C. with a Banbury mixer in the amounts shown in Table 1 and Table 2, and after kneading, transferred to an open roll at around 60 ° C. Then, a vulcanizing agent was added and formed into a sheet shape. This sheet was press vulcanized at a temperature of 160 ° C. for 30 minutes to produce an insulating sheet made of the rubber composition of Examples and Comparative Examples.
なお、表１及び２の組成の欄に記した各成分は以下の製品を用いた。
非油展ＥＰＤＭ：エチレン含量５１ｗｔ％
油展ＥＰＤＭ：エチレン含量６６ｗｔ％
焼成クレー：平均粒径１．４μｍ、比重２．６３、シランカップリング剤で表面処理
カーボンブラック：平均粒径２８ｎｍ、Ｎ−３３０
シリカ：ＳｉＯ２ ９３％以上、比重１．９〜２．０、ｐＨ５．５〜６．５
硫黄：２００メッシュ（ＪＩＳ １種相当品）、灰分０．１％以下
加硫剤：ジクミルパーオキサイド
老化防止剤Ａ：芳香族第二級アミン系 比重１．１１
老化防止剤Ｂ：ベンツイミダゾール系 比重１．３５
ステアリン酸：中和価１９７〜２０７
酸化亜鉛：酸化亜鉛３種
In addition, the following products were used for each component described in the column of the composition in Tables 1 and 2.
Non-oil extended EPDM: ethylene content 51 wt%
Oil-extended EPDM: ethylene content 66wt%
Firing clay: average particle size 1.4 μm, specific gravity 2.63, surface treatment with silane coupling agent Carbon black: average particle size 28 nm, N-330
Silica: SiO 2 93% or more, specific gravity 1.9 to 2.0, pH 5.5 to 6.5
Sulfur: 200 mesh (JIS 1 equivalent), ash content 0.1% or less Vulcanizing agent: Dicumyl peroxide Anti-aging agent A: Aromatic secondary amine specific gravity 1.11
Anti-aging agent B: Benzimidazole specific gravity 1.35
Stearic acid: neutralization number 197-207
Zinc oxide: 3 types of zinc oxide
試験例
実施例および比較例の各絶縁シートにつき、伸び、３００％モジュラス、０℃永久伸びを測定し評価した。結果を表１および２に示す。
（１）伸び
引張り試験は、ＪＩＳ Ｋ ６２５１の加硫ゴムの引張試験方法に準拠して、２３℃で測定した。伸びが６００％以上でないと、常温収縮チューブの拡径作業を容易に行うことができない。
（２）０℃永久伸び
ＪＩＳ Ｋ ６２７３の加硫ゴムの引張永久ひずみ試験方法を元に、実際の拡径作業から現場での施工までを考慮して、予備伸張２００％を行った後常温（２０℃）で１時間放置し、それから１００％伸張状態で保持したサンプルを０℃環境で３時間放置して、解放してから３０分後に測定した。０℃環境での永久伸びが２０％以下でないと、収縮後のチューブのケーブルへの密着性が不十分となる。
（３）３００％モジュラス
ＪＩＳ Ｋ ６２５１に準拠して、２３℃で測定した。３００％伸張時の引張り応力（３００％モジュラス）が大きい場合も容易に拡径が出来ないか、出来たとしても拡径保持材上に乗せて保管している際に、拡径保持材を壊してしまう恐れがある。
３ＭＰa以下であるものを○、３ＭＰa以上であるものを×として、表１および表２に示した。
Test Example For each insulating sheet of Examples and Comparative Examples, the elongation, 300% modulus, and 0 ° C. permanent elongation were measured and evaluated. The results are shown in Tables 1 and 2.
(1) Elongation The tensile test was measured at 23 ° C. according to a JIS K 6251 vulcanized rubber tensile test method. If the elongation is not 600% or more, the diameter expansion work of the room temperature shrinkable tube cannot be easily performed.
(2) Permanent elongation at 0 ° C. Based on the tensile permanent strain test method of vulcanized rubber of JIS K 6273, considering the range from actual diameter expansion work to on-site construction, after pre-stretching 200%, normal temperature ( The sample which was left at 20 ° C. for 1 hour and then held in a 100% stretched state was left to stand for 3 hours in a 0 ° C. environment and measured 30 minutes after release. If the permanent elongation in the 0 ° C. environment is not 20% or less, the adhesion of the tube after shrinkage to the cable becomes insufficient.
(3) 300% modulus It measured at 23 degreeC based on JISK6251. Even when the tensile stress at 300% elongation (300% modulus) is large, the diameter can not be expanded easily, or even when it is stored on the expanded diameter holding material, the expanded diameter holding material is broken. There is a risk that.
The results are shown in Tables 1 and 2 with ◯ indicating 3 MPa or less and X indicating 3 MPa or more.
表１に示されるように、実施例１〜９はいずれも、伸びが６００％以上、０℃環境での永久伸びが２０％以下であり、３００％モジュラスも上記基準を満たしている。特に、シリカを含有する実施例６〜９はカーボンブラックを比較的多量に配合しているが、伸びは６９０％以上あり、永久伸び、および３００％モジュラスも基準値内であった。 As shown in Table 1, in each of Examples 1 to 9, the elongation is 600% or more, the permanent elongation in an environment of 0 ° C. is 20% or less, and the 300% modulus also satisfies the above criteria. In particular, Examples 6 to 9 containing silica contained a relatively large amount of carbon black, but the elongation was 690% or more, and the permanent elongation and 300% modulus were also within the standard values.
これに対し、表２に示されるように、非油展ＥＰＤＭが含まれない比較例１は、０℃の永久伸びが２０％を越えていた。油展ＥＰＤＭが含まれない比較例２は、伸びが６００％未満であった。焼成クレーが多すぎる比較例３は、３００％モジュラスが上記基準を満たさなかった。カーボンブラックが多すぎる比較例４は、３００％モジュラスが上記基準を満たさなかった。プロセスオイルが少なすぎる比較例５は、伸びが６００％未満であり、３００％モジュラスも上記基準を満たさなかった。プロセスオイルが多すぎる比較例６は、０℃の永久伸びが２０％を越えていた。有機過酸化物である加硫剤が少なすぎる比較例７は、０℃の永久伸びが２０％を越えていた。有機過酸化物が多すぎる比較例８は、３００％モジュラスが上記基準を満たさなかった。 On the other hand, as shown in Table 2, in Comparative Example 1 in which the non-oil-extended EPDM was not included, the permanent elongation at 0 ° C. exceeded 20%. In Comparative Example 2 in which no oil-extended EPDM was contained, the elongation was less than 600%. In Comparative Example 3 having too much calcined clay, the 300% modulus did not satisfy the above criteria. In Comparative Example 4 having too much carbon black, the 300% modulus did not satisfy the above criteria. In Comparative Example 5, where the amount of process oil was too small, the elongation was less than 600%, and the 300% modulus did not satisfy the above criteria. In Comparative Example 6 having too much process oil, the permanent elongation at 0 ° C. exceeded 20%. In Comparative Example 7, where the amount of the vulcanizing agent which is an organic peroxide is too small, the permanent elongation at 0 ° C. exceeded 20%. In Comparative Example 8 having too much organic peroxide, the 300% modulus did not satisfy the above criteria.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009163046A JP5184454B2 (en) | 2009-07-09 | 2009-07-09 | Rubber composition with excellent low-temperature shrinkability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009163046A JP5184454B2 (en) | 2009-07-09 | 2009-07-09 | Rubber composition with excellent low-temperature shrinkability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011016940A JP2011016940A (en) | 2011-01-27 |
| JP5184454B2 true JP5184454B2 (en) | 2013-04-17 |
Family
ID=43594962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009163046A Active JP5184454B2 (en) | 2009-07-09 | 2009-07-09 | Rubber composition with excellent low-temperature shrinkability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5184454B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5528597B2 (en) * | 2012-03-28 | 2014-06-25 | 株式会社フジクラ | EP rubber composition, EP rubber material, cable and connecting parts |
| JP6488213B2 (en) * | 2015-08-28 | 2019-03-20 | 昭和電線ケーブルシステム株式会社 | Insulating cold shrink tube for cable connection and cable connection |
| JP7157900B2 (en) * | 2018-06-28 | 2022-10-21 | 住友ゴム工業株式会社 | RUBBER COMPOSITION AND PAPER FEED ROLLER USING THE SAME |
| JP7157901B2 (en) * | 2018-06-28 | 2022-10-21 | 住友ゴム工業株式会社 | RUBBER COMPOSITION AND PAPER FEED ROLLER USING THE SAME |
| CN112126166B (en) * | 2020-09-29 | 2023-04-04 | 一汽解放汽车有限公司 | Ethylene propylene diene monomer composition, rubber tube, and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2692754B2 (en) * | 1992-10-09 | 1997-12-17 | 矢崎総業株式会社 | Oil-bleeding polyolefin rubber composition |
| JP2004210821A (en) * | 2002-12-26 | 2004-07-29 | Inoac Corp | Chlorine water-resistant rubber composition |
| US20050215661A1 (en) * | 2004-03-23 | 2005-09-29 | 3M Innovative Properties Company | NBC-resistant composition |
-
2009
- 2009-07-09 JP JP2009163046A patent/JP5184454B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011016940A (en) | 2011-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI607045B (en) | Process for reducing peroxide migration in crosslinkable ethylene-based polymer compositions | |
| JP5184454B2 (en) | Rubber composition with excellent low-temperature shrinkability | |
| JPH05507104A (en) | Pre-stretched tube with high extensibility elasticity | |
| JP2008031354A (en) | Non-halogen flame-retardant thermoplastic elastomer composition and method for producing the same and electric wire/cable using the same | |
| JP2007070602A (en) | Non-halogen flame retardant thermoplastic elastomer composition, its production method and electric wire/cable using the same | |
| JP2007100069A (en) | Flame-retardant resin composition suppressed in whitening at bending deformation | |
| CN108699300B (en) | Halogen-free and fire-retardant rubber composition and hose | |
| WO2018180689A1 (en) | Flame-retardant crosslinked resin molded article, production method therefor, silane masterbatch, masterbatch mixture, molded article thereof, and flame-retardant product | |
| US10407568B2 (en) | Flexible elastic rubber compounds with improved dielectric and tear strength for cold shrink splices and preparation method thereof | |
| JP5325066B2 (en) | Cold shrink tube for cable connection and cable connection | |
| EP3161073B1 (en) | In-situ compatibilization of silicone rubber/polyolefin elastomer blends by forming ionomers for cold shrink splice and preparation method thereof | |
| JP5588366B2 (en) | Cold shrink tube for cable connection and cable connection | |
| JP6488213B2 (en) | Insulating cold shrink tube for cable connection and cable connection | |
| JP4907291B2 (en) | Rubber mold materials and rubber mold products | |
| JP3813319B2 (en) | Insulating rubber composition | |
| JP2013125740A (en) | Insulation electric wire | |
| JP2013020783A (en) | Insulated wire | |
| JP2003096250A (en) | Resin composition flame-retarded with non-halogen and its molding | |
| JP2015008615A (en) | Atmospheric temperature shrinkable tube for cable connection part, and cable connection part | |
| JP2009132761A (en) | Fluoroelastomer composition | |
| JP2007262279A (en) | Method for recovering shape of shape memory rubber | |
| JP2007169381A (en) | Electrical insulating resin composition and low voltage cable | |
| JP2009149772A (en) | Fluorine-containing elastomer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120531 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121127 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121218 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130116 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5184454 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160125 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160125 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |