JP2774615B2 - EPDM rubber composition - Google Patents
EPDM rubber compositionInfo
- Publication number
- JP2774615B2 JP2774615B2 JP26211589A JP26211589A JP2774615B2 JP 2774615 B2 JP2774615 B2 JP 2774615B2 JP 26211589 A JP26211589 A JP 26211589A JP 26211589 A JP26211589 A JP 26211589A JP 2774615 B2 JP2774615 B2 JP 2774615B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- compression set
- vulcanization
- weight
- epdm
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 29
- 229920002943 EPDM rubber Polymers 0.000 title claims description 20
- -1 Neopentyl polyol Chemical class 0.000 claims description 27
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 27
- 238000004073 vulcanization Methods 0.000 description 24
- 238000007906 compression Methods 0.000 description 23
- 230000006835 compression Effects 0.000 description 23
- 229920001971 elastomer Polymers 0.000 description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 18
- 235000014692 zinc oxide Nutrition 0.000 description 18
- 239000004636 vulcanized rubber Substances 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 14
- 235000012255 calcium oxide Nutrition 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-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
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- KKIJZWOPMWEAIV-UHFFFAOYSA-N 2,2-dimethylpropyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)(C)C KKIJZWOPMWEAIV-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 241000341910 Vesta Species 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229950011392 sorbitan stearate Drugs 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は加硫ゴムの気泡の発生を防止し、且つ加硫ゴ
ムの圧縮永久歪みの優れたEPDMゴム組成物に関する。Description: FIELD OF THE INVENTION The present invention relates to an EPDM rubber composition that prevents the formation of air bubbles in vulcanized rubber and has excellent compression set of vulcanized rubber.
［従来の技術］ EPDMは耐オゾン性、耐候性、耐熱性に優れていること
により自動車窓枠ゴム、ホース類や電線被覆ゴム等に使
用されている。[Prior Art] EPDM is used for automobile window frame rubber, hoses, wire covering rubber, and the like because of its excellent ozone resistance, weather resistance, and heat resistance.
しかるに、そのEPDM加硫製品の製造方法としては、高
周波加硫（UHF）、熱空気加硫（HAV）、流動床加硫（PC
M）、液浴加硫（LCM）等の連続押出加硫製造方式が多く
用いられているが、これらの製造方法では加硫工程でほ
とんど外圧がかからないので、加硫工程の加熱によりゴ
ム材料中に含まれる水分が水蒸気とよりゴム中で膨張し
て加硫ゴム中に気泡が発生する。However, the methods for producing EPDM vulcanized products include high frequency vulcanization (UHF), hot air vulcanization (HAV), and fluidized bed vulcanization (PC
M), liquid bath vulcanization (LCM) and other continuous extrusion vulcanization production methods are often used. However, in these production methods, almost no external pressure is applied in the vulcanization process, so heating in the vulcanization process causes The water contained in the vulcanized rubber expands in the rubber with the water vapor, and bubbles are generated in the vulcanized rubber.
その対策としては、従来、粉末の生石灰をゴム組成物
中に配合することにより、水分を捕捉するという手段が
とられている。しかしながら、粉末の生石灰をゴム組成
物中に配合すると、加硫ゴムの気泡の発生は防止できる
が、圧縮永久歪みが大きくなるという欠点があった。As a countermeasure, conventionally, there has been taken a method of capturing moisture by mixing powdered lime in a rubber composition. However, when powdered quicklime is blended in the rubber composition, generation of air bubbles in the vulcanized rubber can be prevented, but there is a disadvantage that the compression set becomes large.
［発明が解決しようとする課題］ そこで、粉末の生石灰を配合したEPDMゴム組成物の永
久歪みが大きくなる欠点の改善策として炭素原子数10以
上の高級飽和脂肪酸を配合したEPDMゴム組成物（特開昭
56−61439号公報）や本発明者らの発明である炭素原子
数10以上の高級脂肪酸で被覆したゴム組成物配合用生石
灰（特開昭56−67347号公報）の配合や、亜鉛華の増量
配合等が提案されている。しかし、これらの改善策によ
り、ある程度までの改善は図れるが、より以上の改善が
要望されている。[Problems to be Solved by the Invention] Therefore, as a measure for remedying the drawback that the permanent distortion of an EPDM rubber composition containing powdered lime is increased, an EPDM rubber composition containing a higher saturated fatty acid having 10 or more carbon atoms (particularly, Kaisho
No. 56-61439) and the inventor's invention, and the addition of quicklime (Japanese Patent Application Laid-Open No. 56-67347) for compounding a rubber composition coated with a higher fatty acid having 10 or more carbon atoms, and an increase in zinc white. Formulations have been proposed. However, although these improvements can be improved to some extent, further improvements are required.
本発明は上記問題点を解決するためになされたもの
で、その目的は気泡防止のための奪水剤としての粉末の
生石灰を配合したEPDMゴム組成物において、圧縮永久歪
みが改善されたEPDMゴム組成物を提供するものである。The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide an EPDM rubber composition containing powdered quicklime as a water removing agent for preventing air bubbles, and an EPDM rubber having an improved compression set. It provides a composition.
［課題を解決するための手段］ 本発明者は上記の目的を達成するために鋭意検討した
結果、粉末の生石灰を配合したEPDMゴム組成物に特定の
脂肪酸エステルを配合することにより、加硫ゴムの圧縮
永久歪みが改善できることを見出し、本発明を完成し
た。[Means for Solving the Problems] The present inventors have conducted intensive studies to achieve the above object, and as a result, by mixing a specific fatty acid ester with an EPDM rubber composition containing powdered quick lime, a vulcanized rubber was obtained. It has been found that the compression set can be improved, and the present invention has been completed.
すなわち、本発明はEPDM100重量部に対し、粉末の生
石灰１〜20重量部と、ネオペンチルグリコール、トリメ
チロールプロパン及びペンタエリスリトールからなる群
から選択された少なくとも１種のネオペンチルポリオー
ルと炭素数10以上の高級脂肪酸の１種または２種以上と
からなるネオペンチルポリオールの高級脂肪酸エステル
0.2〜５重量部を配合してなる、気泡防止と共に加硫ゴ
ムの圧縮永久歪みが改善されたEPDMゴム組成物に係る。That is, the present invention relates to 100 parts by weight of EPDM, 1 to 20 parts by weight of powdery lime, and at least one neopentyl polyol selected from the group consisting of neopentyl glycol, trimethylolpropane, and pentaerythritol, and 10 or more carbon atoms. Higher fatty acid ester of neopentyl polyol comprising one or more higher fatty acids
The present invention relates to an EPDM rubber composition containing 0.2 to 5 parts by weight and having improved compression set of vulcanized rubber while preventing bubbles.
［作用］ 本発明のEPDMゴム組成物は上記のように粉末の生石灰
とネオペンチルポリオールの高級脂肪酸エステルの特定
量を併せて使用することを特徴とするものであるが、他
に通常のゴム配合剤すなわちカーボンブラック、ホワイ
トカーボン、白色フィラー類、軟化剤、可塑剤、亜鉛
華、スチアリン酸、加硫促進剤、加硫剤、加硫活性剤、
老化防止剤、滑剤、加工助剤、発泡剤、発泡助剤等を適
量混入使用することができる。[Effect] The EPDM rubber composition of the present invention is characterized by using a specific amount of powdered quicklime and a higher fatty acid ester of neopentyl polyol in combination as described above. Agents, namely carbon black, white carbon, white fillers, softener, plasticizer, zinc white, stearic acid, vulcanization accelerator, vulcanizing agent, vulcanizing activator,
Antioxidants, lubricants, processing aids, foaming agents, foaming aids and the like can be used in appropriate amounts.
本発明に使用する粉末の生石灰は石灰石、ドロマイ
ト、炭酸カルシウム、消石灰及びこれらの混合物など
の、焼成することにより酸化カルシウムを生成する物質
を主成分とする物質を分解温度以上で焼成したものを、
必要であれば適当な粉砕助剤を添加して任意の方法によ
り粉末化したものである。この粉末粒子の粒度は微細
で、粗粒子が少ない程好結果が得られ、実用上は150μ
ｍ以下であることが望ましい。Powdered quicklime used in the present invention is limestone, dolomite, calcium carbonate, slaked lime and the like, such as those obtained by calcining a substance mainly containing a substance that generates calcium oxide by calcining at a decomposition temperature or higher,
If necessary, a suitable pulverizing aid is added, and the mixture is pulverized by an arbitrary method. The fineness of the powder particles is fine, and the smaller the coarse particles, the better the results are obtained.
m or less.
この粉末の生石灰の配合量はゴム100重量部当たり１
〜20重量部が適当で、外圧のほとんどかからない連続押
出加硫方式での水分によるゴムの気泡防止には、１重量
部未満の添加量では効果が期待できず、また、20重量部
を超えても、それに応じた効果は期待できない。The amount of quicklime in this powder is 1 per 100 parts by weight of rubber.
2020 parts by weight is appropriate, and in order to prevent rubber bubbles due to moisture in the continuous extrusion vulcanization method that hardly requires external pressure, an effect of less than 1 part by weight cannot be expected, and more than 20 parts by weight However, no effect can be expected.
本発明に使用するネオペンチルポリオールの高級脂肪
酸エステルはネオペンチルポリオールとしてネオペンチ
ルグリコール、トリメチロールプロパン、ペンタエリス
リトールで、高級脂肪酸として炭素数10以上の高級脂肪
酸すなわちカプリン酸、ラウリン酸、ミリスチン酸、パ
リミチン酸、ステアリン酸、オレイン酸、リノール酸等
の単独または混合物の脂肪酸のエステルである。The higher fatty acid ester of neopentyl polyol used in the present invention is neopentyl glycol as neopentyl polyol, trimethylolpropane, or pentaerythritol, and higher fatty acids having 10 or more carbon atoms as higher fatty acids, namely capric acid, lauric acid, myristic acid, and parimitin. Esters of fatty acids, such as acids, stearic acid, oleic acid, linoleic acid, alone or in mixtures.
アルコールとして１価のアルコールや多価アルコール
でもネオペンチルポリオール以外のグリコール、グリセ
リン、ソルビタン等を使用した高級脂肪酸のエステル、
例えばブチルステアレート、ステアリル・ステアレー
ト、エチレングリコール・モノステアレート、グリセリ
ル・モノステアレート、ソルビタン・ステアレート等で
は可塑剤や滑剤としての作用はあるが、目的とする圧縮
永久歪みの改善は図れない。Ester of higher fatty acid using glycol, glycerin, sorbitan or the like other than neopentyl polyol even as monohydric alcohol or polyhydric alcohol as alcohol,
For example, butyl stearate, stearyl stearate, ethylene glycol monostearate, glyceryl monostearate, sorbitan stearate and the like have a function as a plasticizer and a lubricant, but the intended compression set can be improved. Absent.
この理由を考察するに、粉末の生石灰を配合すること
により圧縮永久歪みが悪化する理由が解明されていない
ので定かではないが、加硫工程において生石灰及びそれ
がゴム中で反応して生成する消石灰により加硫促進剤が
安定化されずに分解を促進され、そのために加硫剤のイ
オウやゴム分子が活性化される量が少なくなり、加硫反
応途中にできるゴム分子に結合した促進剤を含む中間体
Rub−Sx−Acc（Rub:ゴム鎖状分子、Sx:x個結合したイオ
ウ原子、Acc:促進剤分子）の生成量が少なく、また、イ
オウの結合においてもｘの多いものとなり、そのため加
硫ゴムの架橋密度が小さく、また、イオウの結合形態も
ポリサルファイド結合になることにより圧縮永久歪みが
悪化するものと推論される。In consideration of this reason, the reason why the compression set is deteriorated by mixing powdered lime is not clear because it has not been clarified, but quick lime and slaked lime generated by its reaction in rubber in the vulcanization process are unknown. As a result, the vulcanization accelerator is not stabilized, and the decomposition is accelerated.Therefore, the amount of the sulfur or rubber molecules of the vulcanization agent to be activated is reduced, and the accelerator bound to the rubber molecules formed during the vulcanization reaction is reduced. Including intermediates
The amount of generated Rub-Sx-Acc (Rub: rubber chain molecule, Sx: x sulfur atoms bonded, Acc: accelerator molecule) is small, and x is also large in the bond of sulfur. It is presumed that the rubber has a low crosslink density and the bonding form of the sulfur is also a polysulfide bond, thereby deteriorating the compression set.
これは後記のように、亜鉛華において活性度の高い活
性亜鉛華や複合活性亜鉛華を増量配合すると、圧縮永久
歪みが改善できるが、その理由として高活性度亜鉛華の
増量配合により加硫促進剤やRub−Sx−Accが安定化で
き、架橋密度が大きく、イオウの結合形態でのｘの数も
小さい加硫ゴムとなり、圧縮永久歪みが改善できるとの
推論とも合致する。This is because, as will be described later, the compression set can be improved by increasing the amount of active zinc white or the compound active zinc white, which is highly active in zinc white, to increase vulcanization. This is consistent with the speculation that the agent and Rub-Sx-Acc can be stabilized, the vulcanized rubber has a high crosslinking density, and the number of x in the form of sulfur bonded is small, and the compression set can be improved.
すなわち、亜鉛華は加硫反応において、ステアリン酸
と反応してステアリン酸Znや安定な促進剤のZn塩となっ
てイオウを活性化したり、ステアリン酸と反応してゴム
に可溶性のZn塩となり、そのZnイオンがゴム分子に結合
した促進剤を含む中間体において、下記（１）のように
キレートを生成してイオウと促進剤（例えばメルカプト
ベンゾチアゾール）の結合をより強固にして加硫ゴムの
イオウの結合形態をポリサルファイド結合を少なくして
ジサルファイド及びモノサルファイド結合を多くした
り、また加硫反応中に生成するH2SとZnSの形で固定化し
て加硫反応を進める役割をするといわれているが、そこ
に生石灰や消石灰が存在すると、促進剤やステアリン酸
と反応してそのCa塩となり、上記のZn塩の生成を阻害し
たり、またCaとイオウとの結合力が弱いために促進剤の
Ca塩が生成しも不安定で、特にテウラム系促進剤では促
進剤の分解が起こり上記のように架橋密度が小さく、ま
たポリサルファイド結合の多い加硫ゴムとなり、圧縮永
久歪みが悪化するものと推定される。そこで生石灰や消
石灰と共存する亜鉛華において亜鉛華の活性度が高いと
上記のZn塩の生成量が多くなり、圧縮永久歪みの悪化が
改善されるものと推定される。In other words, in the vulcanization reaction, zinc white reacts with stearic acid to react with stearic acid to form a Zn salt of a stable accelerator or Zn to activate sulfur, or reacts with stearic acid to form a Zn salt that is soluble in rubber, In an intermediate containing an accelerator in which the Zn ion is bonded to a rubber molecule, a chelate is formed as shown in the following (1) to further strengthen the bond between sulfur and the accelerator (for example, mercaptobenzothiazole) and to form a vulcanized rubber. It said binding form of sulfur or many disulfide or monosulfide bonds with less polysulfide bonds, also to the role of promoting the immobilization to vulcanization reaction in the form of H 2 S and ZnS produced during the vulcanization reaction However, if quicklime or slaked lime is present, it reacts with the accelerator or stearic acid to form its Ca salt, which inhibits the formation of the above-mentioned Zn salt or forms a bond between Ca and sulfur. Of the accelerator
It is presumed that Ca salt is unstable even when it is generated, especially in the case of teuram-based accelerator, the accelerator is decomposed, the crosslink density is low as described above, and it becomes a vulcanized rubber with many polysulfide bonds, and the compression set becomes worse. Is done. Therefore, it is presumed that when the activity of zinc white is high in zinc white which coexists with quicklime and slaked lime, the amount of the above-mentioned Zn salt increases, and the deterioration of compression set is improved.
また、一般にエステルは加熱によって式（３）のよう
に六員環構造の中間体を形成して低エネルギー型（45kc
al/モル）の熱分解を受けると言われている。また一般
的な多価アルコールでは式（２）のグリセリンの例から
もわかるように３個の置換基（CH2OH、CHOH、CH2OH）が
構造上等価ではなく、また、２級炭素原子上に水素原子
をもっている。これに対しネオペンチルポリオールのメ
チロール置換基はいずれも構造上等価であると言われ、
β炭素原子上に水素原子をもたない、いわゆる「ヒンダ
ードアルコール」であるため、式（３）のような六員環
構造を取り得ず、低エネルギー型分解が阻止され、式
（４）のように高温で主としてフリーラジカル的熱分解
（67kcal/モル）の過程をたどる。 In general, an ester forms an intermediate having a six-membered ring structure as shown in formula (3) by heating to form a low energy type (45 kc
al / mol). Further, in general polyhydric alcohols, as can be seen from the example of glycerin of the formula (2), the three substituents (CH 2 OH, CHOH, CH 2 OH) are not structurally equivalent, and the secondary carbon atom Has a hydrogen atom above. On the other hand, the methylol substituent of neopentyl polyol is said to be structurally equivalent,
Since it is a so-called “hindered alcohol” having no hydrogen atom on the β-carbon atom, it cannot have a six-membered ring structure as in formula (3), low energy type decomposition is prevented, and the formula (4) At high temperatures, it follows the process of mainly free radical pyrolysis (67 kcal / mol).
以上のように、ネオペンチルポリオールエステルは加
硫工程での加熱により上記のようなフリーラジカルを生
成し、それが加硫反応で生成するゴムとイオウの結合し
たラジカル（Rub−Sx＊）や促進剤とイオウを結合した
ラジル（Acc−Sy＊）と結合して加硫反応でイオウをよ
り有効に使用するような形の架橋密度の高いイオウの結
合形態でポリサルファイドが少なく、ジサルファイド及
びモノサルファイド結合の多い加硫ゴムが生成し、圧縮
永久歪みが改善できるものと推定される。 As described above, neopentyl polyol ester generates free radicals as described above by heating in the vulcanization step, which generates radicals (Rub-Sx *) in which rubber and sulfur are combined in the vulcanization reaction and promotes free radicals. Low polysulfide, low disulfide and monosulfide in the form of high cross-linking density of sulfur, in which sulfur is more effectively used in the vulcanization reaction by combining with razil (Acc-Sy *) in which the agent is combined with sulfur It is presumed that a vulcanized rubber having a large number of bonds is generated and the compression set can be improved.
なお、炭素数10以下の脂肪酸のネオペンチルポリオー
ルのエステルでは、生石灰及び消石灰と混練中や加工中
に反応するために適当でない。In addition, esters of neopentyl polyol of fatty acids having 10 or less carbon atoms are not suitable because they react with quicklime and slaked lime during kneading and processing.
本発明組成物におけるネオペンチルポリオールの高級
脂肪酸エステルの配合量はゴム100重量部当たり0.2〜５
重量部であり、0.2重量部未満では圧縮永久歪みの改善
には顕著な効果が出ず、また５重量部を超えて配合して
も圧縮永久歪みの改善効果は少なく、その上加硫ゴムの
引張応力の低下やブルームの危険性が大きくなり適当で
ない。The amount of the higher fatty acid ester of neopentyl polyol in the composition of the present invention is 0.2 to 5 per 100 parts by weight of rubber.
If the amount is less than 0.2 part by weight, no significant effect is obtained in improving the compression set, and if the amount is more than 5 parts by weight, the effect of improving the compression set is small. It is not suitable because the risk of tensile stress and bloom increases.
なお、本発明組成物の配合剤としての亜鉛華におい
て、一般に使用されるフランス法やアメリカ法の亜鉛華
をゴム100重量部当たり５重量部配合することに変え
て、活性亜鉛華または複合活性亜鉛華を２〜15重量部配
合することをネオペンチルポリオールの高級脂肪酸エス
テルを配合することと併用すると、前記はしたような理
由により圧縮永久歪みの改善効果はより一層顕著なもの
となる。In addition, in zinc white as a compounding agent of the composition of the present invention, zinc zinc white generally used in the French method or the American method is replaced with 5 parts by weight per 100 parts by weight of rubber, and active zinc white or composite active zinc is used. When the blending of 2 to 15 parts by weight of flower is combined with the blending of a higher fatty acid ester of neopentyl polyol, the effect of improving the compression set becomes more remarkable for the above-described reason.
また、本発明組成物の製造において、ネオペンチルア
ルコールの高級脂肪酸エステルを他の配合剤例えば粉末
生石灰、亜鉛華、活性亜鉛華、複合亜鉛華、充填剤、ス
テアリン酸、加硫促進剤、加硫剤、老化防止剤、滑剤、
可塑剤、軟化剤等と任意の形態で組み合わせたコンパウ
ンドを配合して本発明組成物を製造しても同一の効果の
組成物ができ、この組成物も本発明の範囲内のものであ
ることは勿論である。In the production of the composition of the present invention, the higher fatty acid ester of neopentyl alcohol is mixed with other compounding agents such as powdered lime, zinc white, activated zinc white, composite zinc white, filler, stearic acid, vulcanization accelerator, vulcanization. Agents, anti-aging agents, lubricants,
Even if the composition of the present invention is produced by compounding a compound in any form with a plasticizer, a softener, etc., a composition having the same effect can be obtained, and this composition is also within the scope of the present invention. Of course.
［実 施 例］ 以下に実施例を挙げて本発明組成物を更に説明する。[Example] Hereinafter, the composition of the present invention will be further described with reference to examples.
実施例１〜７ 以下の第１表及び第２表に記載のEPDMポリマー及び配
合剤を第１表及び第２表に記載の割合で配合し、総重量
1.2〜1.4kgになるようにし、BR型1.7バンバリーミキ
サー［（株）神戸製鋼所製］で加硫促進剤、加硫剤を除
くマスターバッチを下記条件で作成した。時間 ポリマー、配合剤 ０分 EPDMポリマー投入 0.5分 亜鉛華（第２表）、ステアリン酸 ネオペンチルポリオールの高級脂肪酸 エステル（第２表） ５分 粉末の生石灰（VESTA PP）投入 得られた組成物を冷却後、８インチロールで加硫促進
剤及びイオウを混練し、シート出ししてEPDMゴム組成物
を作成した。その組成物を冷却後、電熱プレスで加硫し
た加硫ゴムのゴム物性を測定した。Examples 1 to 7 The EPDM polymers and compounding agents described in Tables 1 and 2 below were blended in the proportions shown in Tables 1 and 2 to obtain a total weight.
A master batch excluding the vulcanization accelerator and the vulcanizing agent was prepared using a BR type 1.7 Banbury mixer [manufactured by Kobe Steel Ltd.] under the following conditions. Time Polymer, compounding agent 0 minutes EPDM polymer input 0.5 minutes Zinc flower (Table 2), higher fatty acid ester of neopentyl stearate (Table 2) 5 minutes Powder quicklime (VESTA PP) input The obtained composition After cooling, the vulcanization accelerator and sulfur were kneaded with an 8-inch roll and sheeted to prepare an EPDM rubber composition. After cooling the composition, the rubber physical properties of the vulcanized rubber vulcanized by an electric heat press were measured.
以上の加硫ゴム物性での圧縮永久歪みの結果より、比
較例１及び２においては粉末の生石灰を配合することに
より圧縮永久歪みは悪化するが、比較例２にネオペンチ
ルポリオールの高級脂肪酸エステルを配合した実施例１
〜４では圧縮永久歪みが改善できた。 From the results of the compression set of the above vulcanized rubber properties, in Comparative Examples 1 and 2, the compression set was deteriorated by adding powdered quicklime, but the higher fatty acid ester of neopentyl polyol was used in Comparative Example 2. Example 1 blended
In No. 4 to 4, the compression set was improved.
また、比較例１、比較例３に使用する亜鉛華１号に変
えて活性亜鉛華を配合することにより圧縮永久歪みが改
善できることがわかるが、比較例３にペンタエリスリト
ールステアレートを配合した実施例５では大幅に圧縮永
久歪みを改善することができた。In addition, it can be seen that the compression set can be improved by adding active zinc white instead of zinc white No. 1 used in comparative examples 1 and 3, but it was found that in comparative example 3 pentaerythritol stearate was added. In No. 5, the compression set was significantly improved.
また、実施例５、実施例６、実施例７の本発明のEPDM
ゴム組成物においても、使用する亜鉛華を一般的な亜鉛
華１号から活性亜鉛華や複合亜鉛華に変えて増量使用す
ることにより圧縮永久歪みは更に改善できた。In addition, the EPDM of the present invention in the fifth, sixth and seventh embodiments
Also in the rubber composition, the compression set was further improved by changing the zinc white used from general zinc white No. 1 to activated zinc white or composite zinc white and using it in an increased amount.
［発明の効果］ 本発明のEPDMゴム組成物により、加硫ゴムの気泡防止
のために配合する粉末の生石灰を配合したEPDMゴム組成
物において、加硫ゴムの圧縮永久歪みが悪化する欠点を
大幅に改善することができる。[Effect of the Invention] The EPDM rubber composition of the present invention greatly reduces the disadvantage that the compression set of the vulcanized rubber is deteriorated in the EPDM rubber composition in which the powdered lime compounded to prevent bubbles in the vulcanized rubber is mixed. Can be improved.
Claims (1)
0重量部と、ネオペンチルグリコール、トリメチロール
プロパン及びペンタエリスリトールからなる群から選択
された少なくとも１種のネオペンチルポリオールと炭素
数10以上の高級脂肪酸の１種または２種以上とからなる
ネオペンチルポリオールの高級脂肪酸エステル0.2〜５
重量部を配合してなることを特徴とするEPDMゴム組成
物。(1) 100 parts by weight of EPDM and 1-2 parts of powdered lime.
Neopentyl polyol comprising 0 parts by weight, at least one type of neopentyl polyol selected from the group consisting of neopentyl glycol, trimethylolpropane and pentaerythritol, and one or more types of higher fatty acids having 10 or more carbon atoms Higher fatty acid esters of 0.2-5
EPDM rubber composition characterized by blending parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26211589A JP2774615B2 (en) | 1989-10-09 | 1989-10-09 | EPDM rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26211589A JP2774615B2 (en) | 1989-10-09 | 1989-10-09 | EPDM rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03124749A JPH03124749A (en) | 1991-05-28 |
| JP2774615B2 true JP2774615B2 (en) | 1998-07-09 |
Family
ID=17371254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26211589A Expired - Fee Related JP2774615B2 (en) | 1989-10-09 | 1989-10-09 | EPDM rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2774615B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337375A (en) * | 2018-10-24 | 2019-02-15 | 合盛硅业股份有限公司 | Low compression set silicone rubber material and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7411400B2 (en) * | 2019-12-13 | 2024-01-11 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for anti-vibration rubber and anti-vibration rubber |
| JP7635470B2 (en) * | 2022-09-22 | 2025-02-25 | Nok株式会社 | EPDM composition |
-
1989
- 1989-10-09 JP JP26211589A patent/JP2774615B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337375A (en) * | 2018-10-24 | 2019-02-15 | 合盛硅业股份有限公司 | Low compression set silicone rubber material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03124749A (en) | 1991-05-28 |
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