JPH01168741A - Production of vulcanized ethylene/alpha-olefin copolymer rubber composition - Google Patents
Production of vulcanized ethylene/alpha-olefin copolymer rubber compositionInfo
- Publication number
- JPH01168741A JPH01168741A JP62328854A JP32885487A JPH01168741A JP H01168741 A JPH01168741 A JP H01168741A JP 62328854 A JP62328854 A JP 62328854A JP 32885487 A JP32885487 A JP 32885487A JP H01168741 A JPH01168741 A JP H01168741A
- Authority
- JP
- Japan
- Prior art keywords
- organic peroxide
- vulcanization
- rubber composition
- weight
- olefin copolymer
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 229920001971 elastomer Polymers 0.000 title claims abstract description 21
- 239000005060 rubber Substances 0.000 title claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000005977 Ethylene Substances 0.000 title claims abstract description 13
- 239000004711 α-olefin Substances 0.000 title claims abstract description 12
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001746 injection moulding Methods 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 238000004073 vulcanization Methods 0.000 abstract description 37
- 239000004636 vulcanized rubber Substances 0.000 abstract description 11
- -1 diacyl peroxide Chemical class 0.000 description 8
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 238000010059 sulfur vulcanization Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010060 peroxide vulcanization Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229960004029 silicic acid Drugs 0.000 description 2
- 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
- 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
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-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
- 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
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 102220534194 B-cell lymphoma/leukemia 10_E50R_mutation Human genes 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FPCCSQOGAWCVBH-UHFFFAOYSA-N ketanserin Chemical compound C1=CC(F)=CC=C1C(=O)C1CCN(CCN2C(C3=CC=CC=C3NC2=O)=O)CC1 FPCCSQOGAWCVBH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 230000002028 premature Effects 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- PNWOTXLVRDKNJA-UHFFFAOYSA-N tert-butylperoxybenzene Chemical compound CC(C)(C)OOC1=CC=CC=C1 PNWOTXLVRDKNJA-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- BPSIOYPQMFLKFR-VIFPVBQESA-N trimethoxy-[3-[[(2r)-oxiran-2-yl]methoxy]propyl]silane Chemical compound CO[Si](OC)(OC)CCCOC[C@H]1CO1 BPSIOYPQMFLKFR-VIFPVBQESA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分舒〕
本発明は生産性の高い加硫エチレン／α−オレフィン共
重合ゴム（以下、ＥＯＲという）組成物の製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a highly productive method for producing a vulcanized ethylene/α-olefin copolymer rubber (hereinafter referred to as EOR) composition.
射出成形機は、生産性の高いことから広くゴム組成物の
加硫に用いられているが、この機械による加硫では加硫
後、高温の加硫ゴム組成物を金型より取出す時に引裂き
易い問題を有している。Injection molding machines are widely used for vulcanizing rubber compositions due to their high productivity, but when vulcanizing with this machine, the high-temperature vulcanized rubber composition tends to tear when taken out from the mold after vulcanization. I have a problem.
そのためＥＯＲ等の引裂強度の低いゴムについては、一
般に引裂強度の高い架橋剤として硫黄を用いる組成物（
以下、硫黄加硫系という）が使用される。しかしながら
、硫黄加硫系では早期加硫による加工の不安定性を排除
し、加硫成形時の加硫速度を大きくするには限界があり
、生産性の十分な向上が出来ていない。又、架橋剤とし
て有機過酸化物を用いる組成物（以下、有機過酸化物加
硫系という）は、早期加硫を生じにクク、加硫成形時の
加硫速度は大きいが、引裂強度が小さく、加硫後の高温
の加硫ゴム組成物を金型より取出す時の引裂けによる不
良率が高くて使用出来ないと言われていた。Therefore, for rubbers with low tear strength such as EOR, compositions that use sulfur as a crosslinking agent with high tear strength are generally used.
(hereinafter referred to as sulfur vulcanization) is used. However, in the sulfur vulcanization system, there is a limit to eliminating processing instability due to early vulcanization and increasing the vulcanization rate during vulcanization molding, and productivity cannot be sufficiently improved. In addition, compositions using organic peroxides as crosslinking agents (hereinafter referred to as organic peroxide vulcanization systems) tend to cause premature vulcanization, and although the vulcanization rate during vulcanization molding is high, the tear strength is low. It was said that it could not be used because of its small size and high defect rate due to tearing when the vulcanized rubber composition was taken out of the mold at a high temperature after vulcanization.
本発明者らは、早期加硫が生じに（り、加硫成形時の加
硫速度の大きい有機過酸化物加硫系を用いて、射出成形
機による加硫ゴム組成物を金型から取出す時の引裂けに
よる不良率が低く生産性の高い加硫方法を得るべく鋭意
検討し、本発明に到達した。The present inventors use an organic peroxide vulcanization system that causes early vulcanization and has a high vulcanization rate during vulcanization molding to take out a vulcanized rubber composition from a mold using an injection molding machine. The present invention was achieved through extensive research in order to obtain a vulcanization method with a low defect rate due to tearing and high productivity.
本発明者らは、有機過酸化物加硫系による加硫ゴム組成
物が硫黄加硫系による加硫ゴム組成物に比較して室温の
引裂強度は劣るが、高温時の引裂強度は、両者間でほと
んど差がなくなることを見い出した。即ち、エチレン／
α−オレフィン共重合ゴム１００重量部当り、有機過酸
化物１〜１０重量部添加した未加硫ゴム組成物を射出成
形機を用いて加硫した後、高温の加硫ゴム組成物を金型
より取出す時の引裂き易さは、硫黄加硫系を用いた場合
と同等になることを見つけ出した。The present inventors have discovered that although the tear strength of a vulcanized rubber composition produced by an organic peroxide vulcanization system is inferior to that of a vulcanized rubber composition produced by a sulfur vulcanization system at room temperature, the tear strength at high temperatures is We found that there was almost no difference between the two. That is, ethylene/
After vulcanizing an unvulcanized rubber composition containing 1 to 10 parts by weight of an organic peroxide per 100 parts by weight of α-olefin copolymer rubber using an injection molding machine, the high-temperature vulcanized rubber composition is molded into a mold. It has been found that the ease of tearing when taken out is equivalent to that when a sulfur vulcanization system is used.
又、本発明者らは前記未加硫組成物にシリカ１０〜４０
重量部及びシランカップリング剤０．１〜８！量部添加
することにより、加硫速度を変えることなく引裂強度を
向上させることを見い出した。The present inventors also added 10 to 40 silica to the unvulcanized composition.
Part by weight and silane coupling agent 0.1-8! It has been found that by adding a certain amount, the tear strength can be improved without changing the vulcanization rate.
更に、有機過酸化物として本発明者らが以前に特願昭６
２−２８０４００で得ていた１分半減期温度１６０℃以
下の有機過酸化物と、１分半減期温度１７０℃以上の有
機過酸化物とを１７４〜４／１の割合で組合せることに
より、射出成形機での加硫速度及び早期加硫の生じやす
さをコントロール出来、しかも得られた加硫ゴム組成物
の引張強度が高いことを見い出した。Furthermore, as an organic peroxide, the present inventors previously reported
By combining the organic peroxide with a 1-minute half-life temperature of 160°C or lower obtained in 2-280400 and the organic peroxide with a 1-minute half-life temperature of 170°C or higher in a ratio of 174 to 4/1, It has been found that the vulcanization rate in an injection molding machine and the tendency of early vulcanization to occur can be controlled, and the resulting vulcanized rubber composition has high tensile strength.
本発明において、ＥＯＲとは、エチレンと１種以上のα
−オレフィンよりなる共重合ゴム又はエチレンと１種以
上のα−オレフィンと１種以上の非共役ジエンよりなる
共重合ゴムを意味し、α−オレフィンとしてはプロピレ
ン、１−ブテン、１−ペンテン、１−ヘキセン等が例示
され、非共役ジエンとしてはジシクロペンタジェン、エ
チリデンノルボルネン、１，４−へキサジエン、メチル
テトラヒドロインデン、メチルノルボルネン等が例示さ
れる。In the present invention, EOR refers to ethylene and one or more α
- Means a copolymer rubber consisting of olefin or a copolymer rubber consisting of ethylene, one or more α-olefins, and one or more non-conjugated dienes, and α-olefins include propylene, 1-butene, 1-pentene, 1 Examples of the non-conjugated diene include dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, methyltetrahydroindene, and methylnorbornene.
本発明に用いる有機過酸化物は特に限定されるものでは
なく、ジアシルパーオキサイド、ジアルキル六−オキサ
イド、パーオキシエステル、パーケタールなどの有機過
酸化物の一種以上を用いることができる。The organic peroxide used in the present invention is not particularly limited, and one or more organic peroxides such as diacyl peroxide, dialkyl 6-oxide, peroxy ester, and perketal can be used.
具体的には、ベンゾイルパーオキサイド、ｐ−クロロベ
ンゾイルペルオキシド、２．４−ジクロロベンゾイルペ
ルオキシド、１．１−ジー（ｔ−ブチルペルオキシ）
−８，８，５−トリメチルシクロヘキサン、ジクミルパ
ーオキサイド、ｔ−ブチルパーオキシベンジェ−）、！
ｊ−ｔ−２ ブテルバーオキシジイソブロビルベンゼ
ン、ｔ−ブチルクミルパーオキサイド、２，５−ジメチ
ル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ジ
−ｔ−ブチルパーオキサイド、２．５−ジメチル−２，
５−ジ（ｔ−ブチルペルオキシ）ヘキシ−８９，２，５
−ジメチルヘキサン−２，５−ジヒドロペルオキシド、
２，５−ジメチル−２，５−ジベンゾイルペルオキシヘ
キサンなどがあげられる。Specifically, benzoyl peroxide, p-chlorobenzoyl peroxide, 2.4-dichlorobenzoyl peroxide, 1.1-di(t-butylperoxy)
-8,8,5-trimethylcyclohexane, dicumyl peroxide, t-butylperoxybenzene),!
j-t-2 Buterberoxydiisobrobylbenzene, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, 2 .5-dimethyl-2,
5-di(t-butylperoxy)hexy-89,2,5
-dimethylhexane-2,5-dihydroperoxide,
Examples include 2,5-dimethyl-2,5-dibenzoylperoxyhexane.
そのうち、ベンゾイルパーオキサイド、ｐ−クロルベン
ゾイルペルオキシド、２．４−ジクロロベンゾイルペル
オキシド、１，１−ジー（を−ブチルペルオキシ） −
８，８，５−）リメチルシクロヘキサンが１分半減期温
度１６０℃以下の有機過酸化物に該当し、それと２，５
−ジメチル−２，５−ジベンゾイルペルオキシヘキサン
を除いた他のものが１分半減期温度１７０℃以上の有機
過酸化物に該当する。Among them, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(butylperoxy) -
8,8,5-)limethylcyclohexane is an organic peroxide with a 1-minute half-life temperature of 160°C or less, and 2,5-)
-Dimethyl-2,5-dibenzoylperoxyhexane except for other organic peroxides with a 1-minute half-life temperature of 170°C or higher.
ＥＯＲ１００重量部当りの有機過酸化物の添加量は１〜
１０重量部であり、好ましくは１．５〜５重量部である
。The amount of organic peroxide added per 100 parts by weight of EOR is 1~
The amount is 10 parts by weight, preferably 1.5 to 5 parts by weight.
有機過酸物の添加量が１重量部未満では、得られた加硫
ゴム組成物の架橋度が不十分で圧縮永久歪などの特性が
劣り、添加量が１０重量部を趨えると逆に架橋度が上昇
し、伸びなどの特・性が劣る。If the amount of the organic peracid added is less than 1 part by weight, the degree of crosslinking of the obtained vulcanized rubber composition will be insufficient, resulting in poor properties such as compression set, whereas if the amount added exceeds 10 parts by weight, The degree of crosslinking increases and properties such as elongation are inferior.
又、１分半減期温度１６０℃以下の有機過酸化物と１７
０℃以上の有機過酸化物との割合が１／４〜４／１以外
では加硫速度のコントロールに対する効果が小さい。In addition, organic peroxides with a 1-minute half-life temperature of 160°C or less and 17
If the ratio to the organic peroxide at 0° C. or higher is other than 1/4 to 4/1, the effect on controlling the vulcanization rate is small.
本発明におけるシリカは含水シリカでも無水シリカでも
よいが、価格の点で含水シリカが好ましい。シリカの添
加量が１０重量部未満では引裂強度に対する改良効果が
小さく、添加量が４０重量部を越えるとコンパウンド粘
度の上昇による加工性悪化等の他特性に悪影響を与える
。The silica in the present invention may be hydrated silica or anhydrous silica, but hydrated silica is preferred from the viewpoint of cost. If the amount of silica added is less than 10 parts by weight, the effect of improving tear strength will be small, and if the amount added exceeds 40 parts by weight, it will adversely affect other properties such as deterioration of processability due to increase in compound viscosity.
本発明のシランカップリング剤はビニル基、アミノ基、
メルカプト基、エポキシ基、メタクリロキシ基含有のシ
ランカップリング剤のいずれも使用することが出来るが
、ビニル基を有するシランカップリング剤が好ましい。The silane coupling agent of the present invention has a vinyl group, an amino group,
Although any silane coupling agent containing a mercapto group, an epoxy group, or a methacryloxy group can be used, a silane coupling agent containing a vinyl group is preferred.
具体的には、ビニルトリエトキシシラン、ビニル−トリ
ス（２−メトキシ−エトキシ）シラン、ｒ−メタアクリ
ロオキシ−プロピルトリメトキシシラン、γ−アミノプ
ロピルトリメトオキシシラン、Ｎ−β−（アミノエチル
）−γ−アミノプロピルートリメトキシラン、β−（８
，４−エポキシシクロヘキシル）エチル−トリメトキシ
シラン、ｒ−グリシドオキシプロピルトリメトキシシラ
ン、γ−メルカプトプロピルトリメトキシシランなどが
あげられる。Specifically, vinyltriethoxysilane, vinyl-tris(2-methoxy-ethoxy)silane, r-methacrylooxy-propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl )-γ-aminopropyltrimethoxylan, β-(8
, 4-epoxycyclohexyl)ethyl-trimethoxysilane, r-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.
シランカップリング剤の添加量は０．１〜８重量部、好
ましくは０．５〜２．６Ｎ量部である。０．ＩＭＷ部未
満では加硫速度向上効果が小さり、８重量部を越えると
増電しても加硫速度の向上が小さい。The amount of the silane coupling agent added is 0.1 to 8 parts by weight, preferably 0.5 to 2.6 parts by weight. 0. If it is less than the IMW part, the effect of improving the vulcanization rate will be small, and if it exceeds 8 parts by weight, the improvement in the vulcanization rate will be small even if the electric current is increased.
架橋助剤等を添加することができる。A crosslinking aid and the like can be added.
〈実施例〉
本発明の方法を以下に実施例をあげて更に詳細に説明す
るが、本発明はこれら実施例に何ら限定されるものでは
ない。<Examples> The method of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way.
実施例１〜４、比較例１
表１に示す配合剤ＡをＢＲタイプバンバリーを用いて混
練し、配合剤Ｂを８インチロールにて添加した。表１に
示す加硫条件でプレス加硫を行なった。物性の測定はＪ
ＩＳＫ６８００．６８０１、日本ゴム協会標準規格５Ｒ
ＩＳ８１０２．８１０５ 及びｌ５Ｏ８４に従がって行
なった。その結果を同表に示す。Examples 1 to 4, Comparative Example 1 Compound A shown in Table 1 was kneaded using a BR type Banbury, and Compound B was added using an 8-inch roll. Press vulcanization was performed under the vulcanization conditions shown in Table 1. Measurement of physical properties is J
ISK6800.6801, Japan Rubber Association Standard 5R
Performed according to IS 8102.8105 and 15O84. The results are shown in the same table.
表１に示す未加硫ゴム組成物を下記条件で射出成形機に
よる加硫を行なった。得られた加硫ゴム組成物をＪＩＳ
Ｋ６８０１に従がって物性測定を行った。その結果を表
２に示す。The unvulcanized rubber compositions shown in Table 1 were vulcanized using an injection molding machine under the following conditions. The obtained vulcanized rubber composition was
Physical properties were measured according to K6801. The results are shown in Table 2.
射出成形機による加硫条件
射出成形機：松田製作所製Ｅ５０Ｒ，型締力５８を金
型： １５０Ｘ２００ｘ２箇フイルムゲ一ト金型温
度：２００℃
シリンダ←醜實： ５０℃
射出時間：１０秒
加硫時間二８０．４６．６０１９０秒
表１より、比較例１のエチレン／α−オレフィン共重合
ゴムの一般的な硫黄加硫系に比較して実施例１〜４は、
２８℃の引裂強度はＪＩＳＢ型、トラウザス型とも劣っ
ているが、１５０℃の引裂強度は比較例１以上の値を与
えている。Vulcanization conditions using injection molding machine Injection molding machine: Matsuda Seisakusho E50R, mold clamping force 58
Mold: 150 x 200 x 2 film gate mold Temperature: 200°C Cylinder← Ugility: 50°C Injection time: 10 seconds Vulcanization time: 280.46.60190 seconds From Table 1, ethylene/α-olefin copolymer rubber of Comparative Example 1 In Examples 1 to 4, compared to the general sulfur vulcanization system,
Although the tear strength at 28°C is inferior to both the JISB type and the trousers type, the tear strength at 150°C is higher than Comparative Example 1.
又、射出成形機での加硫温度に近い、１５０℃での引裂
強度が金型より取出時の引裂けに類似しているトラウザ
ウス型で比較例１より高い値を与えている。Furthermore, the tear strength at 150° C., which is close to the vulcanization temperature in an injection molding machine, is higher than that of Comparative Example 1 for the Traussaus mold, which is more similar to tearing when taken out than from a mold.
更に表２の射出成形機による加硫において、２００％引
張応力、伸びが比較例に比べて、実施例はいずれも短い
加硫時間で一定になっており、加硫速度が大きく、生産
性が高いことを示している。Furthermore, in vulcanization using the injection molding machine shown in Table 2, the 200% tensile stress and elongation of the Examples are constant with a shorter vulcanization time than those of the Comparative Examples, and the vulcanization speed is high and the productivity is high. It shows that it is high.
実施例５．６
加硫条件（温度、時間）以外は実施例１〜４と同様に混
線、プレス加硫及び物性測定を行なった。その結果を表
８に示す。実施例１〜４と同様に射出成形機で加硫した
結果を表４に示す。Example 5.6 Crosstalk, press vulcanization, and physical property measurements were carried out in the same manner as in Examples 1 to 4 except for the vulcanization conditions (temperature, time). The results are shown in Table 8. Table 4 shows the results of vulcanization using an injection molding machine in the same manner as in Examples 1 to 4.
表８．４より、１分半減期温度１６０℃以下の有機過酸
化物と１分半減期温度１７０℃以上を
の有機過酸化物φ組合せることにより、加硫速度がコン
トロールされ、表１の実施例２に比較して更に短い加硫
時間で２００％引張応力が一定になっており、より生産
性の高い加硫方法を与えている。From Table 8.4, the vulcanization rate can be controlled by combining an organic peroxide with a 1-minute half-life temperature of 160°C or less and an organic peroxide φ with a 1-minute half-life temperature of 170°C or more. Compared to Example 2, the tensile stress was kept constant at 200% with a shorter vulcanization time, providing a vulcanization method with higher productivity.
本発明により、高温の加硫ゴム組成物を射出成形機の金
型から取出す時の引裂けによる不良率が低く、加硫成型
時の加硫速度が大きい加硫エチレン／α−オレフィン共
重合ゴムの製造方法を提供することが出来る。According to the present invention, the vulcanized ethylene/α-olefin copolymer rubber has a low defect rate due to tearing when taking out the high-temperature vulcanized rubber composition from the mold of an injection molding machine, and has a high vulcanization rate during vulcanization molding. It is possible to provide a manufacturing method for.
表 １
表 １ （読）
表 ２
表 ８
表 ４
米１ エチレンプロピレンエチリデンノルボルネン共重
合体エチレン含量 ７Ｑｗｔ％、ヨウ素価１２ムーニー
粘度 （ＭＬ、＋４１００℃）９０米２ 日本シリカ社
製 含水シリカ
米３ 日本ユニカー社裂ビニルートリス（２−メトキシ
−エトキシコシラン米４ 日本ユニカー社製ビニルトリ
エトキシシラン米５ 住友化学工業社製 加硫促進剤Table 1 Table 1 (Reading) Table 2 Table 8 Table 4 Rice 1 Ethylene propylene ethylidene norbornene copolymer Ethylene content 7Qwt%, Iodine value 12 Mooney viscosity (ML, +4100℃) 90 Rice 2 Made by Nippon Silica Co., Ltd. Hydrous silica rice 3 Japan Unicar Co., Ltd. cracked vinyl lutris (2-methoxy-ethoxysilane rice 4) Nippon Unicar Co., Ltd. vinyltriethoxysilane rice 5 Sumitomo Chemical Co., Ltd. vulcanization accelerator
Claims (1)
当り、有機過酸化物１〜１０重量部添加した未加硫ゴム
組成物を射出成形機を用いて加硫することを特徴とする
加硫エチレン／α−オレフィン共重合ゴム組成物の製造
方法。 ２、未加硫ゴム組成物がエチレン／α−オレフィン共重
合ゴム１００重量部当り、有機過酸化物１〜１０重量部
、シリカ１０〜４０重量部及びシランカップリング剤０
．１〜３重量部添加したものである特許請求の範囲第１
項記載の製造方法。 ３、有機過酸化物が、１分半減期温度１６０℃以下の有
機過酸化物と１分半減期温度１７０℃以上の有機過酸化
物を１／４〜４／１の割合の組合せである特許請求の範
囲第１項又は第２項記載の製造方法。[Claims] 1. An unvulcanized rubber composition containing 1 to 10 parts by weight of an organic peroxide per 100 parts by weight of ethylene/α-olefin copolymer rubber is vulcanized using an injection molding machine. A method for producing a characterized vulcanized ethylene/α-olefin copolymer rubber composition. 2. The unvulcanized rubber composition contains 1 to 10 parts by weight of organic peroxide, 10 to 40 parts by weight of silica, and 0 parts by weight of silane coupling agent per 100 parts by weight of ethylene/α-olefin copolymer rubber.
．． Claim 1 in which 1 to 3 parts by weight are added
Manufacturing method described in section. 3. A patent in which the organic peroxide is a combination of an organic peroxide with a 1-minute half-life temperature of 160°C or less and an organic peroxide with a 1-minute half-life temperature of 170°C or more in a ratio of 1/4 to 4/1. The manufacturing method according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62328854A JPH01168741A (en) | 1987-12-24 | 1987-12-24 | Production of vulcanized ethylene/alpha-olefin copolymer rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62328854A JPH01168741A (en) | 1987-12-24 | 1987-12-24 | Production of vulcanized ethylene/alpha-olefin copolymer rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01168741A true JPH01168741A (en) | 1989-07-04 |
Family
ID=18214832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62328854A Pending JPH01168741A (en) | 1987-12-24 | 1987-12-24 | Production of vulcanized ethylene/alpha-olefin copolymer rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01168741A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1160645A (en) * | 1997-08-27 | 1999-03-02 | Tdk Corp | Heat-resistant low-permitivity polymer material, and film, substrate board, electronic part and heat-resistant resin molding prepared from the same |
| JP2020132809A (en) * | 2019-02-25 | 2020-08-31 | 三井化学株式会社 | Rubber composition and crosslinked body thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54157149A (en) * | 1978-06-02 | 1979-12-11 | Shin Etsu Chem Co Ltd | Rubber composition |
| JPS61138663A (en) * | 1984-12-06 | 1986-06-26 | プラステイツク スペシアルテイ−ズ アンド テクノロジ−ズ，インコ−ポレ−テツド | Powdery elastmer composition and injection molding of elastomer |
| JPH01156354A (en) * | 1987-12-14 | 1989-06-19 | Toray Silicone Co Ltd | Vulcanizable rubber composition |
-
1987
- 1987-12-24 JP JP62328854A patent/JPH01168741A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54157149A (en) * | 1978-06-02 | 1979-12-11 | Shin Etsu Chem Co Ltd | Rubber composition |
| JPS61138663A (en) * | 1984-12-06 | 1986-06-26 | プラステイツク スペシアルテイ−ズ アンド テクノロジ−ズ，インコ−ポレ−テツド | Powdery elastmer composition and injection molding of elastomer |
| JPH01156354A (en) * | 1987-12-14 | 1989-06-19 | Toray Silicone Co Ltd | Vulcanizable rubber composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1160645A (en) * | 1997-08-27 | 1999-03-02 | Tdk Corp | Heat-resistant low-permitivity polymer material, and film, substrate board, electronic part and heat-resistant resin molding prepared from the same |
| WO1999010435A1 (en) * | 1997-08-27 | 1999-03-04 | Tdk Corporation | Heat-resistant, lowly dielectric high-molecular material, and films, substrates, electric components and heat-resistant resin moldings produced therefrom |
| US6500535B1 (en) | 1997-08-27 | 2002-12-31 | Tdk Corporation | Heat resistant, low dielectric polymers, and films, substrates, electronic parts and heat resistant resin molded parts using the same |
| JP2020132809A (en) * | 2019-02-25 | 2020-08-31 | 三井化学株式会社 | Rubber composition and crosslinked body thereof |
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