JP6040283B1 - Protective member for cable connection and cable connection - Google Patents
Protective member for cable connection and cable connection Download PDFInfo
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- 230000001681 protective effect Effects 0.000 title claims abstract description 37
- 150000001993 dienes Chemical class 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000010734 process oil Substances 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 229920001897 terpolymer Polymers 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 230000006835 compression Effects 0.000 claims description 14
- 238000007906 compression Methods 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 12
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- 230000000052 comparative effect Effects 0.000 description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
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- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006242 Semi-Reinforcing Furnace Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
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- 239000011256 inorganic filler Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
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- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical group CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
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- 238000005065 mining Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
Abstract
【課題】機械特性、熱老化特性、寸法安定性に優れたケーブル接続部用保護部材、およびそれを用いたケーブル接続部を提供する。【解決手段】（Ａ）（a-1）エチレン含量５２〜５５質量％、ジエン含量７．４〜８．４質量％、ムーニー粘度ＭＬ１＋４（１００℃）５〜１０のエチレン・プロピレン・ジエン３元共重合体４０〜８０質量％、および（a-2）エチレン含量６２〜６７質量％、ジエン含量４．０〜５．０質量％、ムーニー粘度ＭＬ１＋４（１２５℃）４０〜８０のエチレン・プロピレン・ジエン３元共重合体２０〜６０質量％からなるポリマー成分１００質量部に対して、（Ｂ）プロセスオイル３０〜６０質量部、（Ｃ）カーボンブラック４０〜７０質量部、および（Ｄ）架橋剤２〜４質量部を含有する組成物の架橋体で構成されてなるケーブル接続部用保護部材、並びにそれを備えたケーブル接続部。【選択図】なしPROBLEM TO BE SOLVED: To provide a protective member for a cable connection part excellent in mechanical characteristics, heat aging characteristics and dimensional stability, and a cable connection part using the same. (A) (a-1) Ethylene / propylene / diene ternary having an ethylene content of 52 to 55% by mass, a diene content of 7.4 to 8.4% by mass, and a Mooney viscosity ML1 + 4 (100 ° C.) of 5 to 10. Copolymer 40 to 80% by mass, and (a-2) ethylene / propylene / ethylene having an ethylene content of 62 to 67% by mass, a diene content of 4.0 to 5.0% by mass, and a Mooney viscosity ML1 + 4 (125 ° C.) of 40 to 80 (B) 30-60 parts by mass of process oil, (C) 40-70 parts by mass of carbon black, and (D) a crosslinking agent with respect to 100 parts by mass of the polymer component comprising 20-60% by mass of the diene terpolymer. The protective member for cable connection parts comprised by the crosslinked body of the composition containing 2-4 mass parts, and a cable connection part provided with the same. [Selection figure] None
Description
本発明は、ＣＶケーブル（架橋ポリエチレン絶縁ケーブル）などのケーブルの接続部に使用される保護カバーなどの保護部材、およびそのような保護部材を用いたケーブル接続部に関する。 The present invention relates to a protective member such as a protective cover used for a connecting portion of a cable such as a CV cable (crosslinked polyethylene insulating cable), and a cable connecting portion using such a protective member.
従来、ＣＶケーブルなどの電力ケーブルの中間接続部および終端接続部、あるいは通信ケーブルの端末などにおける接続部においては、防水、保護、絶縁補強などを目的として、エチレンプロピレンゴムをベースとしたゴム材料を射出成型した保護部材が使用されている（例えば、特許文献１参照）。 Conventionally, in an intermediate connection portion and a termination connection portion of a power cable such as a CV cable, or a connection portion in a terminal of a communication cable, a rubber material based on ethylene propylene rubber has been used for the purpose of waterproofing, protection, insulation reinforcement, and the like An injection molded protective member is used (see, for example, Patent Document 1).
エチレンプロピレンゴムは、耐候性、耐水性に優れるうえ、絶縁性も良好であり、屋外で長期に亘って使用されることが多く、かつ絶縁性も要求される上記保護部材の材料として好適であった。しかしながら、このエチレンプロピレンゴムをベースとしたゴム材料には、その加工性を高めるため、プロセスオイルなどの軟化剤を大量に配合する必要があった。軟化剤を大量に配合すると、流動性が高まり加工性が向上する。しかし、その反面、破断強度や圧縮永久歪みなどの機械特性が低下する。また、加熱時の軟化剤の揮発により熱老化特性が低下し、また寸法変化も生じる。このため、従来の保護部材は、機械特性、熱老化特性および寸法安定性がやや不十分であった。 Ethylene propylene rubber is excellent in weather resistance and water resistance, and also has good insulation, is often used outdoors for a long period of time, and is suitable as a material for the protective member that requires insulation. It was. However, it has been necessary to add a large amount of a softening agent such as process oil to the rubber material based on this ethylene propylene rubber in order to improve its processability. When a large amount of the softening agent is blended, fluidity increases and processability is improved. However, on the other hand, mechanical properties such as breaking strength and compression set are deteriorated. In addition, volatilization of the softening agent during heating reduces the heat aging characteristics and causes dimensional changes. For this reason, the conventional protective member has somewhat insufficient mechanical properties, heat aging properties, and dimensional stability.
このような問題に対し、カーボンブラック、クレー、タルクなどの補強材を配合して機械特性を高めることも行われている。しかしながら、少量の添加では効果が小さく、多量に配合すると粘度が上昇し、加工性が低下した。 In order to solve such problems, mechanical properties are also improved by blending reinforcing materials such as carbon black, clay, and talc. However, when added in a small amount, the effect is small, and when added in a large amount, the viscosity increases and the processability decreases.
このため、加工性が良好で、かつ機械特性、熱老化特性および寸法安定性にも優れるエチレンプロピレンゴムをベースとしたゴム材料が求められている。 For this reason, a rubber material based on ethylene propylene rubber that has good processability and excellent mechanical properties, heat aging properties, and dimensional stability is required.
本発明は上記従来の事情に対処してなされたもので、加工性が良好で、かつ機械特性、熱老化特性および寸法安定性にも優れるエチレンプロピレンゴムをベースとしたゴム材料を用いて機械特性、熱老化特性、寸法安定性を向上させたケーブル接続部用保護部材、およびそのような保護部材を備えた高品質、高信頼性のケーブル接続部を提供することを目的とする。 The present invention has been made in response to the above-mentioned conventional circumstances, and has mechanical properties using a rubber material based on ethylene propylene rubber, which has good processability and excellent mechanical properties, thermal aging properties and dimensional stability. An object of the present invention is to provide a cable connection part protection member having improved heat aging characteristics and dimensional stability, and a high-quality, high-reliability cable connection part provided with such a protection member.
上記目的を達成するため、本発明は下記［１］〜［６］の実施形態を有する。
［１］（Ａ）（a-1）エチレン含量５２〜５５質量％、ジエン含量７．４〜８．４質量％、ムーニー粘度ＭＬ１＋４（１００℃）５〜１０のエチレン・プロピレン・ジエン３元共重合体４０〜８０質量％、および（a-2）エチレン含量６２〜６７質量％、ジエン含量４．０〜５．０質量％、ムーニー粘度ＭＬ１＋４（１２５℃）４０〜８０のエチレン・プロピレン・ジエン３元共重合体２０〜６０質量％からなるポリマー成分１００質量部に対して、（Ｂ）プロセスオイル３０〜６０質量部、（Ｃ）カーボンブラック４０〜７０質量部、および（Ｄ）架橋剤２〜４質量部を含有する組成物の架橋体で構成されてなることを特徴とするケーブル接続部用保護部材である。
［２］［１］に記載のケーブル接続部用保護部材において、（Ａ）成分は、（a-1）成分６０〜７０質量％、および（a-2）成分３０〜４０質量％からなることを特徴とするケーブル接続部用保護部材である。
［３］［１］または［２］に記載のケーブル接続部用保護部材において、前記組成物は、（Ａ）成分１００質量部に対し、酸化亜鉛を３〜７質量部、および酸化防止剤を０．５〜３．０質量部さらに含有することを特徴とするケーブル接続部用保護部材である。
［４］［１］乃至［３］のいずれかに記載のケーブル接続部用保護部材において、前記組成物は、（ｉ）ムーニー粘度ＭＬ１＋４（１００℃）１０〜４０、（ii）ムーニースコーチ時間ｔ5（１２５℃）１０〜５０分、（iii）デュロメータ硬さ４５〜６０、（iv）引張伸び ３００〜６００％、および（ｖ）圧縮永久歪み１０〜３０％であることを特徴とするケーブル接続部用保護部材である。
［５］［１］乃至［４］のいずれかに記載のケーブル接続部用保護部材において、ケーブル接続部に当接される面の表面粗さ（Ｒｚ）が４〜８μｍであることを特徴とするケーブル接続部用保護部材である。
［６］［１］乃至［５］のいずれかに記載のケーブル接続部用保護部材を備えたことを特徴とするケーブル接続部。
In order to achieve the above object, the present invention has the following embodiments [1] to [6].
[1] (A) (a-1) Ethylene / propylene / diene ternary having an ethylene content of 52 to 55 mass%, a diene content of 7.4 to 8.4 mass%, and a Mooney viscosity ML 1 + 4 (100 ° C.) of 5 to 10 Copolymer 40 to 80% by mass, and (a-2) ethylene propylene having an ethylene content of 62 to 67% by mass, a diene content of 4.0 to 5.0% by mass, and a Mooney viscosity ML 1 + 4 (125 ° C.) of 40 to 80 -(B) process oil 30-60 mass parts, (C) carbon black 40-70 mass parts, and (D) bridge | crosslinking with respect to 100 mass parts of polymer components which consist of 20-60 mass% of diene terpolymers. It is a protective member for a cable connection part characterized by being comprised by the crosslinked body of the composition containing 2-4 mass parts of agents.
[2] In the cable connection part protection member according to [1], the component (A) is composed of 60 to 70% by mass of the component (a-1) and 30 to 40% by mass of the component (a-2). It is the protection member for cable connection parts characterized by these.
[3] In the protective member for a cable connection part according to [1] or [2], the composition contains 3 to 7 parts by mass of zinc oxide and an antioxidant with respect to 100 parts by mass of the component (A). It is a protective member for cable connection parts characterized by further containing 0.5-3.0 mass parts.
[4] In the protective member for a cable connection part according to any one of [1] to [3], the composition contains (i) Mooney viscosity ML 1 + 4 (100 ° C.) 10 to 40, (ii) Mooney scorch time. t 5 (125 ° C.) 10-50 minutes, (iii) durometer hardness 45-60, (iv) tensile elongation 300-600%, and (v) compression set 10-30% It is a protection member for connection parts.
[5] In the cable connection portion protection member according to any one of [1] to [4], the surface roughness (Rz) of the surface abutting on the cable connection portion is 4 to 8 μm. It is the protection member for cable connection parts.
[6] A cable connection portion comprising the cable connection portion protection member according to any one of [1] to [5].
本発明によれば、加工性が良好で、かつ機械特性、熱老化特性および寸法安定性にも優れるエチレンプロピレンゴムをベースとしたゴム材料を用いて機械特性、熱老化特性、寸法安定性を向上させたケーブル接続部用保護部材、およびそのような保護部材を備えた高品質、高信頼性のケーブル接続部が提供される。 According to the present invention, mechanical properties, heat aging properties and dimensional stability are improved by using a rubber material based on ethylene propylene rubber which has good workability and excellent mechanical properties, heat aging properties and dimensional stability. Provided are a protective member for a cable connection portion, and a high-quality, high-reliability cable connection portion including such a protective member.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明のケーブル接続部用保護部材は、（Ａ）（a-1）エチレン含量５２〜５５質量％、ジエン含量７．４〜８．４質量％、ムーニー粘度ＭＬ１＋４（１００℃）５〜１０のエチレン・プロピレン・ジエン３元共重合体４０〜８０質量％、および（a-2）エチレン含量６２〜６２質量％、ジエン含量４．０〜５．０質量％、ムーニー粘度ＭＬ１＋４（１２５℃）４０〜８０のエチレン・プロピレン・ジエン３元共重合体２０〜６０質量％からなるポリマー成分１００質量部に対して、（Ｂ）プロセスオイル３０〜６０質量部、（Ｃ）カーボンブラック４０〜７０質量部、および（Ｄ）架橋剤２〜４質量部を含有する組成物の架橋体から構成される。 The protective member for a cable connection part of the present invention comprises (A) (a-1) an ethylene content of 52 to 55% by mass, a diene content of 7.4 to 8.4% by mass, and a Mooney viscosity ML 1 + 4 (100 ° C.) of 5 to 10. Ethylene / propylene / diene terpolymer of 40 to 80% by mass, and (a-2) ethylene content of 62 to 62% by mass, diene content of 4.0 to 5.0% by mass, Mooney viscosity ML 1 + 4 (125 ° C. ) With respect to 100 parts by mass of a polymer component composed of 20 to 60% by mass of 40-80 ethylene / propylene / diene terpolymer, (B) 30-60 parts by mass of process oil, and (C) carbon black 40-70. It is comprised from the crosslinked body of the composition containing a mass part and (D) 2-4 mass parts of crosslinking agents.
（Ａ）ポリマー成分として使用される（a-1）成分および（a-2）成分の各エチレン・プロピレン・ジエン３元共重合体は、上記条件を満足するものであれば、ジエン成分の種類などは特に限定されるものではなく、市販のエチレン・プロピレン・ジエン３元共重合体のなかから、それぞれ１種以上を適宜選択して使用することができる。具体的には、例えば、エチレンおよびプロピレンに、ジエン成分としてエチリデンノルボルネン、ジシクロペンタジエン、１，４−ヘキサジエンなどを共重合させたものであって、上記各条件を満たすものが使用される。 (A) The ethylene / propylene / diene terpolymers of the components (a-1) and (a-2) used as the polymer component can be any kind of diene component as long as the above conditions are satisfied. These are not particularly limited, and one or more kinds of commercially available ethylene / propylene / diene terpolymers may be appropriately selected and used. Specifically, for example, ethylene and propylene are copolymerized with ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene or the like as a diene component, and those satisfying the above conditions are used.
（a-1）成分および（a-2）成分の各エチレン・プロピレン・ジエン３元共重合体として使用される市販品を例示すると、（a-1）成分としては、例えば、三井化学（株）製の三井ＥＰＴ Ｘ−４０１０Ｍ（商品名；エチレン含量５４質量％、ジエン含量７．６質量％、ムーニー粘度ＭＬ１＋４（１００℃）８）などが挙げられる。 Examples of commercially available products used as (a-1) component and (a-2) component ethylene / propylene / diene terpolymers include (a-1) component such as Mitsui Chemicals, Inc. Mitsui EPT X-4010M (trade name; ethylene content 54 mass%, diene content 7.6 mass%, Mooney viscosity ML 1 + 4 (100 ° C.) 8) and the like.
また、（a-2）成分としては、例えば、三井化学（株）製の三井ＥＰＴ ３０６２ＥＭ（商品名；エチレン含量６５質量％、ジエン含量４．５質量％、ムーニー粘度ＭＬ１＋４（１００℃）４３、油展量２０ｐｈｒ）、同三井ＥＰＴ ３０７２ＥＭ（商品名；エチレン含量６４質量％、ジエン含量５．４質量％、ムーニー粘度ＭＬ１＋４（１００℃）５１、油展量４０ｐｈｒ）、ＪＳＲ（株）製のＪＳＲ ＥＰ２５（商品名；エチレン含量５９質量％、ジエン含量５．１質量％、ムーニー粘度ＭＬ１＋４（１００℃）６３）、同ＪＳＲ ＥＰ３５（商品名；エチレン含量５２質量％、ジエン含量８．１質量％、ムーニー粘度ＭＬ１＋４（１００℃）５６）、同ＪＳＲ ＥＰ６５（商品名；エチレン含量５４質量％、ジエン含量９．０質量％、ムーニー粘度ＭＬ１＋４（１００℃）４８）、住友化学（株）製のエスプレン５０２（商品名；エチレン含量５６質量％、ジエン含量４．０質量％、ムーニー粘度ＭＬ１＋４（１００℃）６２）、同エスプレン５１２Ｆ（商品名；エチレン含量６５質量％、ジエン含量４．０質量％、ムーニー粘度ＭＬ１＋４（１００℃）６６）などが挙げられる。 As the component (a-2), for example, Mitsui EPT 3062EM (trade name; ethylene content 65 mass%, diene content 4.5 mass%, Mooney viscosity ML 1 + 4 (100 ° C.) 43 manufactured by Mitsui Chemicals, Inc. , Oil extended amount 20 phr), Mitsui EPT 3072EM (trade name; ethylene content 64% by mass, diene content 5.4% by mass, Mooney viscosity ML 1 + 4 (100 ° C.) 51, oil extended amount 40 phr), manufactured by JSR Corporation JSR EP25 (trade name; ethylene content 59% by mass, diene content 5.1% by mass, Mooney viscosity ML 1 + 4 (100 ° C.) 63), JSR EP35 (trade name; ethylene content 52% by mass, diene content 8.1) Mass%, Mooney viscosity ML 1 + 4 (100 ° C.) 56), JSR EP65 (trade name; ethylene content 54 mass%, diene content 9.0 mass%, mu Knee viscosity ML 1 + 4 (100 ° C.) 48), Esprene 502 (trade name; ethylene content 56 mass%, diene content 4.0 mass%, Mooney viscosity ML 1 + 4 (100 ° C.) 62) manufactured by Sumitomo Chemical Co., Ltd. ESPRENE 512F (trade name; ethylene content 65 mass%, diene content 4.0 mass%, Mooney viscosity ML 1 + 4 (100 ° C.) 66), and the like.
上記（a-1）成分および（a-2）成分の混合割合は、（a-1）成分が４０〜８０質量％、好ましくは５０〜７０質量％、より好ましくは６０〜７０質量％、（a-2）成分が２０〜６０質量％、好ましくは３０〜５０質量％、より好ましくは３０〜４０質量％である。（a-1）成分の割合が上記範囲未満、または（a-2）成分の割合が上記範囲を超えると、ゴム組成物のムーニー粘度が高くなり、加工性が低下する。また、（a-2）成分の割合が上記範囲未満、または（a-1）成分の割合が上記範囲を超えると、ゴム組成物のグリーン強度、および硬化後の機械特性が低下する。 The mixing ratio of the component (a-1) and the component (a-2) is such that the component (a-1) is 40 to 80% by mass, preferably 50 to 70% by mass, more preferably 60 to 70% by mass, ( The component a-2) is 20 to 60% by mass, preferably 30 to 50% by mass, and more preferably 30 to 40% by mass. When the proportion of the component (a-1) is less than the above range, or the proportion of the component (a-2) exceeds the above range, the Mooney viscosity of the rubber composition increases, and the processability decreases. On the other hand, when the proportion of the component (a-2) is less than the above range or the proportion of the component (a-1) exceeds the above range, the green strength of the rubber composition and the mechanical properties after curing are lowered.
（Ｂ）成分のプロセスオイルは、主として加工性を改善する作用を有する。プロセスオイルは、特に限定されるものではなく、パラフィン系プロセスオイル、ナフテン系プロセスオイル、および芳香族系プロセスオイルのいずれであってもよいが、機械特性を向上させ、また、押出加工性、耐汚染性、耐候性、熱老化特性などの観点からはパラフィン系プロセスオイルが好ましい。具体的には、例えば、出光興産（株）製のダイアナプロセスオイルＰＷ−９０、同ダイアナプロセスオイルＰＷ−３８０、ＪＸ日鉱日石エネルギー（株）製のスーパーオイルＮ１００（以上、いずれもパラフィン系プロセスオイルの商品名）などが好適に使用される。プロセスオイルは、１種を単独で使用してもよく、２種以上を混合して使用してもよい。 The process oil of component (B) mainly has an effect of improving processability. The process oil is not particularly limited, and may be any of paraffinic process oil, naphthenic process oil, and aromatic process oil. Paraffinic process oils are preferred from the viewpoints of contamination, weather resistance, heat aging characteristics, and the like. Specifically, for example, Diana Process Oil PW-90, Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd., Super Oil N100 manufactured by JX Nippon Mining & Energy Co., Ltd. Oil trade name) is preferably used. One process oil may be used alone, or two or more process oils may be mixed and used.
このプロセスオイルの配合量は、（Ａ）ポリマー成分１００質量部あたり、３０〜６０質量部の範囲が好ましい。配合量が３０質量部未満では、ゴム組成物のムーニー粘度が高くなり、加工性が低下する。また、混練加工時に分散不良などが生ずるおそれがある。６０質量部を超えると、グリーン強度が低下し、硬化後の機械特性も低下する。また、熱老化特性が低下し、加熱時の寸法変化も大きくなる。さらに、加工時に分散不良が生じるおそれがある。プロセスオイルの配合量のより好ましい範囲は、ポリマー成分１００質量部あたり、３０〜４０質量部である。 The blend amount of the process oil is preferably in the range of 30 to 60 parts by mass per 100 parts by mass of the polymer component (A). When the blending amount is less than 30 parts by mass, the Mooney viscosity of the rubber composition increases, and the processability decreases. Moreover, there is a risk of poor dispersion during kneading. When it exceeds 60 parts by mass, the green strength is lowered and the mechanical properties after curing are also lowered. In addition, the heat aging characteristics are reduced, and the dimensional change during heating is increased. Furthermore, there is a risk of poor dispersion during processing. A more preferable range of the blending amount of the process oil is 30 to 40 parts by mass per 100 parts by mass of the polymer component.
（Ｃ）成分のカーボンブラックは、主として機械特性を向上させる作用を有する。カーボンブラックとしては、ファーネスブラック、チャンネルブラック、サーマルブラックなどを用いることができる。なかでも、機械特性向上の観点から、ファーネスブラックが好ましく、良押出性ファーネスカーボンブラック（ＦＥＦ）、汎用ファーネスカーボンブラック（ＧＰＦ）、半補強性ファーネスカーボンブラック（ＳＲＦ）、がより好ましい。具体的には、例えば、旭カーボン（株）製の旭＃６０、旭＃５５、旭＃５０Ｕ、東海カーボン（株）製のシーストＦ、シーストＶ、シーストＳ、新日化カーボン（株）製のニテロン＃１０（以上、いずれも商品名）などが好適に使用される。カーボンブラックは、１種を単独で使用してもよく、２種以上を混合して使用してもよい。 Component (C), carbon black, mainly has an effect of improving mechanical properties. As carbon black, furnace black, channel black, thermal black, etc. can be used. Among these, furnace black is preferable from the viewpoint of improving mechanical properties, and good extrudability furnace carbon black (FEF), general-purpose furnace carbon black (GPF), and semi-reinforcing furnace carbon black (SRF) are more preferable. Specifically, for example, Asahi # 60, Asahi # 55, Asahi # 50U manufactured by Asahi Carbon Co., Ltd., Seast F, Seast V, Seast S manufactured by Tokai Carbon Co., Ltd. Niteron # 10 (all are trade names) and the like are preferably used. Carbon black may be used individually by 1 type, and 2 or more types may be mixed and used for it.
このカーボンブラックの配合量は、（Ａ）ポリマー成分１００質量部あたり、４０〜７０質量部の範囲が好ましい。配合量が４０質量部未満では、機械特性が低下する。また、７０質量部を超えると、ゴム組成物のムーニー粘度が高くなり、加工性が低下する。カーボンブラックの配合量のより好ましい範囲は、ポリマー成分１００質量部あたり、５０〜６０質量部である。 The blending amount of the carbon black is preferably in the range of 40 to 70 parts by mass per 100 parts by mass of the polymer component (A). If the blending amount is less than 40 parts by mass, the mechanical properties are deteriorated. Moreover, when it exceeds 70 mass parts, the Mooney viscosity of a rubber composition will become high and workability will fall. A more preferable range of the compounding amount of carbon black is 50 to 60 parts by mass per 100 parts by mass of the polymer component.
（Ｄ）成分の架橋剤としては、有機過酸化物が好ましい。硫黄や硫黄化合物など、この種のゴムの架橋剤として広く使用されているその他の架橋剤も使用可能であるが、機械特性（特に、圧縮永久歪み特性）、熱老化特性、寸法安定性などを高める観点からは有機過酸化物が好ましい。有機過酸化物としては、ジクミルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド、２，５−ジメチルー２，５−ジ−（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチルー２，５−ジ−（ｔｅｒｔ−ブチルパーオキシ）ヘキシン−３、１，３−ビス（ｔｅｒｔ−ブチルパーオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−シクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルパーオキシ）バレレート、ベンゾイルオキサイド、２，４−ジクロロベンゾイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルパーオキシイソプロピルカーボネート、ジアセチルパーオキサイド、ラウロイルパーオキサイド、ｔｅｒｔ−ブチルクミルパーオキサイドなどが挙げられる。これらは、１種を単独で使用してもよく、２種以上を混合して使用してもよい。架橋剤としては、なかでも製造加工工程において加えられる熱履歴や貯蔵安定性の観点からジクミルパーオキサイド、１，３−ビス（ｔｅｒｔ−ブチルパーオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−シクロヘキサンが好ましく、ジクミルパーオキサイドがより好ましい。有機過酸化物は、（Ａ）ポリマー成分１００質量部に対し、２．０〜４．０質量部配合することが好ましく、２．５〜３．５質量部配合することがより好ましい。配合量が２．０質量部未満では、熱老化特性、寸法安定性、機械特性、特に圧縮永久歪みが低下する。また、配合量が４．０質量部を超えると、引張伸びが低下するおそれがある。 (D) As a crosslinking agent of a component, an organic peroxide is preferable. Other cross-linking agents that are widely used as cross-linking agents for this type of rubber, such as sulfur and sulfur compounds, can also be used, but they have mechanical properties (especially compression set properties), heat aging properties, dimensional stability, etc. From the viewpoint of enhancing the organic peroxide, an organic peroxide is preferable. Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di -(Tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (tert-butylperoxy) -cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl oxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate , Tert-butyl peroxyisopropyl carbonate, diacetyl Oxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among the crosslinking agents, dicumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-) is particularly preferred from the viewpoint of thermal history and storage stability applied in the manufacturing process. Butylperoxy) -cyclohexane is preferred, and dicumyl peroxide is more preferred. The organic peroxide is preferably blended in an amount of 2.0 to 4.0 parts by weight, more preferably 2.5 to 3.5 parts by weight, per 100 parts by weight of the polymer component (A). When the blending amount is less than 2.0 parts by mass, the heat aging characteristics, dimensional stability, mechanical characteristics, particularly compression set are lowered. Moreover, when a compounding quantity exceeds 4.0 mass parts, there exists a possibility that tensile elongation may fall.
なお、架橋剤として有機過酸化物を用いる場合、架橋助剤を配合すると加硫速度の
促進、また、機械特性、特に圧縮永久歪みや熱老化特性をさらに向上させることができる。架橋助剤としては、例えば、アクリル酸亜鉛もしくはその塩、メタクリル酸亜鉛もしくはその塩、エチレングリコールジメタクリレート、Ｎ，Ｎ′−ｍ−フェニレンジマレイミド、トリアリルイソシアヌレート、多官能性メタクリレートモノマーなどが挙げられる。架橋助剤の配合量は、例えば、メタクリル酸亜鉛もしくはその塩では、ポリマー成分１００質量部に対し、通常、１．０〜５．０質量部、好ましくは、２．０〜４．０質量部である。また、Ｎ，Ｎ′−ｍ−フェニレンジマレイミドでは、ポリマー成分１００質量部に対し、通常、０．５〜３．０質量部、好ましくは、０．５〜１．５質量部である。配合量が前記範囲未満では、添加による効果が十分に得られず、前記範囲を超えると、機械特性、特に引張伸びが低下するおそれがある。
When an organic peroxide is used as a crosslinking agent, the addition of a crosslinking aid can accelerate the vulcanization rate and further improve the mechanical properties, particularly compression set and heat aging properties. Examples of the crosslinking aid include zinc acrylate or a salt thereof, zinc methacrylate or a salt thereof, ethylene glycol dimethacrylate, N, N′-m-phenylene dimaleimide, triallyl isocyanurate, and a polyfunctional methacrylate monomer. Can be mentioned. For example, in the case of zinc methacrylate or a salt thereof, the amount of the crosslinking aid is usually 1.0 to 5.0 parts by mass, preferably 2.0 to 4.0 parts by mass with respect to 100 parts by mass of the polymer component. It is. Moreover, in N, N'-m-phenylene dimaleimide, it is 0.5-3.0 mass parts normally with respect to 100 mass parts of polymer components, Preferably, it is 0.5-1.5 mass parts. If the blending amount is less than the above range, the effect of addition cannot be sufficiently obtained, and if it exceeds the above range, mechanical properties, particularly tensile elongation, may be lowered.
本発明のケーブル接続部用保護部材を形成する組成物には、以上の各成分の他、本発明の効果を阻害しない範囲で、この種の組成物に一般に配合される、酸化亜鉛（亜鉛華）、酸化防止剤、滑剤、加工助剤、着色剤、難燃剤、オゾン劣化防止剤、老化防止剤、紫外線吸収剤、中和剤、その他の添加剤を配合することができる。また、カーボンブラック以外の無機充填剤も、本発明の効果を阻害しない範囲で使用してもよい。 The composition for forming the protective member for a cable connection portion of the present invention includes, in addition to the above-mentioned components, zinc oxide (zinc white) generally blended in this type of composition within a range not impairing the effects of the present invention. ), Antioxidants, lubricants, processing aids, colorants, flame retardants, ozone degradation inhibitors, antioxidants, UV absorbers, neutralizers, and other additives. Moreover, you may use inorganic fillers other than carbon black in the range which does not inhibit the effect of this invention.
酸化亜鉛（亜鉛華）は、ポリマー成分１００質量部に対して、通常、３〜７質量部、好ましくは、４〜６質量部配合される。 Zinc oxide (zinc white) is usually 3 to 7 parts by mass, preferably 4 to 6 parts by mass, per 100 parts by mass of the polymer component.
酸化防止剤は、ポリマー成分１００質量部に対して、通常、０．５〜３．０質量部、好ましくは、１．０〜２．０質量部配合される。酸化防止剤としては、例えば、ヒンダードフェノール系酸化防止剤、ベンズイミダゾール系酸化防止剤、キノリン系酸化防止剤などが知られているが、いずれも使用可能であり、これらの中から１種以上を適宜選択して使用することができる。ヒンダードフェノール系酸化防止剤の市販品としては、例えば、Ｉｒｇａｎｏｘ １０１０、Ｉｒｇａｎｏｘ １０７６（以上、いずれもＢＡＳＦ製 商品名）などが例示される。ベンズイミダゾール系酸化防止剤としては、例えば、ノクラックＭＢ（大内新興化学工業（株）製 商品名）などが例示される。キノリン系酸化防止剤としては、ノンフレックスＲＤ（精工化学（株）製 商品名）などが例示される。 The antioxidant is usually blended in an amount of 0.5 to 3.0 parts by mass, preferably 1.0 to 2.0 parts by mass with respect to 100 parts by mass of the polymer component. As the antioxidant, for example, a hindered phenol-based antioxidant, a benzimidazole-based antioxidant, a quinoline-based antioxidant, etc. are known, and any of them can be used, and one or more of these can be used. Can be appropriately selected and used. Examples of commercially available hindered phenol antioxidants include Irganox 1010, Irganox 1076 (both are trade names manufactured by BASF) and the like. Examples of the benzimidazole antioxidant include NOCRACK MB (trade name, manufactured by Ouchi Shinsei Chemical Co., Ltd.). Non-flex RD (trade name, manufactured by Seiko Chemical Co., Ltd.) is exemplified as a quinoline antioxidant.
カーボンブラック以外の無機充填剤としては、例えば、シリカ、クレー、タルク、マイカ、炭酸カルシウム、水酸化マグネシウム、水酸化アルミニウム、硫酸バリウム、酸化チタン、ガラス繊維などが挙げられる。 Examples of inorganic fillers other than carbon black include silica, clay, talc, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, and glass fiber.
本発明のケーブル接続部用保護部材は、（Ａ）ポリマー成分、（Ｂ）プロセスオイル、（ｃ）カーボンブラック、（Ｄ）架橋剤、および必要に応じて配合される各種成分を、バンバリーミキサー、インターナルミキサー、ニーダー、ロールなどの通常の混練機を用いて均一に混合してゴムコンパウンドを得、これを射出成型などにより所定の形状に成形し架橋させることにより得られる。ゴムコンパウンドを得る際の各成分の配合方法は特に限定されず、架橋剤および架橋助剤などの架橋系成分以外の配合成分を予め混練してマスターバッチとし、残りの成分を添加してさらに混練する方法、各成分を任意の順序で添加し混練する方法、全成分を同時に添加して混練する方法などのいずれであってもよい。 The protective member for a cable connection part of the present invention comprises (A) a polymer component, (B) process oil, (c) carbon black, (D) a crosslinking agent, and various components blended as necessary. It is obtained by uniformly mixing using a normal kneader such as an internal mixer, a kneader, or a roll to obtain a rubber compound, which is molded into a predetermined shape by injection molding or the like and crosslinked. The blending method of each component when obtaining a rubber compound is not particularly limited, and blending components other than crosslinking components such as a crosslinking agent and a crosslinking aid are kneaded in advance to obtain a master batch, and the remaining components are added and further kneaded Or a method of adding and kneading the components in an arbitrary order, a method of adding all the components simultaneously and kneading them, or the like.
このようにして得られるケーブル接続部用保護部材は、プロセスオイルおよびカーボンブラックの配合量が抑えられた組成物で形成されているので、機械特性が良好で、熱老化特性、寸法安定性にも優れている。しかも、組成物は流動性が良好で加工性に優れているため、射出成型やトランスファー成型が適用可能であり、外観に優れる成型品を効率よく製造することができる。したがってまた、これを用いて信頼性の高いケーブル接続部を効率よく形成することができる。 The cable connection protective member thus obtained is formed of a composition in which the blending amount of process oil and carbon black is suppressed, so that the mechanical properties are good, and the heat aging characteristics and dimensional stability are also good. Are better. Moreover, since the composition has good fluidity and excellent processability, injection molding and transfer molding can be applied, and a molded product having excellent appearance can be efficiently produced. Therefore, a highly reliable cable connection part can be efficiently formed using this.
なお、本発明のケーブル接続部用保護部材を形成する組成物は、（ｉ）ムーニー粘度ＭＬ１＋４（１００℃）が１０〜４０であることが好ましく、１０〜３０であることがより好ましい。ムーニー粘度ＭＬ１＋４（１００℃）が１０未満では、ゴムコンパウンド製造時および製品加工時にリボン切れなどを起こして生産性が低下し、４０を超えると、加工性が低下する。また（ii）ムーニースコーチ時間ｔ5（１２５℃）が１０〜５０分であることが好ましく、２０〜４０分であることがより好ましい。ムーニースコーチ時間ｔ5（１２５℃）が１０分未満では、ゴムコンパウンド製造時および製品加工時にスコーチ（ヤケ）が発生し、５０分を超えると、加硫時間が長くなり生産性が低下する。
ムーニー粘度ＭＬ１＋４（１００℃）およびムーニースコーチ時間ｔ5（１２５℃）は、架橋前の組成物について、ＪＩＳ Ｋ ６３００−１（未加硫ゴム―物理特性―第１部：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）に準拠して測定される。
In addition, it is preferable that (i) Mooney viscosity ML1 + 4 (100 degreeC) is 10-40, and, as for the composition which forms the protection member for cable connection parts of this invention, it is more preferable that it is 10-30. When the Mooney viscosity ML 1 + 4 (100 ° C.) is less than 10, the ribbon is broken at the time of rubber compound production and product processing, and the productivity is lowered. When the viscosity exceeds 40, the workability is lowered. The (ii) it is preferably a Mooney scorch time t 5 (125 ℃) is 10 to 50 minutes, more preferably 20 to 40 minutes. When the Mooney scorch time t 5 (125 ° C.) is less than 10 minutes, scorch (burning) occurs during rubber compound production and product processing, and when it exceeds 50 minutes, the vulcanization time becomes longer and the productivity decreases.
The Mooney viscosity ML 1 + 4 (100 ° C.) and the Mooney scorch time t 5 (125 ° C.) are JIS K 6300-1 (unvulcanized rubber—physical properties—part 1: viscosity by Mooney viscometer And scorch time).
また、本発明のケーブル接続部用保護部材を形成する組成物は、（iii）デュロメータ硬さが４５〜６０であることが好ましく、５０〜６０であることがより好ましい。デュロメータ硬さが４５未満では、製品に荷重がかかった際につぶれるおそれがあり、６０を超えると、硬すぎて保護材としてケーブルに装着できないおそれがある。
デュロメータ硬さは、ＪＩＳ Ｋ ６２５３−３（加硫ゴムおよび熱可塑性ゴム―硬さの求め方）に準拠してタイプＡデュロメータにより測定される。
Moreover, it is preferable that the composition which forms the protection member for cable connection parts of this invention has (iii) durometer hardness of 45-60, and it is more preferable that it is 50-60. If the durometer hardness is less than 45, the product may be crushed when a load is applied to it, and if it exceeds 60, the product may be too hard to be attached to the cable as a protective material.
The durometer hardness is measured by a type A durometer in accordance with JIS K 6253-3 (vulcanized rubber and thermoplastic rubber—how to obtain hardness).
また、本発明のケーブル接続部用保護部材を形成する組成物は、（iv）引張伸びが３００〜６００％であることが好ましく、４００〜５００％であることがより好ましい。引張伸びが３００％未満では、使用時に破損するおそれがあり、６００％を超えると、ケーブル装着時の密着性が低下するおそれがある。
引張伸びは、ＪＩＳ Ｋ ６２５１（加硫ゴムおよび熱可塑性ゴム―引張特性の求め方）に準拠して測定される。
Moreover, it is preferable that the composition which forms the protection member for cable connection parts of this invention is (iv) tensile elongation 300-600%, and it is more preferable that it is 400-500%. If the tensile elongation is less than 300%, it may be damaged during use, and if it exceeds 600%, the adhesion at the time of cable attachment may be reduced.
The tensile elongation is measured in accordance with JIS K 6251 (vulcanized rubber and thermoplastic rubber—how to obtain tensile properties).
また、本発明のケーブル接続部用保護部材を形成する組成物は、（ｖ）圧縮永久ひずみが１０〜３０％であることが好ましく、１３〜２２％であることがより好ましい。圧縮永久ひずみが３０％を超えると使用時に形状を保持できないおそれがあり、また密着性が低下するおそれもある。一方、１０％に満たないとケーブルへの装着が困難なるおそれがある。
圧縮永久ひずみは、ＪＩＳ Ｋ ６２６２（加硫ゴムおよび熱可塑性ゴム―常温，高温および低温における圧縮永久ひずみの求め方）に準拠し測定される。
Moreover, it is preferable that the composition which forms the protection member for cable connection parts of this invention is (v) compression set 10-30%, and it is more preferable that it is 13-22%. If the compression set exceeds 30%, the shape may not be maintained at the time of use, and the adhesion may be lowered. On the other hand, if it is less than 10%, it may be difficult to attach the cable.
The compression set is measured according to JIS K 6262 (vulcanized rubber and thermoplastic rubber—how to obtain compression set at normal temperature, high temperature and low temperature).
また、本発明のケーブル接続部用保護部材を形成する組成物は、熱老化（１２１℃、６時間）後の引張伸び残率が９０％以上であることが好ましく、また、重量変化率が−３〜０％であることが好ましい。引張伸び残率が９０％未満であるか、または重量変化率が−３％未満、すなわち、重量変化が前記範囲より大きくなると、寸法安定性の低下などによりケーブル接続部への装着後、保護部材として機能しなくなるおそれがある。 Further, the composition forming the cable connection part protective member of the present invention preferably has a residual tensile elongation after heat aging (121 ° C., 6 hours) of 90% or more, and the weight change rate is − It is preferable that it is 3 to 0%. When the tensile elongation residual ratio is less than 90% or the weight change rate is less than −3%, that is, when the weight change is larger than the above range, the protective member is attached to the cable connection portion due to a decrease in dimensional stability or the like. May not function as
また、本発明のケーブル接続部用保護部材は、ケーブル接続部に装着された際にケーブル接続部に当接される面の表面粗さが十点平均粗さ（Ｒｚ：ＪＩＳ Ｂ ０６０１−１９９４）で４〜８μｍであることが好ましく、５〜７μｍであることがより好ましい。表面粗さ（Ｒｚ）が４μｍ未満では成形型からの離形が難しくなり、表面粗さ（Ｒｚ）が８μｍを超えると、機械特性の低下と共にケーブル接続部と保護部材との界面に雨水などが侵入し、絶縁性能が大きく低下するおそれがある。 Further, the protective member for a cable connection part of the present invention has a ten-point average roughness (Rz: JIS B 0601-1994) of the surface of the surface that comes into contact with the cable connection part when mounted on the cable connection part. 4 to 8 μm is preferable, and 5 to 7 μm is more preferable. When the surface roughness (Rz) is less than 4 μm, it is difficult to release from the mold, and when the surface roughness (Rz) exceeds 8 μm, rainwater and the like are present at the interface between the cable connection portion and the protective member as the mechanical properties deteriorate. There is a risk that the insulation performance will be greatly reduced.
なお、保護部材の表面は、保護部材の成型に用いる成型型内面の表面状態がほぼ転写される。このため、成型型内面の表面粗さを制御することにより、保護部材の表面粗さを所望の範囲に調節することができる。すなわち、成型型内面の表面粗さ（Ｒｚ）を４〜８μｍの範囲に設定すれば、保護部材の表面を、ほぼそれに対応した表面粗さ（Ｒｚ）４〜８μｍを有する表面に形成することができる。成型型内面の表面粗さは、内面仕上げ時に使用する研磨材などを適宜選択することによって任意に制御することができる。 The surface state of the inner surface of the molding die used for molding the protective member is almost transferred to the surface of the protective member. For this reason, the surface roughness of the protection member can be adjusted to a desired range by controlling the surface roughness of the inner surface of the mold. That is, if the surface roughness (Rz) of the inner surface of the mold is set in a range of 4 to 8 μm, the surface of the protective member can be formed on a surface having a surface roughness (Rz) of 4 to 8 μm corresponding to the surface. it can. The surface roughness of the inner surface of the molding die can be arbitrarily controlled by appropriately selecting an abrasive used for finishing the inner surface.
本発明のケーブル接続部用保護部材は、電力ケーブルをはじめ、各種ケーブルの接続部に装着する保護部材として幅広く用いることができる。接続部は終端接続部であっても中間接続部であってもよい。従来に比べ、機械特性、熱老化特性および寸法安定性が向上しているため、屋外のような厳しい条件下で長期間使用するケーブル接続部における用途に特に有用である。 The protection member for a cable connection part of the present invention can be widely used as a protection member to be attached to a connection part of various cables including a power cable. The connection part may be a terminal connection part or an intermediate connection part. Since mechanical characteristics, heat aging characteristics, and dimensional stability are improved as compared with the prior art, it is particularly useful for applications in cable connection parts that are used for a long time under harsh conditions such as outdoors.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、実施例および比較例で用いた成分は以下の通りである。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all. In addition, the component used by the Example and the comparative example is as follows.
ＥＰＤＭ（エチレン・プロピレン・ジエン３元共重合体）（１）：
三井化学（株）製 商品名 三井ＥＰＴ Ｘ−４０１０Ｍ；
エチレン含量５４質量％、ジエン含量７．６質量％、
ムーニー粘度ＭＬ１＋４（１００℃）８
ＥＰＤＭ（エチレン・プロピレン・ジエン３元共重合体）（２）：
三井化学（株）製 商品名 三井ＥＰＴ ３０６２ＥＭ；
エチレン含量６５質量％、ジエン含量４．５質量％、
ムーニー粘度ＭＬ１＋４（１２５℃）４３、油展量２０ｐｈｒ
カーボンブラック：
旭カーボン（株）製 商品名 旭＃５０Ｕ
パラフィン系プロセスオイル：
出光興産（株）製 商品名 ダイアナプロセスオイルＰＷ−９０
酸化亜鉛：
三井金属（株）製 商品名 酸化亜鉛二種
酸化防止剤：
ＢＡＳＦ製 商品名 Ｉｒｇａｎｏｘ１０１０
有機過酸化物：ジクミルパーオキサイド
日油（株）製 商品名 パークミルＤ−４０
硫黄：
細井化学工業（株）製 商品名 硫黄２００メッシュ
加硫促進剤：
大内新興化学工業（株）製 商品名 ノクセラーＴＴ−Ｐ
EPDM (ethylene / propylene / diene terpolymer) (1):
Product name: Mitsui EPT X-4010M, manufactured by Mitsui Chemicals, Inc.
Ethylene content 54% by weight, diene content 7.6% by weight,
Mooney viscosity ML 1 + 4 (100 ° C) 8
EPDM (ethylene / propylene / diene terpolymer) (2):
Product name: Mitsui EPT 3062EM, manufactured by Mitsui Chemicals, Inc.
Ethylene content 65% by weight, diene content 4.5% by weight,
Mooney viscosity ML 1 + 4 (125 ° C) 43, oil extended amount 20 phr
Carbon black:
Asahi Carbon Co., Ltd. Product name Asahi # 50U
Paraffinic process oil:
Idemitsu Kosan Co., Ltd. Product Name Diana Process Oil PW-90
Zinc oxide:
Product name: Mitsui Kinzoku Co., Ltd. Product name: Zinc oxide type 2
Product name Irganox1010 made by BASF
Organic peroxide: Dicumyl peroxide NOF Corporation Brand name Park Mill D-40
sulfur:
Product name Sulfur 200 mesh Vulcanization accelerator manufactured by Hosoi Chemical Co., Ltd .:
Ouchi Shinsei Chemical Co., Ltd. Product Name Noxeller TT-P
（実施例１）
ＥＰＤＭ（１）７０質量部、ＥＰＤＭ（２）（ポリマー成分量として）３０質量部、カーボンブラック５５質量部、パラフィン系プロセスオイル３０質量部、酸化亜鉛５質量部、酸化防止剤１質量部および有機過酸化物２．５質量部をニーダーにて均一に混練してゴム組成物を得た。
得られたゴム組成物を射出成型し、外径４０ｍｍ、長さ１００ｍｍの円筒状のケーブル接続部用保護カバーを作製した。また、これとは別に、ゴム組成物を８インチロールでシート状に押し出し、プレス成形加硫を行って、２ｍｍ厚のシートを作製した。
Example 1
EPDM (1) 70 parts by mass, EPDM (2) (as polymer component amount) 30 parts by mass, carbon black 55 parts by mass, paraffinic process oil 30 parts by mass, zinc oxide 5 parts by mass, antioxidant 1 part by mass and organic A rubber composition was obtained by uniformly kneading 2.5 parts by mass of peroxide with a kneader.
The obtained rubber composition was injection-molded to produce a cylindrical cable connection part protective cover having an outer diameter of 40 mm and a length of 100 mm. Separately, the rubber composition was extruded into a sheet shape with an 8-inch roll and subjected to press molding vulcanization to produce a 2 mm thick sheet.
（実施例２〜６、比較例１〜３）
実施例１と同様にして、表１に示す成分を表１に示す量で用いて、ケーブル接続部用保護カバーおよびシートを作製した。
(Examples 2-6, Comparative Examples 1-3)
In the same manner as in Example 1, the components shown in Table 1 were used in the amounts shown in Table 1, and a protective cover for a cable connection portion and a sheet were produced.
各実施例および各比較例で得られたシートについて、デュロメータ硬さ、引張伸び、および圧縮永久歪みを測定した。また、熱老化試験を行い熱老化特性を評価した。また、架橋前のゴム組成物のムーニー粘度ＭＬ１＋４およびムーニースコーチ時間ｔ5をそれぞれ１００℃および１２５℃で測定した。さらに、各実施例および各比較例で得られたケーブル接続部用保護カバーの外観から成型性を評価した。測定方法、評価方法などは次の通りである。 About the sheet | seat obtained by each Example and each comparative example, durometer hardness, tensile elongation, and compression set were measured. In addition, a heat aging test was performed to evaluate heat aging characteristics. In addition, the Mooney viscosity ML 1 + 4 and Mooney scorch time t 5 of the rubber composition before crosslinking were measured at 100 ° C. and 125 ° C., respectively. Furthermore, the moldability was evaluated from the appearance of the protective cover for cable connection obtained in each example and each comparative example. The measurement method and evaluation method are as follows.
［ムーニー粘度ＭＬ１＋４、ムーニースコーチ時間ｔ5］
ＪＩＳ Ｋ ６３００−１に準拠して測定した。
［デュロメータ硬さ］
ＪＩＳ Ｋ ６２５３−３に規定するタイプＡデュロメータにより測定した。
［引張伸び］
ＪＩＳ Ｋ ６２５１に基づき、３号試験片を用いて測定した。
［圧縮永久歪み］
ＪＩＳ Ｋ ６２６２に準拠し、１００℃で７０時間の条件で圧縮率２５％として測定した。
［熱老化特性］
ＪＩＳ Ｋ ６２５７に準拠し、１２１℃で１６８時間の熱老化後、上記と同様にして引張伸びを測定し、次式より引張伸び残率を算出した。また、熱老化前後の重量を測定し次式よりその変化率を算出した。
引張伸び残率（％）
＝［（熱老化後引張伸び）／（初期引張伸び）］×１００
重量変化率（％）
＝［｛（熱老化後重量）−（熱老化前重量）｝／（熱老化前重量）］×１００
［成型性］
得られたケーブル接続部用保護カバーの外観を目視にて観察し、下記の基準で評価した。
◎：外観良好
○：外観概ね良好（僅かに材料のフロー痕あり）
△：外観不良
×：材料の流動性が悪く成型できず
[Mooney viscosity ML 1 + 4 , Mooney scorch time t 5 ]
It measured based on JISK6300-1.
[Durometer hardness]
It measured with the type A durometer prescribed | regulated to JISK6253-3.
[Tensile elongation]
Based on JIS K 6251, measurement was performed using a No. 3 test piece.
[Compression set]
In accordance with JIS K 6262, the compression rate was 25% under the conditions of 100 ° C. and 70 hours.
[Heat aging characteristics]
Based on JIS K 6257, after thermal aging at 121 ° C. for 168 hours, the tensile elongation was measured in the same manner as described above, and the residual tensile elongation was calculated from the following formula. Further, the weight before and after heat aging was measured, and the rate of change was calculated from the following formula.
Tensile elongation residual rate (%)
= [(Tensile elongation after heat aging) / (Initial tensile elongation)] × 100
Weight change rate (%)
= [{(Weight after heat aging) − (weight before heat aging)} / (weight before heat aging)] × 100
[Moldability]
The appearance of the obtained protective cover for cable connection part was visually observed and evaluated according to the following criteria.
◎: Appearance is good ○: Appearance is generally good (slight material flow marks)
△: Appearance defect ×: Poor material flowability
これらの結果を表１下欄に示す。 These results are shown in the lower column of Table 1.
表１から明らかなように、実施例１〜５はいずれも、加工性の指標であるムーニー粘度およびムーニースコーチ時間、デュロメータ硬さ、および引張伸び、圧縮永久歪み、熱老化特性、成型性において、良好な結果が得られた。 As is clear from Table 1, Examples 1 to 5 all have Mooney viscosity and Mooney scorch time, durometer hardness, and tensile elongation, compression set, heat aging characteristics, and moldability, which are indexes of workability. Good results were obtained.
本発明のケーブル接続部用保護部材は、従来に比べ、機械特性、熱老化特性および寸法安定性が改善されており、かつ外観も良好であることから、各種ケーブルの接続部に装着する保護部材として有用である。 The protective member for a cable connection part of the present invention has improved mechanical properties, heat aging characteristics and dimensional stability as compared with the prior art, and has a good appearance. Therefore, the protective member is attached to the connection part of various cables. Useful as.
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| JP2013035965A (en) * | 2011-08-09 | 2013-02-21 | Fujikura Ltd | Insulating composition and molding |
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