WO2003057775A1 - Vulcanizable rubber composition and vulcanizate - Google Patents
Vulcanizable rubber composition and vulcanizate Download PDFInfo
- Publication number
- WO2003057775A1 WO2003057775A1 PCT/JP2002/013764 JP0213764W WO03057775A1 WO 2003057775 A1 WO2003057775 A1 WO 2003057775A1 JP 0213764 W JP0213764 W JP 0213764W WO 03057775 A1 WO03057775 A1 WO 03057775A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- parts
- copolymer rubber
- rubber
- nitrile group
- Prior art date
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 144
- 239000005060 rubber Substances 0.000 title claims abstract description 144
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 229920001577 copolymer Polymers 0.000 claims abstract description 83
- 239000000178 monomer Substances 0.000 claims abstract description 40
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 31
- 239000011630 iodine Substances 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 28
- 150000002825 nitriles Chemical class 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002560 nitrile group Chemical group 0.000 claims description 64
- 150000001993 dienes Chemical class 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 14
- 238000007906 compression Methods 0.000 abstract description 14
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 30
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000009661 fatigue test Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 1
- FPFVPEGEWVRCGK-UHFFFAOYSA-N 1-ethenoxy-2-fluoroethane Chemical compound FCCOC=C FPFVPEGEWVRCGK-UHFFFAOYSA-N 0.000 description 1
- CFMTUIKADIKXIQ-UHFFFAOYSA-N 1-ethenoxy-3-fluoropropane Chemical compound FCCCOC=C CFMTUIKADIKXIQ-UHFFFAOYSA-N 0.000 description 1
- VGWWQZSCLBZOGK-UHFFFAOYSA-N 1-ethenyl-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C=C VGWWQZSCLBZOGK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QSAMQSXFHVHODR-UHFFFAOYSA-N Cl.C=CC#N Chemical compound Cl.C=CC#N QSAMQSXFHVHODR-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- TZBJGXHYKVUXJN-UHFFFAOYSA-N genistein Natural products C1=CC(O)=CC=C1C1=COC2=CC(O)=CC(O)=C2C1=O TZBJGXHYKVUXJN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 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
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
Definitions
- the present invention relates to a vulcanizate of a nitrile group-containing copolymer rubber excellent in dynamic characteristics and heat resistance and having a small compression set, and a vulcanizable rubber composition as a material thereof.
- nitrile group-containing copolymer rubber such as acrylonitrile-butadiene copolymer rubber has excellent oil resistance.
- hydrogenated acrylonitrile-butadiene copolymer rubber obtained by hydrogenating acrylonitrile-butadiene copolymer rubber for the purpose of improving heat resistance, chemical resistance, weather resistance, tensile strength and the like is known.
- the hydrogenated acrylonitrile-butadiene copolymer rubber has a problem that the compression set is larger than that of the acrylonitrile-butadiene copolymer rubber before hydrogenation.
- An object of the present invention is to provide a nitrile group-containing copolymer rubber vulcanized with sulfur, which has excellent dynamic characteristics and heat resistance, and has a small compression elongation, in view of the above prior art, and a material thereof. It is to provide a vulcanizable rubber composition.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, when two types of nitrile group-containing copolymer rubbers having an iodine value in a specific range are used in combination, even if a small amount of sulfur is used, a strong copolymer is formed between the two.
- the present inventors have found that vulcanization occurs, and have completed the present invention based on this finding.
- A 5 to 50 parts by weight and a nitrile group-containing copolymer rubber having an ⁇ ,) 3-ethylenically unsaturated nitrile monomer unit content of 10 to 60% by weight and an iodine value of 40 to 100
- Ii 100 to 100 parts by weight of a rubber component consisting of 50 to 95 parts by weight, and at least one vulcanizing agent selected from sulfur and 4,4'-dithiodimorpholine in terms of sulfur content of 0.1.
- a vulcanizable rubber composition containing up to 1.5 parts by weight.
- the vulcanizable rubber composition containing the nitrile group-containing copolymer rubber ( ⁇ ), the nitrile group-containing copolymer rubber ( ⁇ ) and a sulfur-based vulcanizing agent is vulcanized.
- a vulcanizate is provided.
- the vulcanizable rubber composition of the present invention comprises a rubber component 1 comprising 5 to 50% by weight of a nitrile group-containing copolymer rubber ( ⁇ ) and 50 to 95% by weight of a nitrile group-containing copolymer rubber ( ⁇ ). It contains 0.1 parts by weight and 0.1 to 1.5 parts by weight of sulfur in terms of sulfur and at least one selected from 4,4'-dithiodimorpholine as a vulcanizing agent.
- Examples of the ⁇ , / 3-ethylenically unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, and acrylonitrile monochloride, with acrylonitrile being preferred.
- the content of the ⁇ ,) 3-ethylenically unsaturated nitrile monomer unit in the nitrile group-containing copolymer rubber ( ⁇ ) is 10 to 60% by weight, preferably 12 to 55% by weight, Preferably it is 15 to 50% by weight. If the content of ⁇ , / 3_ethylenically unsaturated nitrile monomer is too low, the oil resistance of the vulcanizate is poor, and if it is too high, the cold resistance is poor.
- the monomers to be copolymerized with the ⁇ , J3-ethylenically unsaturated nitrile monomer include a conjugated diene monomer, a non-conjugated diene monomer and For example, freerefin is exemplified. These monomers can be copolymerized alone or in combination of two or more. Of these monomers, conjugated diene monomers are preferred. Examples of the conjugated diene monomer include 1,3-butane gen, isoprene, 2,3-dimethyl-1,3-butadiene and 1,3-pentene gen.
- the non-conjugated diene monomer preferably has 5 to 12 carbon atoms, and examples thereof include 1,4-pentene, 1,4-hexadiene, vinylnorbornene, and dicyclopentene.
- the ⁇ -olefin those having 2 to 12 carbon atoms are preferable, and examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 11-hexene, and 1-octene.
- the amount of the unit of the monomer copolymerized with the , / 3-ethylenically unsaturated nitrile monomer is 40 to 90% by weight, It is preferably from 45 to 88% by weight, more preferably from 50 to 85% by weight.
- an aromatic vinyl monomer a fluorine-containing vinyl monomer, [3] -ethylenically unsaturated monocarboxylic acid, [3], i3-ethylenically unsaturated polycarboxylic acid
- an anhydride thereof, a copolymerizable antioxidant, or the like may be copolymerized.
- Examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, vinyl pyridine and the like.
- Examples of fluorine-containing vinyl monomers include, for example, full Examples include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, penfluorovinyl benzoate, difluoroethylene, tetrafluoroethylene and the like.
- Examples of the a, i3-ethylenically unsaturated monocarboxylic acid include acrylic acid and methyl methacrylate.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acid include itaconic acid, fumaric acid, and maleic acid.
- Examples of the / 3-ethylenically unsaturated polycarboxylic anhydride include itaconic anhydride and maleic anhydride.
- Examples of copolymerizable antioxidants include ⁇ — (4-anilinophenyl) acrylamide, ⁇ - (4-anilinophenyl) methacrylamide, ⁇ — (4-anilinophenyl) cinnamamide, ⁇ — (4-anilinophenyl) crotonamide , ⁇ -phenyl-4- (3-vinylbenzyloxy) aniline, ⁇ -phenyl-4_ (4-vinylpentyloxy) aniline and the like.
- the iodine value of the nitrile group-containing copolymer rubber ( ⁇ ) is from 180 to 430, preferably from 200 to 400, more preferably from 230 to 380. If the iodine value is too small, the vulcanizate will have poor rubber elasticity. Conversely, if the iodine value is too large, the vulcanizate will have poor oil resistance and heat resistance, and it will be difficult to covulcanize with the nitrile group-containing copolymer rubber (II).
- the iodine value is a value indicating the amount of unsaturated bonds in the main chain, and is determined mainly by the content of conjugated gen monomer units. If necessary, the iodine value may be adjusted by hydrogenating the nitrile group-containing copolymer rubber (II) to saturate unsaturated bonds by a known method.
- the nitrile group-containing copolymer rubber ( ⁇ ) preferably has a viscosity (ML 1 + 4 , 100) of 20 to 300, more preferably 30 to 250, and particularly preferably 30 to 250. 40 to 200. If the Mooney viscosity is too low, the mechanical properties of the vulcanizate may be poor, and if too high, the workability may be poor.
- ML 1 + 4 , 100 a viscosity
- the nitrile group-containing copolymer rubber (B) which accounts for 50 to 95 parts by weight in 100 parts by weight of the rubber component contained in the vulcanizable rubber composition of the present invention, is a nitrile group-containing copolymer rubber. Similar to (A), it is a rubber obtained by copolymerizing a /, 3-ethylenically unsaturated nitrile monomer with another monomer. Unit content 1 0 ⁇ 60% by weight.
- the nitrile group-containing copolymer rubber (B) has an iodine value of 40 to 100.
- the ⁇ ,] 3-ethylenically unsaturated nitrile monomer content of the nitrile group-containing copolymer rubber (B) is from 10 to 60% by weight, preferably from 12 to 55% by weight, more preferably It is 15 to 50% by weight. If the content of ⁇ ,] 3-ethylenically unsaturated nitrile monomer is too small, the vulcanizate has poor oil resistance, while if it is too large, the vulcanizate has poor cold resistance.
- the iodine value of the nitrile group-containing copolymer rubber ( ⁇ ) is from 40 to 100, preferably from 45 to 90, more preferably from 50 to 80. If the iodine value is too small, the compression set of the vulcanizate will increase, and it will be difficult to vulcanize with the nitrile group-containing copolymer rubber (II). Conversely, if the iodine value is too large, heat resistance is poor.
- the nitrile group-containing copolymer rubber contains a large amount of conjugated diene monomer units, and therefore has a large number of unsaturated bonds in the main chain and a high iodine value
- hydrogenation is carried out by a known method to obtain an unsatisfactory main chain.
- the iodine value may be adjusted to a small value by reducing the number of saturated bonds.
- the Mooney viscosity (ML 1 + 4 , 100 ° C.) of the nitrile group-containing copolymer rubber ( ⁇ ) is preferably from 10 to 300, more preferably from 20 to 250, and particularly preferably. Is from 30 to 200. If the viscosity is too low, the mechanical properties of the vulcanizate may be poor, and if too high, the workability may be poor.
- the relative proportions of the nitrile group-containing copolymer rubber (A) and the nitrile group-containing copolymer rubber (B) in the rubber component contained in the vulcanizable rubber composition of the present invention are as follows. 5 to 50 parts by weight, preferably 10 to 45 parts by weight, more preferably 20 to 40 parts by weight, and more preferably 20 to 40 parts by weight of nitrile group-containing copolymer rubber, based on 100 parts by weight.
- the amount of the copolymer rubber (B) is from 95 to 50 parts by weight, preferably from 90 to 55 parts by weight, and more preferably from 80 to 60 parts by weight. If the relative proportion of the nitrile group-containing copolymer rubber (A) is too small, the vulcanizate has a large compression set. Conversely, if it is too large, the vulcanizate is still poor in constant elongation fatigue.
- the rubber component may additionally contain a rubber other than the nitrile group-containing copolymer rubber (A) and the nitrile group-containing copolymer rubber (B), but the amount of the rubber component is 100% by weight.
- the amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less.
- the vulcanizable rubber composition of the present invention contains, as a vulcanizing agent, at least one selected from sulfur and 4,4′-dithiodimorpholine.
- sulfur powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur and the like are usually used.
- the content of the vulcanizing agent is 0.1 to 1.5 parts by weight, preferably 0.2 to 1 part by weight, more preferably 0.3 to 1.3 parts by weight based on 100 parts by weight of the rubber component. ⁇ 0.8 parts by weight. If the amount of the vulcanizing agent is too small, sufficient vulcanization will not be performed and the strength of the vulcanized product will be insufficient. And the elongation is greatly reduced, resulting in poor heat resistance. Also, the permanent set is large.
- the sulfur and Z or 4,4'-dithiodimorpholine vulcanizing agent used in the present invention is usually used in combination with a vulcanization accelerator.
- vulcanization accelerators include zinc white, sulfenamide-based vulcanization accelerator, guanidine-based vulcanization accelerator, thiazol-based vulcanization accelerator, and thiuram, which are used in combination with sulfur or sulfur-containing vulcanization agents.
- Vulcanization accelerators and dithioate vulcanization accelerators are used in combination with sulfur or sulfur-containing vulcanization agents.
- the amount of the vulcanization accelerator used is not particularly limited, and may be determined according to the use of the vulcanized product, the required performance, the type of the vulcanization accelerator, and the like.
- the vulcanizable rubber composition of the present invention includes a compounding agent used for general rubber, for example, a reinforcing agent such as carbon black, silica, and short fiber; a calcium carbonate, a clay, a silver salt, a calcium gayate, and the like. Fillers; metal salts of ethylenically unsaturated carboxylic acids; plasticizers; pigments; antioxidants; tackifiers; processing aids; anti-scorch agents;
- a reinforcing agent such as carbon black, silica, and short fiber
- a calcium carbonate, a clay, a silver salt, a calcium gayate, and the like Fillers; metal salts of ethylenically unsaturated carboxylic acids; plasticizers; pigments; antioxidants; tackifiers; processing aids; anti-scorch agents;
- the method for preparing the vulcanizable rubber composition of the present invention is not particularly limited, and may be prepared by a general method for preparing a vulcanizable rubber composition. May be kneaded. However, after blending the vulcanizing agent and the vulcanization accelerator, the blended composition is kneaded while maintaining the temperature below the vulcanization starting temperature.
- the vulcanizate of the present invention is obtained by vulcanizing the above vulcanizable rubber composition.
- the method for vulcanizing the rubber composition may include heating the vulcanizable rubber composition. Generally, heating is performed after molding, or heating is performed simultaneously with molding.
- the temperature at the time of vulcanization is preferably from 100 to 200, more preferably from 130 to 19 ° 5 ° C, and particularly preferably from 140 to 190. If the temperature is too low, the vulcanization time may be long and the vulcanization density may be low. Temperature is too high In this case, molding may be defective.
- the vulcanization time varies depending on the vulcanization method, vulcanization temperature, shape, etc., but is preferably 1 minute to 4 hours in terms of vulcanization density and production efficiency.
- the heating method for vulcanization may be appropriately selected from the methods used for vulcanization of rubber, such as press heating, steam heating, oven heating, and hot air heating.
- the surface may be vulcanized but the inside may not be vulcanized.
- secondary vulcanization for maintaining a high temperature state may be performed.
- the properties of the rubber vulcanizate were evaluated by the following methods.
- the prepared vulcanizable rubber composition was vulcanized at 160 at a press pressure of 1 OMPa for 20 minutes to obtain a sheet having a thickness of 2 mm. This sheet was punched out to produce a test piece. Using these test specimens, the tensile strength and elongation of the vulcanizate were measured in accordance with Japanese Industrial Standard JISK 6251, and the vulcanizate was measured using a Durometer overnight hardness tester type ⁇ ⁇ ⁇ in accordance with JIS ⁇ 6253. The hardness was measured.
- the specimen was kept at 120, and after 168 hours and 336 hours, the tensile strength (MPa), elongation (%) and hardness of the vulcanized product were measured, respectively.
- the rate of change (%) of those measured values before holding at a high temperature was examined. The larger the change, the lower the heat resistance.
- a flexometer test specified in ASTM D 623-78 was applied. evaluated. The test was performed using a Goodrich Flexometer at a test temperature of 100 ° C, an initial load of 25 pounds (11.34 kg), a dynamic displacement of 4.45 mm, and a dynamic displacement of 25 minutes, with the HBU applied. (Calorific value [in]: measured The difference between the temperature of the test piece and the ambient temperature of 1 oot: was defined as the exothermic temperature) and PS (permanent strain) (%) were measured. The smaller the HBU and PS, the better the dynamic characteristics. Constant elongation fatigue
- the prepared vulcanizable rubber composition was vulcanized at 16 O for 20 minutes under a pressure of 1 OMPa to obtain a sheet having a thickness of 2 mm. This sheet was punched out using a No. 3 dumbbell to prepare a test piece. Using these test pieces, fix both ends with a gripper so that the distance between them is 75 mm, and repeat reciprocating motion at 23 ° C 300 times per minute so that the test pieces can be extended 0 to 100%. And the number of times the test piece was broken was measured.
- the vulcanizable rubber composition was vulcanized at 160 at a press pressure of 10 MPa for 25 minutes to obtain a test piece.
- the compression set (%) was measured in accordance with JIS K 6262 using these test specimens after maintaining them in a 25% compressed state at 120 ° C. for 70 hours and after maintaining them for 168 hours.
- Nitrile group-containing copolymer rubber A-1 Nipo 1 DN 1042AL, manufactured by Nippon Zeon Co., Ltd., acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 33.5%, iodine value about 313, ML 1 + 4 , (100) 46) 40 parts, nitrile group-containing copolymer rubber B (Z etpol 2030L, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 36.2 %, Iodine value approx.
- Example 1 The same treatment as in Example 1 was conducted except that the amount of the nitrile group-containing copolymer rubber A-1 was changed from 40 parts to 20 parts and the amount of the nitrile group-containing copolymer rubber B was changed from 60 parts to 80 parts. Table 1 shows the results.
- nitrile group-containing copolymer rubber A-2 (Nipol D 1201 L, manufactured by Zeon Corporation, acrylonitrile-butene-isoprene copolymer rubber, acrylonitrile
- the treatment was carried out in the same manner as in Example 1 except that a unit content of 35%, an iodine value of about 280, and a muny viscosity ML 1 + 4 ( 100 :) 46) were used. Table 1 shows the results.
- Example 1 The procedure was as in Example 1, except that the amount of sulfur was changed to 1.3 parts. The results are shown in Table 1.
- Example 1 The same procedure as in Example 1 was carried out except that instead of 0.8 parts of powdered sulfur, 3 parts of 4,4′-dithiodimorpholine (equivalent to 0.91 part of sulfur) was used. Table 1 shows the results. Comparative Example 1
- Example 1 The same treatment as in Example 1 was carried out except that the nitrile group-containing copolymer rubber A-1 was not used and the amount of the nitrile group-containing copolymer rubber B was changed from 60 parts to 100 parts. The results are shown in Table 1.
- Example 1 The processing was performed in the same manner as in Example 1 except that the amount of the nitrile group-containing copolymer rubber A-1 was changed from 40 parts to 100 parts, and the nitrile group-containing copolymer rubber B was not used. Table 1 shows the results.
- Comparative Example 3 The same treatment as in Example 1 was carried out except that the amount of the nitrile group-containing copolymer rubber A-1 was changed from 40 parts to 70 parts and the amount of the nitrile group-containing copolymer rubber B was changed from 60 parts to 30 parts. Table 1 shows the results.
- nitrile group-containing copolymer rubber B instead of nitrile group-containing copolymer rubber B, nitrile group-containing copolymer rubber b (Ze tpo 1 2020, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 36.2%, iodine value
- nitrile group-containing copolymer rubber b Ze tpo 1 2020, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 36.2%, iodine value
- Table 1 shows the results.
- Example 1 The procedure was as in Example 1, except that the amount of sulfur powder was changed from 0.8 parts to 2.5 parts. Table 1 shows the results.
- the vulcanizate of the rubber composition containing no nitrile group-containing copolymer rubber (A) having a high iodine value has a large compression set and a constant elongation fatigue test. The number of breaks at is small.
- the vulcanizate of the rubber composition containing no nitrile group-containing copolymer rubber (B) having a low iodine value has a small number of breaks in the constant elongation fatigue test.
- the vulcanizate of a rubber composition containing a large amount of nitrile group-containing copolymer rubber having a large iodine value (A) and a small amount of a nitrile group-containing copolymer rubber having a small iodine value (B) (Comparative Example 3) is as follows. Small number of breaks in constant elongation fatigue test. The vulcanizate (Comparative Example 4) of the rubber composition using the nitrile group-containing copolymer rubber (b) having an iodine value that is too small has too large a compression set.
- the vulcanizate of the rubber composition having an excessive amount of sulfur (Comparative Example 5) has a small elongation even in normal physical properties, but the rate of elongation decreases greatly when heat is applied, and the heat resistance is poor. It is also inferior to PS.
- the vulcanizates of the rubber composition of the present invention (Examples 1 to 5) have a small compression set, excellent heat resistance, small HBU and PS, and a low number of fractures in the low elongation fatigue test. Large and difficult to break. Industrial applicability
- the vulcanizate of the nitrile group-containing copolymer rubber of the present invention has excellent dynamic characteristics and heat resistance, and has characteristics of low compression set. Therefore, this vulcanized product is useful as hoses, tubes, seals, gaskets, boots, rolls, belts, diaphragms, etc., in which these characteristics are utilized, but especially for rolls and belts used in dynamic conditions. It is suitable for boots, diaphragms and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A vulcanizable rubber composition which comprises: 100 parts by weight of a rubber ingredient comprising (A) 5 to 50 parts by weight of a nitrile copolymer rubber having a content of α,ß-ethylenically unsaturated nitrile monomer units of 10 to 60 wt.% and having an iodine value of 180 to 430 and (B) 50 to 95 parts by weight of a nitrile copolymer rubber having a content of α,ß-ethylenically unsaturated nitrile monomer units of 10 to 60 wt.% and having an iodine value of 40 to 100; and 0.1 to 1.5 parts by weight of at least one vulcanizing agent selected between sulfur and 4,4'-dithiodimorpholine, in terms of sulfur amount. The vulcanizable rubber composition gives a vulcanizate excellent in dynamic properties and heat resistance and reduced in compression set.
Description
明細書 加硫性ゴム組成物および加硫物 技術分野 Description Vulcanizable rubber composition and vulcanizate
本発明は、 動特性および耐熱性に優れ、 圧縮永久ひずみが小さな二トリル基含 有共重合体ゴム加硫物、 およびその材料となる加硫性ゴム組成物に関する。 背景技術 The present invention relates to a vulcanizate of a nitrile group-containing copolymer rubber excellent in dynamic characteristics and heat resistance and having a small compression set, and a vulcanizable rubber composition as a material thereof. Background art
ァクリロ二トリルーブタジエン共重合ゴムのような二トリル基含有共重合体ゴ ムは、 耐油性に優れることが一般的に知られている。 さらに、 耐熱性、耐薬品性、 耐候性、 引張強度などの向上を目的として、 アクリロニトリル—ブタジエン共重 合ゴムを水素添加した水素化ァクリロニトリル一ブタジエン共重合ゴムが知られ ている。 しかし、 水素化アクリロニトリル—ブタジエン共重合ゴムは水素化前の ァクリロニトリル—ブタジエン共重合ゴムと比較して、 圧縮永久歪みが大きいと いう問題があった。 It is generally known that nitrile group-containing copolymer rubber such as acrylonitrile-butadiene copolymer rubber has excellent oil resistance. Further, hydrogenated acrylonitrile-butadiene copolymer rubber obtained by hydrogenating acrylonitrile-butadiene copolymer rubber for the purpose of improving heat resistance, chemical resistance, weather resistance, tensile strength and the like is known. However, the hydrogenated acrylonitrile-butadiene copolymer rubber has a problem that the compression set is larger than that of the acrylonitrile-butadiene copolymer rubber before hydrogenation.
そこで、 アクリロニトリル—ブタジェン共重合ゴムと水素化ァクリロニトリル —ブ夕ジェン共重合ゴムをブレンドして、 ブレンド物を硫黄で加硫することが提 案されている (特開昭 6 3 _ 1 4 2 0 4 6号) 。 しかし、 この提案された技術で は、 水素化アクリロニトリル—ブタジエン共重合ゴムとして、 ヨウ素価が 3 0以 下のものを用いていることから、 二種類のゴムの不飽和結合量が大きく異なるた めに、 加硫速度が大きく異なり、 共加硫が困難であり、 これを解決するために、 硫黄をゴム成分 1 0 0重量部当たり 2〜1 0重量部と多量に使用して加硫してい る。 ところが、 このようにして得られる加硫物は、 硫黄が多量のため、 熱老化に より硬さが上昇しやすく、 伸びが低下しやすく、 やはり圧縮永久歪みが大きくな るという問題を有している。 Therefore, it has been proposed to blend acrylonitrile-butadiene copolymer rubber and hydrogenated acrylonitrile-butadiene copolymer rubber and vulcanize the blend with sulfur (Japanese Patent Application Laid-Open No. 63-142020). 4 No. 6). However, in this proposed technology, since the hydrogenated acrylonitrile-butadiene copolymer rubber having an iodine value of 30 or less is used, the amount of unsaturated bonds between the two types of rubber is significantly different. In addition, the vulcanization rates differ greatly, making co-vulcanization difficult.To solve this, vulcanization is carried out using a large amount of sulfur, 2 to 10 parts by weight per 100 parts by weight of the rubber component. You. However, the vulcanizates obtained in this way have a problem that, due to the large amount of sulfur, hardness tends to increase due to heat aging, elongation tends to decrease, and compression set also increases. I have.
一方、 この二種のプレンドゴムを硫黄に代えて有機過酸化物で加硫した加硫ゴ ムも提案されている (特開平 9— 6 7 4 7 1号) 。 しかし、 この加硫ゴムは、 悪 臭を有するという問題があつた。
発明の開示 On the other hand, a vulcanized rubber obtained by vulcanizing these two types of blend rubber with an organic peroxide instead of sulfur has also been proposed (Japanese Patent Application Laid-Open No. 9-647471). However, this vulcanized rubber had a problem of having a bad odor. Disclosure of the invention
本発明の目的は、 上記の従来技術に鑑み、 動特性および耐熱性に優れ、 圧縮永 久ひずみが小さな硫黄で加硫した二トリル基含有共重合体ゴム加硫物、 およびそ の材料となる加硫性ゴム組成物を提供することにある。 An object of the present invention is to provide a nitrile group-containing copolymer rubber vulcanized with sulfur, which has excellent dynamic characteristics and heat resistance, and has a small compression elongation, in view of the above prior art, and a material thereof. It is to provide a vulcanizable rubber composition.
本発明者らは、 上記課題を達成すべく鋭意検討した結果、 ヨウ素価が特定範囲 の二種の二トリル基含有共重合体ゴムを併用すれば、 少量の硫黄でも両者の間に 強固な共加硫が起こることを見出し、 この知見に基づいて、 本発明を完成するに 至った。 The present inventors have conducted intensive studies to achieve the above object, and as a result, when two types of nitrile group-containing copolymer rubbers having an iodine value in a specific range are used in combination, even if a small amount of sulfur is used, a strong copolymer is formed between the two. The present inventors have found that vulcanization occurs, and have completed the present invention based on this finding.
かくして、 本発明によれば、 ひ,)3—エチレン性不飽和二トリル単量体単位含 有量 1 0〜6 0重量%、 ヨウ素価 1 8 0〜4 3 0の二トリル基含有共重合ゴム Thus, according to the present invention, (ii) a copolymer containing a nitrile group having a 3-ethylenically unsaturated nitrile monomer unit content of from 10 to 60% by weight and an iodine value of from 180 to 430. Rubber
(A) 5〜5 0重量部および α,)3—エチレン性不飽和二トリル単量体単位含有 量 1 0〜6 0重量%、 ヨウ素価 4 0〜1 0 0のニトリル基含有共重合ゴム (Β) 5 0〜9 5重量部からなるゴム成分 1 0 0重量部と、 硫黄および 4 , 4 '—ジチ ォジモルホリンの中から選ばれた少なくとも一種の加硫剤を硫黄量換算で 0 . 1 〜 1 . 5重量部含有する加硫性ゴム組成物が提供される。 (A) 5 to 50 parts by weight and a nitrile group-containing copolymer rubber having an α,) 3-ethylenically unsaturated nitrile monomer unit content of 10 to 60% by weight and an iodine value of 40 to 100 (Ii) 100 to 100 parts by weight of a rubber component consisting of 50 to 95 parts by weight, and at least one vulcanizing agent selected from sulfur and 4,4'-dithiodimorpholine in terms of sulfur content of 0.1. There is provided a vulcanizable rubber composition containing up to 1.5 parts by weight.
さらに、 本発明によれば、 上記の二トリル基含有共重合ゴム (Α) 、 二トリル 基含有共重合ゴム (Β ) および硫黄系加硫剤を含有する加硫性ゴム組成物を加硫 してなる加硫物が提供される。 発明を実施するための最良の形態 Further, according to the present invention, the vulcanizable rubber composition containing the nitrile group-containing copolymer rubber (Α), the nitrile group-containing copolymer rubber (Β) and a sulfur-based vulcanizing agent is vulcanized. A vulcanizate is provided. BEST MODE FOR CARRYING OUT THE INVENTION
本発明の加硫性ゴム組成物は、二トリル基含有共重合ゴム(Α) 5〜 5 0重量% および二トリル基含有共重合ゴム (Β) 5 0〜9 5重量%からなるゴム成分 1 0 0重量部と、 加硫剤として、 硫黄量換算で 0 . 1〜1 . 5重量部の硫黄および 4, 4 'ージチォジモルホリンの中から選ばれた少なくと一種を含有する。 The vulcanizable rubber composition of the present invention comprises a rubber component 1 comprising 5 to 50% by weight of a nitrile group-containing copolymer rubber (Α) and 50 to 95% by weight of a nitrile group-containing copolymer rubber (Β). It contains 0.1 parts by weight and 0.1 to 1.5 parts by weight of sulfur in terms of sulfur and at least one selected from 4,4'-dithiodimorpholine as a vulcanizing agent.
本発明の加硫性ゴム組成物に含有されるゴム成分 1 0 0重量部中 5〜5 0重量 部をしめる二トリル基含有共重合ゴム (Α) は、 α , )3 _エチレン性不飽和ニト リル単量体を他の単量体と共重合して得られるゴムであり、 α , ]3 _エチレン性
不飽和二トリル単量体単位含有量 1 0〜 6 0重量%、 ョゥ素価 1 8 0〜 4 3 0の ものである。 The nitrile group-containing copolymer rubber (Α), which accounts for 5 to 50 parts by weight of 100 parts by weight of the rubber component contained in the vulcanizable rubber composition of the present invention, is α,) 3_ethylenically unsaturated A rubber obtained by copolymerizing a nitrile monomer with other monomers. It has an unsaturated nitrile monomer unit content of 10 to 60% by weight and an iodine value of 180 to 430.
α, /3—エチレン性不飽和二トリル単量体としては、 例えば、 ァクリロ二トリ ル、 メタクリロニトリル、 ひ一クロ口アクリロニトリルなどが挙げられ、 ァクリ ロニトリルが好ましい。 二トリル基含有共重合ゴム (Α) 中の α,)3—エチレン 性不飽和二トリル単量体単位含有量は、 1 0〜 6 0重量%、 好ましくは 1 2〜 5 5重量%、 より好ましくは 1 5〜 5 0重量%である。 α , /3 _エチレン性不飽和 二トリル単量体含有量が少なすぎると加硫物の耐油性が劣り、 逆に多すぎると耐 寒性に劣る。 Examples of the α, / 3-ethylenically unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, and acrylonitrile monochloride, with acrylonitrile being preferred. The content of the α,) 3-ethylenically unsaturated nitrile monomer unit in the nitrile group-containing copolymer rubber (Α) is 10 to 60% by weight, preferably 12 to 55% by weight, Preferably it is 15 to 50% by weight. If the content of α, / 3_ethylenically unsaturated nitrile monomer is too low, the oil resistance of the vulcanizate is poor, and if it is too high, the cold resistance is poor.
二トリル基含有共重合ゴム (Α) において、 α, J3 -エチレン性不飽和二トリ ル単量体と共重合させる単量体としては、 共役ジェン単量体、 非共役ジェン単量 体、 およびひ—ォレフィンなどが例示される。 これらの単量体は単独で、 または 2種以上を組合わせて共重合することができる。 これらの単量体の中では共役ジ ェン単量体が好ましい。 共役ジェン単量体としては、 例えば、 1 , 3—ブ夕ジェ ン、 イソプレン、 2 , 3—ジメチル一 1 , 3—ブタジエン、 1, 3—ペン夕ジェ ンなどが挙げられ、 1, 3—ブタジエン、 イソプレンが好ましく、 1 , 3—ブ夕 ジェンが特に好ましい。 非共役ジェン単量体は、 好ましくは炭素数が 5〜 1 2の ものであり、 1, 4—ペン夕ジェン、 1, 4—へキサジェン、 ビニルノルボルネ ン、 ジシクロペン夕ジェンなどが例示される。 α—才レフインとしては、 炭素数 が 2〜 1 2のものが好ましく、 エチレン、 プロピレン、 1—ブテン、 4一メチル — 1—ペンテン、 1 一へキセン、 1—ォクテンなどが例示される。 二トリル基含 有共重合ゴム (Α) 中の、 ひ, /3—エチレン性不飽和二トリル単量体と共重合さ れる単量体の単位の量は、 4 0〜 9 0重量%、 好ましくは 4 5〜 8 8重量%、 よ り好ましくは 5 0〜 8 5重量%である。 In the nitrile group-containing copolymer rubber (Α), the monomers to be copolymerized with the α, J3-ethylenically unsaturated nitrile monomer include a conjugated diene monomer, a non-conjugated diene monomer and For example, freerefin is exemplified. These monomers can be copolymerized alone or in combination of two or more. Of these monomers, conjugated diene monomers are preferred. Examples of the conjugated diene monomer include 1,3-butane gen, isoprene, 2,3-dimethyl-1,3-butadiene and 1,3-pentene gen. Butadiene and isoprene are preferred, and 1,3-butane is particularly preferred. The non-conjugated diene monomer preferably has 5 to 12 carbon atoms, and examples thereof include 1,4-pentene, 1,4-hexadiene, vinylnorbornene, and dicyclopentene. As the α-olefin, those having 2 to 12 carbon atoms are preferable, and examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 11-hexene, and 1-octene. In the nitrile group-containing copolymer rubber (Α), the amount of the unit of the monomer copolymerized with the , / 3-ethylenically unsaturated nitrile monomer is 40 to 90% by weight, It is preferably from 45 to 88% by weight, more preferably from 50 to 85% by weight.
さらに、 上記単量体に加えて、 芳香族ビニル単量体、 フッ素含有ビニル単量体、 ひ, ]3—エチレン性不飽和モノカルボン酸、 ひ, i3—エチレン性不飽和多価カルボ ン酸またはその無水物、 共重合性の老化防止剤などを共重合してもよい。 Further, in addition to the above monomers, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, [3] -ethylenically unsaturated monocarboxylic acid, [3], i3-ethylenically unsaturated polycarboxylic acid Alternatively, an anhydride thereof, a copolymerizable antioxidant, or the like may be copolymerized.
芳香族ビニル単量体としては、 例えば、 スチレン、 α—メチルスチレン、 ビニ ルビリジンなどが挙げられる。 フッ素含有ビニル単量体としては、 例えば、 フル
ォロェチルビニルエーテル、 フルォロプロピルビニルエーテル、 o—トリフルォ ロメチルスチレン、 ペン夕フルォロ安息香酸ビニル、 ジフルォロェチレン、 テト ラフルォロエチレンなどが挙げられる。 a , i3—エチレン性不飽和モノカルボン 酸としては、 例えば、 アクリル酸、 メ夕クリル酸などが挙げられる。 α, β—ェ チレン性不飽和多価カルボン酸としては、 例えば、 ィタコン酸、 フマル酸、 マレ イン酸など力 s挙げられる。 ひ, /3—エチレン性不飽和多価カルボン酸無水物とし ては、 例えば、 無水ィタコン酸、 無水マレイン酸などが挙げられる。 共重合性の 老化防止剤としては、 例えば、 Ν— ( 4—ァニリノフエニル) アクリルアミド、 Ν - ( 4—ァニリノフエニル) メ夕クリルアミド、 Ν— ( 4—ァニリノフエニル) シンナムアミド、 Ν— ( 4—ァニリノフエニル) クロトンアミド、 Ν—フエニル —4— ( 3—ビニルベンジルォキシ) ァニリン、 Ν—フエ二ルー 4 _ ( 4ービニ ルペンジルォキシ) ァニリンなどが挙げられる。 Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyl pyridine and the like. Examples of fluorine-containing vinyl monomers include, for example, full Examples include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, penfluorovinyl benzoate, difluoroethylene, tetrafluoroethylene and the like. Examples of the a, i3-ethylenically unsaturated monocarboxylic acid include acrylic acid and methyl methacrylate. Examples of the α, β-ethylenically unsaturated polycarboxylic acid include itaconic acid, fumaric acid, and maleic acid. Examples of the / 3-ethylenically unsaturated polycarboxylic anhydride include itaconic anhydride and maleic anhydride. Examples of copolymerizable antioxidants include Ν— (4-anilinophenyl) acrylamide, Ν- (4-anilinophenyl) methacrylamide, Ν— (4-anilinophenyl) cinnamamide, Ν— (4-anilinophenyl) crotonamide , Ν-phenyl-4- (3-vinylbenzyloxy) aniline, Ν-phenyl-4_ (4-vinylpentyloxy) aniline and the like.
二トリル基含有共重合ゴム (Α) のヨウ素価は、 1 8 0〜 4 3 0、 好ましくは 2 0 0〜4 0 0、 より好ましくは 2 3 0〜 3 8 0である。 ヨウ素価が小さすぎる と加硫物はゴム弾性に劣る。 逆に、 ヨウ素価が大きすぎると加硫物の耐油性およ び耐熱性に劣り、 また、 二トリル基含有共重合ゴム (Β ) との共加硫が困難にな る。 ヨウ素価は、 主鎖の不飽和結合量を示す価であり、 主として共役ジェン単量 体単位含有量によって決められる。 必要に応じて、 公知の方法で、 二トリル基含 有共重合ゴム (Α) を水素添加によって不飽和結合を飽和させ、 ヨウ素価を調整 してもよい。 The iodine value of the nitrile group-containing copolymer rubber (Α) is from 180 to 430, preferably from 200 to 400, more preferably from 230 to 380. If the iodine value is too small, the vulcanizate will have poor rubber elasticity. Conversely, if the iodine value is too large, the vulcanizate will have poor oil resistance and heat resistance, and it will be difficult to covulcanize with the nitrile group-containing copolymer rubber (II). The iodine value is a value indicating the amount of unsaturated bonds in the main chain, and is determined mainly by the content of conjugated gen monomer units. If necessary, the iodine value may be adjusted by hydrogenating the nitrile group-containing copolymer rubber (II) to saturate unsaturated bonds by a known method.
二トリル基含有共重合ゴム (Α) のム一二一粘度 (M L 1+4, 1 0 0 ) は、 好ましくは 2 0〜 3 0 0、 より好ましくは 3 0〜 2 5 0、 特に好ましくは 4 0〜 2 0 0である。 ムーニー粘度が小さすぎると加硫物の機械的物性が劣る場合があ り、 逆に大きすぎると加工性に劣る場合がある。 The nitrile group-containing copolymer rubber (Α) preferably has a viscosity (ML 1 + 4 , 100) of 20 to 300, more preferably 30 to 250, and particularly preferably 30 to 250. 40 to 200. If the Mooney viscosity is too low, the mechanical properties of the vulcanizate may be poor, and if too high, the workability may be poor.
本発明の加硫性ゴム組成物に含有されるゴム成分 1 0 0重量部中 5 0〜 9 5重 量部をしめる二トリル基含有共重合ゴム(B )は、二トリル基含有共重合ゴム(A) と同様に、 ひ, /3—エチレン性不飽和二トリル単量体を他の単量体と共重合して 得られるゴムであり、 ひ, /3—エチレン性不飽和二トリル単量体単位含有量 1 0
〜6 0重量%のものである。 二トリル基含有共重合ゴム (B) は、 ヨウ素価 4 0 〜1 0 0を有する。 The nitrile group-containing copolymer rubber (B), which accounts for 50 to 95 parts by weight in 100 parts by weight of the rubber component contained in the vulcanizable rubber composition of the present invention, is a nitrile group-containing copolymer rubber. Similar to (A), it is a rubber obtained by copolymerizing a /, 3-ethylenically unsaturated nitrile monomer with another monomer. Unit content 1 0 ~ 60% by weight. The nitrile group-containing copolymer rubber (B) has an iodine value of 40 to 100.
二トリル基含有共重合ゴム (B) の α, ]3—エチレン性不飽和二トリル単量体 含有量は、 1 0〜6 0重量%、 好ましくは 1 2〜5 5重量%、 より好ましくは 1 5〜5 0重量%である。 α , ]3—エチレン性不飽和二トリル単量体含有量が少な すぎると加硫物の耐油性に劣り、 逆に多すぎると加硫物の耐寒性に劣る。 The α,] 3-ethylenically unsaturated nitrile monomer content of the nitrile group-containing copolymer rubber (B) is from 10 to 60% by weight, preferably from 12 to 55% by weight, more preferably It is 15 to 50% by weight. If the content of α,] 3-ethylenically unsaturated nitrile monomer is too small, the vulcanizate has poor oil resistance, while if it is too large, the vulcanizate has poor cold resistance.
二トリル基含有共重合ゴム (Β) のヨウ素価は、 4 0〜1 0 0、 好ましくは 4 5〜9 0、 より好ましくは 5 0〜8 0である。 ヨウ素価が小さすぎると加硫物の 圧縮永久ひずみが大きくなり、 また、 二トリル基含有共重合ゴム (Α) との共加 硫が困難になる。 逆に、 ヨウ素価が大きすぎると耐熱性に劣る。 二トリル基含有 共重合ゴム中の共役ジェン単量体単位量が多く、 そのため主鎖の不飽和結合が多 く、 ヨウ素価が大きい場合は、 公知の方法で水素添加して、 主鎖の不飽和結合を 減らすことによって、 ヨウ素価を小さく調整して用いればよい。 The iodine value of the nitrile group-containing copolymer rubber (Β) is from 40 to 100, preferably from 45 to 90, more preferably from 50 to 80. If the iodine value is too small, the compression set of the vulcanizate will increase, and it will be difficult to vulcanize with the nitrile group-containing copolymer rubber (II). Conversely, if the iodine value is too large, heat resistance is poor. When the nitrile group-containing copolymer rubber contains a large amount of conjugated diene monomer units, and therefore has a large number of unsaturated bonds in the main chain and a high iodine value, hydrogenation is carried out by a known method to obtain an unsatisfactory main chain. The iodine value may be adjusted to a small value by reducing the number of saturated bonds.
二トリル基含有共重合ゴム (Β) のム一ニー粘度 (ML1+4, 1 0 0 °C) は、 好ましくは 1 0〜 3 0 0、 より好ましくは 2 0〜2 5 0、 特に好ましくは 3 0〜 2 0 0である。 ム一二一粘度が小さすぎると加硫物の機械的物性が劣る場合があ り、 逆に大きすぎると加工性に劣る場合がある。 The Mooney viscosity (ML 1 + 4 , 100 ° C.) of the nitrile group-containing copolymer rubber (Β) is preferably from 10 to 300, more preferably from 20 to 250, and particularly preferably. Is from 30 to 200. If the viscosity is too low, the mechanical properties of the vulcanizate may be poor, and if too high, the workability may be poor.
本発明の加硫性ゴム組成物に含有されるゴム成分中の二トリル基含有共重合ゴ ム (A) と二トリル基含有共重合ゴム (B) の量の相対的割合は、 ゴム成分 1 0 0重量部に対し、 二トリル基含有共重合ゴム (A) が 5〜 5 0重量部、 好ましく は 1 0〜 4 5重量部、 より好ましくは 2 0〜 4 0重量部および二トリル基含有共 重合ゴム (B) が 9 5〜5 0重量部、 好ましくは 9 0〜5 5重量部、 より好まし くは 8 0〜6 0重量部である。 二トリル基含有共重合ゴム (A) の相対的割合が 小さすぎると、 加硫物は圧縮永久ひずみが大きい。 逆に、 大きすぎると、 加硫物 はやはり定伸長疲労性に劣る。 The relative proportions of the nitrile group-containing copolymer rubber (A) and the nitrile group-containing copolymer rubber (B) in the rubber component contained in the vulcanizable rubber composition of the present invention are as follows. 5 to 50 parts by weight, preferably 10 to 45 parts by weight, more preferably 20 to 40 parts by weight, and more preferably 20 to 40 parts by weight of nitrile group-containing copolymer rubber, based on 100 parts by weight. The amount of the copolymer rubber (B) is from 95 to 50 parts by weight, preferably from 90 to 55 parts by weight, and more preferably from 80 to 60 parts by weight. If the relative proportion of the nitrile group-containing copolymer rubber (A) is too small, the vulcanizate has a large compression set. Conversely, if it is too large, the vulcanizate is still poor in constant elongation fatigue.
ゴム成分は、二トリル基含有共重合ゴム(A)と二トリル基含有共重合ゴム(B ) 以外のゴムを付加的に含有していてもよいが、 その量は、 ゴム成分 1 0 0重量部 中、 好ましくは 3 0重量部以下、 より好ましくは 2 0重量部以下、 特に好ましく は 1 0重量部以下である。
本発明の加硫性ゴム組成物は、 加硫剤として、 硫黄および 4, 4 '—ジチォジ モルホリンの中から選ばれた少なくとも一種を含有する。 硫黄としては、通常、 粉末硫黄、 沈降硫黄、 コロイド硫黄、 不溶性硫黄などが用いられる。 加硫剤の含 有量は、 上記ゴム成分 1 0 0重量部に対し、 硫黄量換算で 0. 1〜1 . 5重量部、 好ましくは 0. 2〜1重量部、 より好ましくは 0. 3〜0. 8重量部である。 加 硫剤の量が少なすぎると十分な加硫が行われず、 加硫物の強度が不十分になり、 逆に、加硫剤の量が多すぎると伸びが劣るだけでなく、 熱を加えると伸びが大幅 に低下し、 耐熱性に劣る。 また、 永久ひずみが大きい。 The rubber component may additionally contain a rubber other than the nitrile group-containing copolymer rubber (A) and the nitrile group-containing copolymer rubber (B), but the amount of the rubber component is 100% by weight. The amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less. The vulcanizable rubber composition of the present invention contains, as a vulcanizing agent, at least one selected from sulfur and 4,4′-dithiodimorpholine. As the sulfur, powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur and the like are usually used. The content of the vulcanizing agent is 0.1 to 1.5 parts by weight, preferably 0.2 to 1 part by weight, more preferably 0.3 to 1.3 parts by weight based on 100 parts by weight of the rubber component. ~ 0.8 parts by weight. If the amount of the vulcanizing agent is too small, sufficient vulcanization will not be performed and the strength of the vulcanized product will be insufficient. And the elongation is greatly reduced, resulting in poor heat resistance. Also, the permanent set is large.
本発明で用いる硫黄および Zまたは 4, 4 '—ジチォジモルホリン加硫剤には、 通常、 加硫促進剤を併用する。 加硫促進剤としては、 従来から、 硫黄または硫黄 含有加硫剤に併用される亜鉛華、 スルフェンアミド系加硫促進剤、 グァニジン系 加硫促進剤、 チアゾ一ル系加硫促進剤、 チウラム系加硫促進剤、 ジチォ酸塩系加 硫促進剤などが挙げられる。 加硫促進剤の使用量は特に限定されず、 加硫物の 用途、 要求性能、 加硫促進剤の種類などに応じて決めればよい。 The sulfur and Z or 4,4'-dithiodimorpholine vulcanizing agent used in the present invention is usually used in combination with a vulcanization accelerator. Conventionally, vulcanization accelerators include zinc white, sulfenamide-based vulcanization accelerator, guanidine-based vulcanization accelerator, thiazol-based vulcanization accelerator, and thiuram, which are used in combination with sulfur or sulfur-containing vulcanization agents. Vulcanization accelerators and dithioate vulcanization accelerators. The amount of the vulcanization accelerator used is not particularly limited, and may be determined according to the use of the vulcanized product, the required performance, the type of the vulcanization accelerator, and the like.
本発明の加硫性ゴム組成物には、 一般的なゴムに使用される配合剤、 例えば、 カーボンブラック、 シリカ、 短繊維などの補強剤;炭酸カルシウム、 クレー、 夕 ルク、 ゲイ酸カルシウムなどの充填剤; ひ エチレン性不飽和カルボン酸金 属塩;可塑剤;顔料;老化防止剤;粘着付与剤;加工助剤;スコーチ防止剤;な どや樹脂を含有せしめてもよい。 The vulcanizable rubber composition of the present invention includes a compounding agent used for general rubber, for example, a reinforcing agent such as carbon black, silica, and short fiber; a calcium carbonate, a clay, a silver salt, a calcium gayate, and the like. Fillers; metal salts of ethylenically unsaturated carboxylic acids; plasticizers; pigments; antioxidants; tackifiers; processing aids; anti-scorch agents;
本発明の加硫性ゴム組成物の調製方法は特に限定されず、 一般的な加硫性ゴム 組成物の調製方法で調製すればよく、 密閉式混合機やオープンロールなどを用い て、 所要成分を混練すればよい。 ただし、 加硫剤および加硫促進剤の配合後は、 配合組成物が加硫開始温度未満に維持しながら混練する。 The method for preparing the vulcanizable rubber composition of the present invention is not particularly limited, and may be prepared by a general method for preparing a vulcanizable rubber composition. May be kneaded. However, after blending the vulcanizing agent and the vulcanization accelerator, the blended composition is kneaded while maintaining the temperature below the vulcanization starting temperature.
本発明の加硫物は、 上記加硫性ゴム組成物を加硫したものである。 ゴム組成物 を加硫する方法は、 加硫性ゴム組成物を加熱すればよい。 一般的には、 成形して おいて加熱するか、 成形と同時に加熱する。 The vulcanizate of the present invention is obtained by vulcanizing the above vulcanizable rubber composition. The method for vulcanizing the rubber composition may include heating the vulcanizable rubber composition. Generally, heating is performed after molding, or heating is performed simultaneously with molding.
加硫時の温度は、 好ましくは 1 0 0〜2 0 0で、 より好ましくは 1 3 0〜1 9 ■5 °C、 特に好ましくは 1 4 0〜 1 9 0 である。 温度が低すぎると加硫時間が長 時間必要となったり、 加硫密度が低くなつたりする場合がある。 温度が高すぎる
場合は、 成形不良になる場合がある。 また、 加硫時間は、 加硫方法、 加硫温度、 形状などにより異なるが、 1分間〜 4時間が加硫密度と生産効率の面から好まし い。 The temperature at the time of vulcanization is preferably from 100 to 200, more preferably from 130 to 19 ° 5 ° C, and particularly preferably from 140 to 190. If the temperature is too low, the vulcanization time may be long and the vulcanization density may be low. Temperature is too high In this case, molding may be defective. The vulcanization time varies depending on the vulcanization method, vulcanization temperature, shape, etc., but is preferably 1 minute to 4 hours in terms of vulcanization density and production efficiency.
加硫するための加熱方法としては、 プレス加熱、 蒸気加熱、 オーブン加熱、 熱 風加熱などのゴムの加硫に用いられる方法から適宜選択すればよレ 。 The heating method for vulcanization may be appropriately selected from the methods used for vulcanization of rubber, such as press heating, steam heating, oven heating, and hot air heating.
加硫物の形状、 大きさなどによっては、 表面は加硫していても、 内部が加硫し ないことがある。 そのような場合、 上記のように加硫した後、 高温状態に維持す る二次加硫を行なつてもよい。 Depending on the shape and size of the vulcanized product, the surface may be vulcanized but the inside may not be vulcanized. In such a case, after vulcanization as described above, secondary vulcanization for maintaining a high temperature state may be performed.
以下に実施例、 比較例を挙げて、 本発明を具体的に説明する。 これらの例にお いて、部および%は、 特に記載のない限り、 重量基準である。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In these examples, parts and percentages are by weight unless otherwise indicated.
なお、 ゴム加硫物の特性は下記方法によって評価した。 The properties of the rubber vulcanizate were evaluated by the following methods.
常態物性 Normal physical properties
調製した加硫性ゴム組成物を 160 で 20分間、 プレス圧 1 OMP aで加硫 を行って、 厚さ 2mmのシートを得た。 このシートを打ち抜いて、 試験片を作製 した。 これらの試験片を用いて、 日本工業規格 J I S K 6251に従い、 加硫 物の引張強さおよび伸びを測定し、 J I S Κ 6253に従い、 デュロメ一夕硬 さ試験機タイプ Α型を用いて加硫物の硬さを測定した。 The prepared vulcanizable rubber composition was vulcanized at 160 at a press pressure of 1 OMPa for 20 minutes to obtain a sheet having a thickness of 2 mm. This sheet was punched out to produce a test piece. Using these test specimens, the tensile strength and elongation of the vulcanizate were measured in accordance with Japanese Industrial Standard JISK 6251, and the vulcanizate was measured using a Durometer overnight hardness tester type に 従 い in accordance with JIS Κ 6253. The hardness was measured.
耐熱性 Heat-resistant
上記常態物性を測定した後、 試験片を 120でに保持し、 168時間後と 33 6時間後に、 それぞれ、 加硫物の引張強さ (MP a) 、 伸び (%) および硬さを 測定し、 それらの測定値の高温保持前に対する変化率 (%) を調べた。 変化の大 きいものほど耐熱性に劣る。 After measuring the above normal physical properties, the specimen was kept at 120, and after 168 hours and 336 hours, the tensile strength (MPa), elongation (%) and hardness of the vulcanized product were measured, respectively. The rate of change (%) of those measured values before holding at a high temperature was examined. The larger the change, the lower the heat resistance.
動特性 Dynamic characteristics
直径 17. 8±0. lmm、 高さ 25±0. 15 mmの円柱状の試験片を、 1 60°Cで 20分間加硫した後、 ASTM D 623— 78で規定されるフレクソ メーター試験で評価した。 試験は、 グッドリッチフレクソメーターを用いて、 試 験温度 100°C、 初期荷重 25ポンド (11. 34kg) 、 動的変位 4. 45m mの条件で 25分間動的変位を加えて行い、 HBU (発熱量 [で] :測定された
試験片の温度と雰囲気温度 1 o ot:との差を発熱温度とした) および PS (永久 ひずみ) (%) を測定した。 HBUと PSは小さいほど動特性が優れている。 定伸長疲労性 After vulcanizing a cylindrical test specimen with a diameter of 17.8 ± 0.1 mm and a height of 25 ± 0.15 mm at 160 ° C for 20 minutes, a flexometer test specified in ASTM D 623-78 was applied. evaluated. The test was performed using a Goodrich Flexometer at a test temperature of 100 ° C, an initial load of 25 pounds (11.34 kg), a dynamic displacement of 4.45 mm, and a dynamic displacement of 25 minutes, with the HBU applied. (Calorific value [in]: measured The difference between the temperature of the test piece and the ambient temperature of 1 oot: was defined as the exothermic temperature) and PS (permanent strain) (%) were measured. The smaller the HBU and PS, the better the dynamic characteristics. Constant elongation fatigue
調製した加硫性ゴム組成物を 16 O で 20分間、 プレス圧 1 OMP aで加硫 を行い、 厚さ 2 mmのシートを得た。 このシートを 3号形ダンベルを用いて打ち 抜いて、 試験片を作製した。 これらの試験片を用いて、 両端をつかみ具でその間 の距離が 75 mmになるように固定し、 試験片が 0〜100%伸張を与えられる よう毎分 300回、 23 °Cで繰返し往復運動をおこない、 試験片が破断にいたる 回数を測定した。 The prepared vulcanizable rubber composition was vulcanized at 16 O for 20 minutes under a pressure of 1 OMPa to obtain a sheet having a thickness of 2 mm. This sheet was punched out using a No. 3 dumbbell to prepare a test piece. Using these test pieces, fix both ends with a gripper so that the distance between them is 75 mm, and repeat reciprocating motion at 23 ° C 300 times per minute so that the test pieces can be extended 0 to 100%. And the number of times the test piece was broken was measured.
圧縮永久ひずみ Compression set
直径 29mm、厚さ 12. 5 mmの金型を用いて、加硫性ゴム組成物を 160 で 25分間、プレス圧 10 M P aで加硫して、試験片を得た。圧縮永久ひずみ(%) は、 J I S K 6262に従い、 これらの試験片を用いて、 25%圧縮状態で 1 20°Cにて 70時間保持した後と、 168時間保持した後、 測定した。 Using a mold having a diameter of 29 mm and a thickness of 12.5 mm, the vulcanizable rubber composition was vulcanized at 160 at a press pressure of 10 MPa for 25 minutes to obtain a test piece. The compression set (%) was measured in accordance with JIS K 6262 using these test specimens after maintaining them in a 25% compressed state at 120 ° C. for 70 hours and after maintaining them for 168 hours.
実施例 1 Example 1
二トリル基含有共重合ゴム A— 1 (N i p o 1 DN 1042AL、 日本ゼォ ン社製、 アクリロニトリル—ブタジエン共重合ゴム、 アクリロニトリル単位含有 量 33. 5%、 ヨウ素価約 313、 ム一二一粘度 ML1+4, (100 ) 46) 40部、 二トリル基含有共重合ゴム B (Z e t po l 2030 L、 日本ゼオン 社製、 水素化アクリロニトリル一ブタジエン共重合ゴム、 アクリロニトリル単位 含有量 36. 2%、 ヨウ素価約 56、 ム一二一粘度 ML1+4, (100 ) 57. 5) 60部、 カーボンブラック (N762、 旭 # 50、 旭力一ボン社製) 65部、 ステアリン酸 1部、 酸化亜鉛 5部、 トリー (2 -ェチルへキシル) トリメリテー ト (可塑剤) 8部、 2, 2, 4一トリメチル— 1, 2—ジヒドロキノリン重合物Nitrile group-containing copolymer rubber A-1 (Nipo 1 DN 1042AL, manufactured by Nippon Zeon Co., Ltd., acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 33.5%, iodine value about 313, ML 1 + 4 , (100) 46) 40 parts, nitrile group-containing copolymer rubber B (Z etpol 2030L, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 36.2 %, Iodine value approx. 56, mu-viscosity ML 1 + 4 , (100) 57.5) 60 parts, carbon black (N762, Asahi # 50, Asahi Rikibon Co., Ltd.) 65 parts, stearic acid 1 part , Zinc oxide 5 parts, tree (2-ethylhexyl) trimellitate (plasticizer) 8 parts, 2,2,4-trimethyl-1,2-dihydroquinoline polymer
(老化防止剤、 No c r a c 224、 大内新興社製) 1. 5部、 N—イソプロ ピル一 N'—フエニル一 p—フエ二レンジァミン (老化防止剤) 1. 5部、 ヮッ クス (サン夕イト S、 精工科学社製) 1部、 粉末硫黄 (325メッシュ通過品) 0. 8部、 加硫促進剤 (テトラメチルチウラムジスルフイド 1. 5部および N— シクロへキシル— 2—ベンゾチアジルスルフェンアミド 1.5部) 3部を、 50t:
でロール混練して加硫性ゴム組成物を調製した。この加硫性ゴム組成物を用いて、 加硫し、 各試験片を製造し、 耐熱性、 動特性、 定伸長疲労性および圧縮永久ひず みを評価した。 結果を表 1に示す。 (Anti-aging agent, No crac 224, manufactured by Ouchi Shinko Co., Ltd.) 1.5 parts, N-isopropyl-1-N'-phenyl-p-phenylenediamine (anti-aging agent) 1.5 parts, Pex Light S (manufactured by Seiko Kagaku Co., Ltd.) 1 part, powdered sulfur (pass through 325 mesh) 0.8 part, vulcanization accelerator (1.5 parts tetramethylthiuram disulphide) and N-cyclohexyl-2-benzothia 1.5 parts of jilsulfenamide) 3 parts, 50t: And kneaded in a roll to prepare a vulcanizable rubber composition. Using this vulcanizable rubber composition, vulcanization was performed to produce each test piece, and heat resistance, dynamic characteristics, constant elongation fatigue resistance, and permanent compression strain were evaluated. Table 1 shows the results.
実施例 2 Example 2
二トリル基含有共重合ゴム A— 1の量を 40部から 20部に、 二トリル基含有 共重合ゴム Bの量を 60部から 80部に変えた他は実施例 1と同様に処理した。 結果を表 1に示す。 The same treatment as in Example 1 was conducted except that the amount of the nitrile group-containing copolymer rubber A-1 was changed from 40 parts to 20 parts and the amount of the nitrile group-containing copolymer rubber B was changed from 60 parts to 80 parts. Table 1 shows the results.
実施例 3 Example 3
二トリル基含有共重合ゴム A— 1の代わりに二トリル基含有共重合ゴム A— 2 (N i po l D 1201 L、 日本ゼオン社製、 アクリロニトリル—ブ夕ジェ ン一イソプレン共重合ゴム、 アクリロニトリル単位含有量 35 %、 ヨウ素価約 2 80、 ム一ニー粘度 ML1+4, (l O O :) 46) を用いた他は実施例 1と同様 に処理した。 結果を表 1に示す。 Instead of nitrile group-containing copolymer rubber A-1, nitrile group-containing copolymer rubber A-2 (Nipol D 1201 L, manufactured by Zeon Corporation, acrylonitrile-butene-isoprene copolymer rubber, acrylonitrile The treatment was carried out in the same manner as in Example 1 except that a unit content of 35%, an iodine value of about 280, and a muny viscosity ML 1 + 4 ( 100 :) 46) were used. Table 1 shows the results.
実施例 4 Example 4
硫黄の量を 1. 3部に変えた他は実施例 1と同様に処理した。 結果を表 1に示 す。 The procedure was as in Example 1, except that the amount of sulfur was changed to 1.3 parts. The results are shown in Table 1.
実施例 5 Example 5
粉末硫黄 0. 8部の代わりに 4, 4'ージチォジモルホリン 3部 (硫黄換算量 0. 91部) を用いた他は実施例 1と同様に処理した。 結果を表 1に示す。 比較例 1 The same procedure as in Example 1 was carried out except that instead of 0.8 parts of powdered sulfur, 3 parts of 4,4′-dithiodimorpholine (equivalent to 0.91 part of sulfur) was used. Table 1 shows the results. Comparative Example 1
二トリル基含有共重合ゴム A— 1を用いず、 ニトリル基含有共重合ゴム Bの量 を 60部から 100部に変えた他は実施例 1と同様に処理した。 結果を表 1に示 す。 The same treatment as in Example 1 was carried out except that the nitrile group-containing copolymer rubber A-1 was not used and the amount of the nitrile group-containing copolymer rubber B was changed from 60 parts to 100 parts. The results are shown in Table 1.
比較例 2 Comparative Example 2
二トリル基含有共重合ゴム A— 1の量を 40部から 100部に変え、 二トリル 基含有共重合ゴム Bを用いなかった他は実施例 1と同様に処理した。 結果を表 1 に示す。 The processing was performed in the same manner as in Example 1 except that the amount of the nitrile group-containing copolymer rubber A-1 was changed from 40 parts to 100 parts, and the nitrile group-containing copolymer rubber B was not used. Table 1 shows the results.
比較例 3
二トリル基含有共重合ゴム A— 1の量を 40部から 70部に、 二トリル基含有 共重合ゴム Bの量を 60部から 30部に変えた他は実施例 1と同様に処理した。 結果を表 1に示す。 Comparative Example 3 The same treatment as in Example 1 was carried out except that the amount of the nitrile group-containing copolymer rubber A-1 was changed from 40 parts to 70 parts and the amount of the nitrile group-containing copolymer rubber B was changed from 60 parts to 30 parts. Table 1 shows the results.
比較例 4 Comparative Example 4
二トリル基含有共重合ゴム Bに代えて二トリル基含有共重合ゴム b (Ze t p o 1 2020、 日本ゼオン社製、 水素化アクリロニトリル一ブタジエン共重合 ゴム、 アクリロニトリル単位含有量 36. 2%、 ヨウ素価約 28、 ムーニー粘度 ML1+4, (100°C) 78) を用いた他は実施例 1と同様に処理した。 結果を 表 1に示す。 Instead of nitrile group-containing copolymer rubber B, nitrile group-containing copolymer rubber b (Ze tpo 1 2020, manufactured by Zeon Corporation, hydrogenated acrylonitrile-butadiene copolymer rubber, acrylonitrile unit content 36.2%, iodine value The same treatment as in Example 1 was carried out except that about 28, Mooney viscosity ML 1 + 4 , (100 ° C) 78) was used. Table 1 shows the results.
比較例 5 Comparative Example 5
粉末硫黄の量を 0. 8部から 2. 5部に変えた他は実施例 1と同様に処理した。 結果を表 1に示す。
The procedure was as in Example 1, except that the amount of sulfur powder was changed from 0.8 parts to 2.5 parts. Table 1 shows the results.
表 1に示されるように、ヨウ素価の大きい二トリル基含有共重合ゴム (A) を 含有しないゴム組成物の加硫物 (比較例 1 ) は、 圧縮永久ひずみが大きく、 定伸 長疲労試験での破断回数が小さい。 ョゥ素価の小さい二トリル基含有共重合ゴム (B) を含有しないゴム組成物の加硫物 (比較例 2 ) は、 定伸長疲労試験での破 断回数が小さい。 ヨウ素価の大きい二トリル基含有共重合ゴム (A) が多く、 ョ ゥ素価の小さい二トリル基含有共重合ゴム(B)が少ないゴム組成物の加硫物(比 較例 3 ) は、 定伸長疲労試験での破断回数が小さい。 ヨウ素価の小さすぎるニト リル基含有共重合ゴム (b ) を用いたゴム組成物の加硫物 (比較例 4 ) は、 圧縮 永久ひずみが大きすぎる。硫黄量の多すぎるゴム組成物の加硫物(比較例 5 ) は、 常態物性でも伸びが小さいが、 熱を加えると伸びの低下の割合が大きく、 而 ί熱性 に劣る。 また、 P Sにも劣る。 As shown in Table 1, the vulcanizate of the rubber composition containing no nitrile group-containing copolymer rubber (A) having a high iodine value (Comparative Example 1) has a large compression set and a constant elongation fatigue test. The number of breaks at is small. The vulcanizate of the rubber composition containing no nitrile group-containing copolymer rubber (B) having a low iodine value (Comparative Example 2) has a small number of breaks in the constant elongation fatigue test. The vulcanizate of a rubber composition containing a large amount of nitrile group-containing copolymer rubber having a large iodine value (A) and a small amount of a nitrile group-containing copolymer rubber having a small iodine value (B) (Comparative Example 3) is as follows. Small number of breaks in constant elongation fatigue test. The vulcanizate (Comparative Example 4) of the rubber composition using the nitrile group-containing copolymer rubber (b) having an iodine value that is too small has too large a compression set. The vulcanizate of the rubber composition having an excessive amount of sulfur (Comparative Example 5) has a small elongation even in normal physical properties, but the rate of elongation decreases greatly when heat is applied, and the heat resistance is poor. It is also inferior to PS.
それに対し、 本発明のゴム組成物の加硫物 (実施例 1 ~ 5 ) は、 圧縮永久ひず みが小さく、 耐熱性にも優れ、 H B Uと P Sが小さく、 低伸長疲労試験での破断 回数が大きく、 破断しにくい。 産業上の利用可能性 On the other hand, the vulcanizates of the rubber composition of the present invention (Examples 1 to 5) have a small compression set, excellent heat resistance, small HBU and PS, and a low number of fractures in the low elongation fatigue test. Large and difficult to break. Industrial applicability
本発明の二トリル基含有共重合ゴム加硫物は、 動特性および耐熱性に優れ、 圧 縮永久ひずみが小さいという特性を有する。 従って、 この加硫物は、 これらの特 性が活用されるホース、 チューブ、 シール、 ガスケット、 ブーツ、 ロール、 ベル ト、 ダイアフラムなどとして有用であるが、 特に動的状態で使用されるロール、 ベルト、 ブーツ、 ダイアフラムなどに好適である。
The vulcanizate of the nitrile group-containing copolymer rubber of the present invention has excellent dynamic characteristics and heat resistance, and has characteristics of low compression set. Therefore, this vulcanized product is useful as hoses, tubes, seals, gaskets, boots, rolls, belts, diaphragms, etc., in which these characteristics are utilized, but especially for rolls and belts used in dynamic conditions. It is suitable for boots, diaphragms and the like.
Claims
1. ひ, /3—ェチレン性不飽和二トリル単量体単位含有量 10〜 60重量%、 ヨウ素価 180〜 430の二トリル基含有共重合ゴム (A) 5〜 50重量部およ び α, )3—ェチレン性不飽和二トリル単量体単位含有量 10〜60重量%、 ヨウ 素価 40〜100のニトリル基含有共重合ゴム (Β) 50〜95重量部からなる ゴム成分 100重量部と、 硫黄および 4, 4'—ジチォジモルホリンの中から選 ばれた少なくとも一種の加硫剤を硫黄量換算で 0. 1〜: 1. 5重量部含有する加 硫性ゴム組成物。 1. A copolymer rubber containing a nitrile group having a unit content of 10/3 to 60% by weight of a 3 / 3-ethylenically unsaturated nitrile monomer and an iodine value of 180 to 430 (A) 5 to 50 parts by weight and α ,) 3-nitrile unsaturated nitrile monomer unit content 10 to 60% by weight, iodine value 40 to 100 nitrile group-containing copolymer rubber (I) 50 to 95 parts by weight Rubber component 100 parts by weight And 0.1 to 1.5 parts by weight of sulfur and at least one vulcanizing agent selected from 4,4'-dithiodimorpholine in terms of sulfur amount.
2. ニトリル基含有共重合ゴム (Α) および二トリル基含有共重合ゴム (Β) が、 ひ, /3—ェチレン性不飽和二トリル単量体単位 10〜 60重量%と、共役ジェ ン単量体、 非共役ジェン単量体および α—ォレフィン単量体の中から選ばれた少 なくとも一種の単量体の単位 40〜90重量%とからなる共重合ゴムである請求 項 1記載の加硫性ゴム組成物。 2. The nitrile group-containing copolymer rubber (Α) and the nitrile group-containing copolymer rubber (、) consist of 10 to 60% by weight of ひ / 3-ethylenically unsaturated nitrile monomer unit and The copolymer rubber according to claim 1, which is a copolymer rubber comprising units of at least one monomer selected from a monomer, a non-conjugated diene monomer and an α-olefin monomer in an amount of 40 to 90% by weight. Vulcanizable rubber composition.
3. ニトリル基含有共重合ゴム (Α) および二トリル基含有共重合ゴム (Β) が、 ひ, ]3 _エチレン性不飽和二トリル単量体単位 10〜60重量%と共役ジェ ン単量体単位 40〜 90重量%とからなる共重合ゴムである請求項 1記載の加硫 性ゴム組成物。 3. The nitrile group-containing copolymer rubber (Α) and the nitrile group-containing copolymer rubber (Β) consist of 10% to 60% by weight of [3] ethylenically unsaturated nitrile monomer unit and 10% by weight of conjugated gen. 2. The vulcanizable rubber composition according to claim 1, which is a copolymer rubber comprising 40 to 90% by weight of a body unit.
4. 二トリル基含有共重合ゴム (Α) がョゥ素価 200〜 400を有するも のである請求項 1〜 3のいずれかに記載の加硫性ゴム組成物。 4. The vulcanizable rubber composition according to any one of claims 1 to 3, wherein the nitrile group-containing copolymer rubber (Α) has an iodine value of 200 to 400.
5. 二トリル基含有共重合ゴム (Β) がヨウ素価 45〜 90を有するもので ある請求項 1〜4のいずれかに記載の加硫性ゴム組成物。 5. The vulcanizable rubber composition according to any one of claims 1 to 4, wherein the nitrile group-containing copolymer rubber (Β) has an iodine value of 45 to 90.
6. 二トリル基含有共重合ゴム (Α) がム一二一粘度 (ML1+4, 10 O :) 20〜 300を有するものである請求項 1〜 5のいずれかに記載の加硫性ゴム組 成物。 6. The vulcanizability according to any one of claims 1 to 5, wherein the nitrile group-containing copolymer rubber (Α) has a viscosity of 221 (ML 1 + 4 , 10 O :) 20 to 300. Rubber composition.
7. 二トリル基含有共重合ゴム (B) がム一二一粘度 (ML1+4, 100で) 10〜300を有するものである請求項 1〜6のいずれかに記載の加硫性ゴム組 成物。
7. The vulcanizable rubber according to any one of claims 1 to 6, wherein the nitrile group-containing copolymer rubber (B) has a viscosity of 10 to 300 (ML 1 + 4 , 100). Composition.
8 . ゴム成分が、 該ゴム成分 1 0 0重量部に基づき、 二トリル基含有共重合 ゴム (A) 1 0〜4 5重量部および二トリル基含有共重合ゴム (B ) 5 5〜9 0 重量部からなる請求項 1〜 7のいずれかに記載の加硫性ゴム組成物。 8. The rubber component is composed of 100 to 45 parts by weight of the nitrile group-containing copolymer rubber (A) and 100 to 45 parts by weight of the nitrile group-containing copolymer rubber (B) 55 to 90 based on 100 parts by weight of the rubber component. The vulcanizable rubber composition according to any one of claims 1 to 7, comprising parts by weight.
9 . ゴム成分 1 0 0重量部に基づき、 該加硫剤を硫黄量換算で 0 . 2〜 1重 量部含有する請求項 1〜 8のいずれかに記載の加硫性ゴム組成物。 9. The vulcanizable rubber composition according to any one of claims 1 to 8, wherein the vulcanizing agent is contained in an amount of 0.2 to 1 part by weight in terms of sulfur based on 100 parts by weight of the rubber component.
1 0 . 請求項 1〜 9のいずれかに記載の加硫性ゴム組成物を加硫してなる加 硫物。
10. A vulcanizate obtained by vulcanizing the vulcanizable rubber composition according to any one of claims 1 to 9.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001398663A JP2003192834A (en) | 2001-12-28 | 2001-12-28 | Vulcanizable rubber composition and vulcanizate |
JP2001-398663 | 2001-12-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003057775A1 true WO2003057775A1 (en) | 2003-07-17 |
Family
ID=19189377
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/013764 WO2003057775A1 (en) | 2001-12-28 | 2002-12-27 | Vulcanizable rubber composition and vulcanizate |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2003192834A (en) |
WO (1) | WO2003057775A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115011026A (en) * | 2022-07-11 | 2022-09-06 | 北京化工大学 | A kind of high temperature resistant oil resistant high barrier thermoplastic vulcanizate and preparation method thereof |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3006498A4 (en) * | 2013-05-30 | 2017-01-18 | Zeon Corporation | Nitrile copolymer rubber composition, crosslinkable rubber composition, and crosslinked rubber |
JP6389055B2 (en) * | 2014-04-16 | 2018-09-12 | 株式会社ブリヂストン | Rubber composition for hose and hydraulic hose |
CN111386307B (en) | 2017-11-24 | 2021-03-16 | Nok株式会社 | NBR composition for rubber laminate metal |
CN110724319A (en) * | 2019-11-19 | 2020-01-24 | 江苏创合橡塑有限公司 | Formula of high-hardness low-pressure-change nitrile rubber composition material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63142046A (en) * | 1986-12-03 | 1988-06-14 | Chugoku Rubber Kogyo Kk | Rubber composition |
JPH0967471A (en) * | 1995-08-31 | 1997-03-11 | Mitsubishi Cable Ind Ltd | Composition for sealing material and sealing material |
WO1998049227A1 (en) * | 1997-04-30 | 1998-11-05 | Nippon Zeon Co., Ltd. | Vulcanizable rubber composition |
-
2001
- 2001-12-28 JP JP2001398663A patent/JP2003192834A/en active Pending
-
2002
- 2002-12-27 WO PCT/JP2002/013764 patent/WO2003057775A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63142046A (en) * | 1986-12-03 | 1988-06-14 | Chugoku Rubber Kogyo Kk | Rubber composition |
JPH0967471A (en) * | 1995-08-31 | 1997-03-11 | Mitsubishi Cable Ind Ltd | Composition for sealing material and sealing material |
WO1998049227A1 (en) * | 1997-04-30 | 1998-11-05 | Nippon Zeon Co., Ltd. | Vulcanizable rubber composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115011026A (en) * | 2022-07-11 | 2022-09-06 | 北京化工大学 | A kind of high temperature resistant oil resistant high barrier thermoplastic vulcanizate and preparation method thereof |
CN115011026B (en) * | 2022-07-11 | 2023-08-29 | 北京化工大学 | A kind of high temperature resistant oil resistant high barrier thermoplastic vulcanizate and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2003192834A (en) | 2003-07-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101652424B (en) | nitrile copolymer rubber composition and nitrile copolymer latex composition | |
CN103703073B (en) | Highly saturated copolymer rubber composition containing nitrile group | |
CN106068290B (en) | Nitrile group-containing copolymer rubber, cross-linkable rubber composition and rubber cross-linked product | |
EP0704479B1 (en) | Composite of highly saturated nitrile rubber with fiber, and belt composed thereof | |
EP3284781B1 (en) | Composition for rubber and use thereof | |
US4965323A (en) | Method of vulcanizing rubber at pH 5 to 10 | |
KR102488924B1 (en) | Hydrogenated nitrile-diene-carboxylic acid ester copolymer | |
CN110352217B (en) | Nitrile group-containing copolymer rubber and crosslinked nitrile group-containing copolymer rubber | |
EP2746330A1 (en) | Nitrile copolymer rubber composition and rubber crosslink | |
EP1277796B1 (en) | Nitrile rubber composition, vulcanizable nitrile rubber composition, and vulcanizate | |
WO2015136792A1 (en) | Rubber composition and vulcanized product thereof | |
US6812312B1 (en) | Rubber, rubber composition, and crosslinked object | |
WO2003057775A1 (en) | Vulcanizable rubber composition and vulcanizate | |
JP7422266B1 (en) | Rubber composition and tire bladder | |
WO2017146046A1 (en) | Nitrile copolymer rubber composition, crosslinkable rubber composition and rubber crosslinked product | |
CN118974159A (en) | Dip-molded article, chloroprene polymer, and method for producing dip-molded article | |
JP4019808B2 (en) | Crosslinkable acrylic rubber composition | |
JP2004250645A (en) | Nitrile copolymer rubber composition and cross-linked molded article | |
JP2004323629A (en) | Rubber composition, vulcanizate and air intake hose | |
JP2017141369A (en) | Rubber composition, vulcanizate and molded article of the same | |
CN105229072A (en) | Lonitrile copolymer rubber combination, bridging property rubber combination and rubber cross thing | |
KR20200098516A (en) | Nitrile-diene-carboxylic acid ester copolymer | |
WO2019163482A1 (en) | Nitrile copolymer rubber composition, crosslinkable rubber composition, crosslinked rubber object, and hose | |
JPH08231769A (en) | Vulcanizable nitrile-based rubber composition | |
JP3562018B2 (en) | Vulcanizable nitrile rubber composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SI SK TR |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
122 | Ep: pct application non-entry in european phase |