JPH02225546A - Oil-resistant and heat-resistant blended rubber composition - Google Patents
Oil-resistant and heat-resistant blended rubber compositionInfo
- Publication number
- JPH02225546A JPH02225546A JP4750089A JP4750089A JPH02225546A JP H02225546 A JPH02225546 A JP H02225546A JP 4750089 A JP4750089 A JP 4750089A JP 4750089 A JP4750089 A JP 4750089A JP H02225546 A JPH02225546 A JP H02225546A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- propylene
- ethylene
- resistant
- oil
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 229920001897 terpolymer Polymers 0.000 claims abstract description 23
- 150000001993 dienes Chemical class 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 abstract description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VGYFVNQYBUPXCQ-UHFFFAOYSA-N ethene;2-methyloxirane Chemical group C=C.CC1CO1 VGYFVNQYBUPXCQ-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- -1 thiuram sulfides Chemical class 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-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
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-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
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- ALFBVRJANQBXBC-UHFFFAOYSA-N n-phenyl-n-(trichloromethyl)benzenesulfonothioamide Chemical compound C=1C=CC=CC=1S(=O)(=S)N(C(Cl)(Cl)Cl)C1=CC=CC=C1 ALFBVRJANQBXBC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical compound [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- NEYNBSGIXOOZGZ-UHFFFAOYSA-L zinc;butoxymethanedithioate Chemical compound [Zn+2].CCCCOC([S-])=S.CCCCOC([S-])=S NEYNBSGIXOOZGZ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐油性及び耐熱性をバランスよく兼ね億えたブ
レンドゴム組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a blend rubber composition that has oil resistance and heat resistance in a well-balanced manner.
（従来の技術と発明が解決しようとする課題）プロピレ
ンオキシド−エチレンオキシド−アリルグリシジルエー
テル三元共重合体ゴムは耐候性。(Prior art and problems to be solved by the invention) Propylene oxide-ethylene oxide-allyl glycidyl ether terpolymer rubber is weather resistant.
耐熱老化性、耐寒性、耐油性１反発弾性等にバランスの
とれた性能を有するゴムであるが、その熱老化傾向が軟
化型劣化である欠点を有している。Although this rubber has well-balanced performance in terms of heat aging resistance, cold resistance, oil resistance, impact resilience, etc., it has the disadvantage that its heat aging tendency is a softening type deterioration.
他方エチレン−プロピレン−非共役ジエン三元共重合体
ゴムは耐候性、耐オゾン性、耐熱性等に優れたゴムであ
ることが知られているが、耐油性に欠点があった。この
耐油性を補うものとしてプロピレンオキシド−アリルグ
リシジルエーテル二元共重合体ゴムとのブレンドが従来
公知である（特公昭４６−２７５７４＠公報参照。）が
、このブレンド物の耐油性は充分満足できるものではな
かった。On the other hand, ethylene-propylene-nonconjugated diene terpolymer rubber is known to be a rubber with excellent weather resistance, ozone resistance, heat resistance, etc., but has a drawback in oil resistance. As a supplement to this oil resistance, a blend with propylene oxide-allyl glycidyl ether binary copolymer rubber has been known (see Japanese Patent Publication No. 46-27574@), but the oil resistance of this blend is sufficiently satisfactory. It wasn't something.
（ｖＲ題を解決するための手段及び作用）本発明者らは
上記の点に鑑み、耐油性及び耐熱性をバランスよく兼ね
備えたゴム組成物を）ｑる目的で鋭意検討した。その結
果プロピレンオキシド−エチレンオキシド−アリルグリ
シジルエーテル三元共重合体ゴムとエチレン−プロピレ
ン−非共役ジエン三元共重合体ゴムを特定比率でブレン
ドして加硫したものが優れた機械的強度を示すと共に耐
油性及び耐熱性をバランスよく兼ね備えていることを見
出し本発明を完成させるに至ったものである。(Means and effects for solving the vR problem) In view of the above points, the present inventors have conducted extensive studies with the aim of developing a rubber composition that has both oil resistance and heat resistance in a well-balanced manner. As a result, a blend of propylene oxide-ethylene oxide-allyl glycidyl ether terpolymer rubber and ethylene-propylene-nonconjugated diene terpolymer rubber in a specific ratio and vulcanization exhibited excellent mechanical strength. The present invention was completed after discovering that it has a well-balanced combination of oil resistance and heat resistance.
本発明は ａ）プロピレンオキシド、エチレンオキシド
及びアリルグリシジルエーテルを構成成分とし、その構
成割合が夫々４０〜８９モル％、 ５０〜１０モル％及
び１０〜１モル％であるポリエーテル系三元共重合体ゴ
ム９５〜５重量％ ｂ）エチレン−プロピレン−非共役
ジエン三元共重合体ゴム５〜９５重量％ 上記ａ）、ｂ
）よりなるゴム成分及び加硫剤を含むことを特徴とする
耐油耐熱性ブレンドゴム組成物を提供するものである。The present invention is directed to a) a polyether terpolymer comprising propylene oxide, ethylene oxide and allyl glycidyl ether as constituent components, the constituent proportions of which are 40 to 89 mol%, 50 to 10 mol% and 10 to 1 mol%, respectively. Rubber 95-5% by weight b) Ethylene-propylene-nonconjugated diene terpolymer rubber 5-95% by weight Above a), b)
) and a vulcanizing agent.
本発明に用いるポリエーテル系三元共重合体ゴムはプロ
ピレンオキシド４０〜８９モル％、エチレンオキシド５
０〜１０モル％及びアリルグリシジルエーテル１０〜１
モル％からなるものである。プロピレンオキシドが４０
モル％未満即ちエチレンオキシドが５０モル％を超える
と耐水性が低下する等の問題が生じ、一方プロピレンオ
キシドが８９モル％超即ちエチレンオキシドが１０モル
％未満では耐油性が低下する。本発明で用いるポリエー
テル系三元共重合体ゴムの重合度はムーニー粘度表示で
ＭＬ１＋４ （１００℃）２０〜１００程度のものが好
ましい。The polyether terpolymer rubber used in the present invention contains 40 to 89 mol% of propylene oxide and 5% of ethylene oxide.
0-10 mol% and allyl glycidyl ether 10-1
It consists of mol%. Propylene oxide is 40
If the amount of propylene oxide is less than 89 mol %, that is, if the ethylene oxide content is less than 10 mol %, problems such as decreased water resistance will occur, whereas if the ethylene oxide content is less than 10 mol %, oil resistance will be decreased. The degree of polymerization of the polyether terpolymer rubber used in the present invention is preferably about ML1+4 (100 DEG C.) 20 to 100 in Mooney viscosity.
本発明に用いるエチレン−プロピレン−非共役ジエン三
元共重合体ゴムは本発明の技術分野でよく知られた触媒
、特にデーグラ−・ナツタ系触媒を用いて公知の方法に
よってエチレン、プロピレン及び非共役ジエンを三元共
重合して製逃されるもので、エチレン４０〜８４モル％
、プロピレン５０〜１５モル％及び非共役ジエン１０〜
１モル％からなるものである。非共役ジエンとしては、
１，４−へキサジエン、ジシクロペンタジェン、メチレ
ンノルボルネン、エチリデンノルボルネン、メチルテト
ラヒドロインデン等を挙げることができる。本発明で用
いるエチレン−プロピレン−非共役ジエン三元共重合体
の重合度はムーニー粘度表示でＭＬ１＋ａ （１００℃
＞２０〜１００程度のものが好ましい。The ethylene-propylene-nonconjugated diene terpolymer rubber used in the present invention is produced by a method known in the art using a catalyst well known in the technical field of the present invention, particularly a Daegler-Natsuta catalyst. It is produced by ternary copolymerization of diene, and contains 40 to 84 mol% of ethylene.
, 50-15 mol% of propylene and 10-15 mol% of non-conjugated diene
It consists of 1 mol%. As a non-conjugated diene,
Examples include 1,4-hexadiene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, and methyltetrahydroindene. The degree of polymerization of the ethylene-propylene-nonconjugated diene terpolymer used in the present invention is ML1+a (100°C
>20 to about 100 is preferred.
本発明の耐油耐熱性ブレンドゴム組成物のゴム成分は前
記ポリエーテル系三元共重合体ゴムとエチレン−プロピ
レン−非共役ジエン三元共重合体ゴムとを夫々９５〜５
重量％及び５〜９５重量％の割合で混合したものであり
、耐油性の観点からは、夫々９５〜２０重量％及び５〜
８０重ω％の割合で混合するのが好ましい。特に耐油性
を要求される場合はポリエーテル系三元共重合体ゴムの
方を多く、また特に耐熱性を要求される場合はエチレン
−プロピレン−非共役ジエン三元共重合体ゴムの方を本
発明の構成割合の範囲内でより多く用いるのが好ましい
。The rubber components of the oil- and heat-resistant blend rubber composition of the present invention include the polyether terpolymer rubber and the ethylene-propylene-nonconjugated diene terpolymer rubber, each containing 95 to 95% of the rubber component.
% by weight and 5 to 95% by weight, and from the viewpoint of oil resistance, 95 to 20% by weight and 5 to 95% by weight, respectively.
It is preferable to mix at a ratio of 80 wt ω%. In particular, when oil resistance is required, polyether terpolymer rubber is preferred, and when heat resistance is required, ethylene-propylene-nonconjugated diene terpolymer rubber is preferred. It is preferable to use a larger amount within the range of the composition ratio of the invention.
従来耐油性ゴムと非耐油性ゴムとは相溶性に乏しいこと
、加硫用薬剤の溶解性に差があるためブレンド状態で両
者を共に充分加硫せしめるのは困難であることが知られ
ていた。本発明者らはエチレンオキシドによって耐油性
を強化した上記ポリエーテル系三元共重合体ゴムと非耐
油性のエチレン−プロピレン−非共役ジエン系ゴムとが
、常識に反して、極めて良好なブレンド加硫物性を与え
ることを見出し、本発明の完成に達したのである。It was previously known that oil-resistant rubber and non-oil-resistant rubber had poor compatibility and that it was difficult to sufficiently vulcanize both in a blended state due to differences in the solubility of vulcanizing chemicals. . The present inventors have discovered that, contrary to common sense, the polyether terpolymer rubber whose oil resistance has been reinforced with ethylene oxide and the non-oil resistant ethylene-propylene-nonconjugated diene rubber exhibit extremely good blend vulcanization. It was discovered that this material imparts physical properties, and the present invention was completed.
本発明に用いる加硫用薬剤としては、公知の不飽和ゴム
用加硫用薬剤を用いることができる。このような薬剤の
例を挙げると、加硫剤としては硫黄、硫黄供与性化合物
、所謂樹脂加硫剤、所謂オキシム加硫剤等が挙げられ、
これらと組合わぜて使用される加硫促進剤としては、硫
黄化合物系促進剤、アミン系促進剤等が挙げられ、他に
加硫遅延剤、更には加硫促進助剤となる金属化合物等を
挙げることができる。これらの薬剤を具体的に例示する
と、硫黄供与性化合物としてモルホリンジスルフィド等
のモルホリンポリスルフィド類或いはテトラメチルチウ
ラムジスルフィド、ジベンタメチレンヂウラムテトラス
ルフィド等のチウラムスルフィド類等、所謂樹脂加硫剤
としてアルキルフェノールホルムアルデヒド樹脂等、所
謂オキシム加硫剤としてｐ−キノンジオキシム、Ｄ、ｐ
−ジベンゾイルキノンジオキシム等、硫黄化合物系促進
剤としてテトラメチルチウラムジスルフィド等のチウラ
ムモノスルフィド系促進剤、２−メルカプトベンゾチア
ゾール、ジベンゾチアジルジスルフィド、２−メルカプ
トベンゾチアゾールの亜鉛塩等のベンゾチアゾール系促
進剤、Ｎ−シクロへキシル−２−ベンゾチアジルスルフ
ェンアミド。As the vulcanizing agent used in the present invention, known vulcanizing agents for unsaturated rubber can be used. Examples of such agents include sulfur, sulfur-donating compounds, so-called resin vulcanizing agents, so-called oxime vulcanizing agents, etc.
Examples of vulcanization accelerators used in combination with these include sulfur compound accelerators, amine accelerators, etc., as well as vulcanization retarders, and metal compounds that serve as vulcanization accelerating aids. can be mentioned. Specific examples of these agents include morpholine polysulfides such as morpholine disulfide as sulfur-donating compounds, thiuram sulfides such as tetramethylthiuram disulfide and dibentamethylene diuram tetrasulfide, and alkylphenol formaldehyde as a so-called resin vulcanizing agent. p-quinone dioxime, D, p as a so-called oxime vulcanizing agent for resins, etc.
- Dibenzoylquinone dioxime, etc., sulfur compound accelerators such as thiuram monosulfide accelerators such as tetramethylthiuram disulfide, benzothiazole such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, zinc salt of 2-mercaptobenzothiazole, etc. System promoter, N-cyclohexyl-2-benzothiazylsulfenamide.
Ｎ−オキシジエチレン−２−ベンゾチアジルスルフェン
アミド等のスルフェンアミド系促進剤、ジメチルジチオ
カルバミン酸ナトリウム、ジブチルジチオカルバミン酸
亜鉛等のジチオカーバメート系促進剤、イソプロピルキ
サントゲン酸ナトリウム、ブチルキサントゲン酸亜鉛等
のザンテート系促進剤等が挙げられ、アミン系促進剤と
してジフェニルグアニジン、オルソ−トリルビグアニド
等のグアニジン系促進剤、ヘキサメチレンテトラミン等
のアルデヒドアンモニア系促進剤、ｎ−ブチルアルデヒ
ド・アニリン縮合物等のアルデヒドアミン系促進剤等が
挙げられる。加硫遅延剤としては、サリチル酸、無水フ
タルｌ、Ｎ−シクロヘキシルチオフタルイミド、Ｎ−フ
ェニル−Ｎ−トリクロロメチルチオベンゼンスルホンア
ミド等が挙げられ、加硫促進助剤となる金属化合物とし
ては、酸化亜鉛、酸化マグネシウム、リサージ、鉛丹。Sulfenamide accelerators such as N-oxydiethylene-2-benzothiazylsulfenamide, dithiocarbamate accelerators such as sodium dimethyldithiocarbamate, zinc dibutyldithiocarbamate, sodium isopropylxanthate, zinc butylxanthate, etc. Examples include xanthate-based accelerators, and amine-based accelerators include guanidine-based accelerators such as diphenylguanidine and ortho-tolyl biguanide, aldehyde ammonia-based accelerators such as hexamethylenetetramine, and aldehydes such as n-butyraldehyde/aniline condensates. Examples include amine accelerators. Examples of vulcanization retarders include salicylic acid, phthalic anhydride, N-cyclohexylthiophthalimide, N-phenyl-N-trichloromethylthiobenzenesulfonamide, and examples of metal compounds that serve as vulcanization accelerators include zinc oxide, Magnesium oxide, resurge, red lead.
過酸化鉛、酸化カドミウム、酸化カルシウム、水酸化カ
ルシウム、塩化第一錫、ステアリン酸亜鉛等を挙げるこ
とができる。Examples include lead peroxide, cadmium oxide, calcium oxide, calcium hydroxide, stannous chloride, and zinc stearate.
これら加硫用薬剤の添加団はゴム成分の組成。The additive group of these vulcanizing agents is the composition of the rubber component.
薬剤の種類、ゴムの使用目的等によって定められるが通
常ゴム成分１００重量部に対して夫々０．０５〜４０重
四部程度、好ましくは０．１〜２０重量部程置部ある。Although it is determined depending on the type of drug, the purpose of use of the rubber, etc., the amount is usually about 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the rubber component.
本ゴム組成物には、更に、加工上必要な、或いは実用上
の諸物性の調整に必要な各種の補強剤。The present rubber composition further contains various reinforcing agents necessary for processing or for adjusting various physical properties in practical use.
充填剤、可塑剤、加工助剤、安定剤、老化防止剤。Fillers, plasticizers, processing aids, stabilizers, anti-aging agents.
紫外線吸収剤、顔料、１１燃剤等を任意に配合すること
ができる。Ultraviolet absorbers, pigments, 11 fuel agents, etc. can be optionally blended.
本発明のブレンドゴム組成物の混合方法は特に制限され
ず、例えば２本ロール、バンバリーミキサ−、ニーダ−
等を用い、ブレンド法、マスターバッチ法等によること
ができる。混合温度は通常４０〜１５０℃である。The method of mixing the blended rubber composition of the present invention is not particularly limited, and examples include a two-roll mixer, a Banbury mixer, a kneader, etc.
A blending method, a masterbatch method, etc. can be used. The mixing temperature is usually 40 to 150°C.
本発明の組成物は通常１００〜２５０℃に加熱されるこ
とによって加硫物とすることができる。加熱時間は加熱
温度によって異なるが、通常１〜３００分間が適当であ
る。The composition of the present invention can be made into a vulcanizate by heating to usually 100 to 250°C. Although the heating time varies depending on the heating temperature, 1 to 300 minutes is usually appropriate.
また加硫成型の方法としては、金型による加圧成型、射
出成型、スチーム罐、エアーバス、或いは赤外線、マイ
クロウェーブ等による加熱等任意の方法が利用できる。Further, as a method for vulcanization molding, any method such as pressure molding using a mold, injection molding, steam can, air bath, or heating using infrared rays, microwaves, etc. can be used.
以下本発明を実施例によって具体的に説明する。The present invention will be explained in detail below using examples.
実施例１＝５． 比較例１〜４
第１表に示す各配合物を６０〜７０℃のオープンロール
で充分混練し、シート化したものを金型に入れ、１７０
℃、 ８０ｋ（７／ｃｍで１５分間加圧成型した。）ｑ
られた各加硫物の物性試験（ＪＩＳＫ６３０１ に拠る
）の結果を第２表に示した。Example 1=5. Comparative Examples 1 to 4 Each compound shown in Table 1 was thoroughly kneaded with an open roll at 60 to 70°C, and the sheet was put into a mold and heated to 170°C.
°C, 80k (pressure molded at 7/cm for 15 minutes)q
Table 2 shows the results of physical property tests (according to JIS K6301) for each vulcanizate.
第２表を見ると、本発明ブレンドゴム組成物が優れた機
械的強度を示すと共に、耐熱老化性、耐油性、耐水性等
にバランスのとれた諸物性を示しており（比較例３にお
いてエチレンオキシドを含まぬ場合耐油性に劣り、比較
例４においてエチレンオキシドを過剰に含む場合耐水性
に劣る。）、両ゴム夫々単独（実施例゛１〜５対比較例
１〜２）或いは従来公知のプロピレンオキシド−アリル
グリシジルエーテル二元共重合体ゴムとエチレンプロピ
レン−非共役ジエン三元共重合体ゴムとのブレンドゴム
組成物（実施例４対比較例３）に比べてもはるかに優れ
ていることが分る。Looking at Table 2, the blended rubber composition of the present invention exhibits excellent mechanical strength as well as well-balanced physical properties such as heat aging resistance, oil resistance, and water resistance (in Comparative Example 3, ethylene oxide (Examples 1 to 5 vs. Comparative Examples 1 to 2) or conventionally known propylene oxide. It was found to be far superior to the blended rubber composition of -allyl glycidyl ether binary copolymer rubber and ethylene propylene-nonconjugated diene terpolymer rubber (Example 4 vs. Comparative Example 3). Ru.
（発明の効果）
本発明のブレンドゴム組成物はプロピレンオキシド−エ
チレンオキシド−アリルグリシジルエーテル三元共重合
体ゴムとエチレン−プロピレン−非共役ジエン三元共重
合体ゴムをブレンドしたゴム成分と加硫剤を含んでなる
ものであって、耐熱性、耐油性、耐寒性、耐水性等の優
れた物性をバランスよく併せ備えたものであり、各種産
業分野で広く使用することができる。(Effects of the Invention) The blended rubber composition of the present invention comprises a rubber component that is a blend of propylene oxide-ethylene oxide-allyl glycidyl ether terpolymer rubber and ethylene-propylene-nonconjugated diene terpolymer rubber, and a vulcanizing agent. It has a well-balanced combination of excellent physical properties such as heat resistance, oil resistance, cold resistance, and water resistance, and can be widely used in various industrial fields.
Claims (1)
グリシジルエーテルを構成成分とし、その構成割合が夫
々４０〜８９モル％、５０〜１０モル％及び１０〜１モ
ル％であるポリエーテル系三元共重合体ゴム９５〜５重
量％ ｂ）エチレン−プロピレン−非共役ジエン三元共重合体
ゴム５〜９５重量％ 上記ａ）、ｂ）よりなるゴム成分及び加硫剤を含むこと
を特徴とする耐油耐熱性ブレンドゴム組成物。[Scope of Claims] a) A polyether ternary comprising propylene oxide, ethylene oxide and allyl glycidyl ether as constituent components, the constituent proportions of which are 40 to 89 mol%, 50 to 10 mol% and 10 to 1 mol%, respectively. 95 to 5% by weight of copolymer rubber b) 5 to 95% by weight of ethylene-propylene-nonconjugated diene terpolymer rubber A rubber component consisting of a) and b) above and a vulcanizing agent are included. Oil and heat resistant blend rubber composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1047500A JPH0643536B2 (en) | 1989-02-27 | 1989-02-27 | Oil and heat resistant blended rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1047500A JPH0643536B2 (en) | 1989-02-27 | 1989-02-27 | Oil and heat resistant blended rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02225546A true JPH02225546A (en) | 1990-09-07 |
| JPH0643536B2 JPH0643536B2 (en) | 1994-06-08 |
Family
ID=12776831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1047500A Expired - Fee Related JPH0643536B2 (en) | 1989-02-27 | 1989-02-27 | Oil and heat resistant blended rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643536B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270158A (en) * | 1996-04-17 | 2007-10-18 | Nippon Zeon Co Ltd | Ethylene oxide/propylene oxide/unsaturated epoxide terpolymer |
| JP4564367B2 (en) * | 2005-01-31 | 2010-10-20 | 大日本印刷株式会社 | How to use a combination of double-sided concealment label and postcard |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01131915A (en) * | 1986-07-02 | 1989-05-24 | Acushnet Co | Keyboard, elestic pad for keyboard and manufacture thereof |
-
1989
- 1989-02-27 JP JP1047500A patent/JPH0643536B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01131915A (en) * | 1986-07-02 | 1989-05-24 | Acushnet Co | Keyboard, elestic pad for keyboard and manufacture thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270158A (en) * | 1996-04-17 | 2007-10-18 | Nippon Zeon Co Ltd | Ethylene oxide/propylene oxide/unsaturated epoxide terpolymer |
| JP4564367B2 (en) * | 2005-01-31 | 2010-10-20 | 大日本印刷株式会社 | How to use a combination of double-sided concealment label and postcard |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0643536B2 (en) | 1994-06-08 |
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