JPWO2007026707A1 - Nitrile copolymer rubber cross-linked product, nitrile copolymer rubber composition, and method for producing the composition - Google Patents
Nitrile copolymer rubber cross-linked product, nitrile copolymer rubber composition, and method for producing the composition Download PDFInfo
- Publication number
- JPWO2007026707A1 JPWO2007026707A1 JP2007533262A JP2007533262A JPWO2007026707A1 JP WO2007026707 A1 JPWO2007026707 A1 JP WO2007026707A1 JP 2007533262 A JP2007533262 A JP 2007533262A JP 2007533262 A JP2007533262 A JP 2007533262A JP WO2007026707 A1 JPWO2007026707 A1 JP WO2007026707A1
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- JP
- Japan
- Prior art keywords
- copolymer rubber
- weight
- nitrile copolymer
- nitrile
- plasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 152
- 239000005060 rubber Substances 0.000 title claims abstract description 152
- 229920001577 copolymer Polymers 0.000 title claims abstract description 130
- 239000000203 mixture Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 104
- -1 ester compound Chemical class 0.000 claims abstract description 62
- 239000004014 plasticizer Substances 0.000 claims abstract description 51
- 150000002825 nitriles Chemical class 0.000 claims abstract description 45
- 239000003502 gasoline Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000035699 permeability Effects 0.000 claims abstract description 29
- 150000001875 compounds Chemical group 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004816 latex Substances 0.000 claims description 21
- 229920000126 latex Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 150000001993 dienes Chemical class 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 12
- SCABKEBYDRTODC-UHFFFAOYSA-N bis[2-(2-butoxyethoxy)ethyl] hexanedioate Chemical compound CCCCOCCOCCOC(=O)CCCCC(=O)OCCOCCOCCCC SCABKEBYDRTODC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 7
- 239000008247 solid mixture Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical group CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- IHTSDBYPAZEUOP-UHFFFAOYSA-N bis(2-butoxyethyl) hexanedioate Chemical compound CCCCOCCOC(=O)CCCCC(=O)OCCOCCCC IHTSDBYPAZEUOP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010058 rubber compounding Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 45
- 235000019441 ethanol Nutrition 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000010410 layer Substances 0.000 description 24
- 238000004132 cross linking Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003431 cross linking reagent Substances 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 239000000446 fuel Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-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
- 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
- 241001441571 Hiodontidae Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 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
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000011243 crosslinked material Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- 230000005068 transpiration Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- ZMQWRASVUXJXGM-VOTSOKGWSA-N (e)-4-cyclohexyloxy-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C\C(=O)OC1CCCCC1 ZMQWRASVUXJXGM-VOTSOKGWSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- SBZHWGCCMZJOGI-WQMAPKSTSA-N (z)-but-2-enedioic acid;(z)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(O)=O.CCOC(=O)\C=C/C(O)=O SBZHWGCCMZJOGI-WQMAPKSTSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
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- WDRCVXGINNJWPH-UHFFFAOYSA-N tris(6-methylheptyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C(C(=O)OCCCCCC(C)C)=C1 WDRCVXGINNJWPH-UHFFFAOYSA-N 0.000 description 1
- YPDXSCXISVYHOB-UHFFFAOYSA-N tris(7-methyloctyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC(C)C)C(C(=O)OCCCCCCC(C)C)=C1 YPDXSCXISVYHOB-UHFFFAOYSA-N 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- 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)
- Laminated Bodies (AREA)
Abstract
α、β−エチレン性不飽和ニトリル単量体単位５５〜８０重量％を有するニトリル共重合体ゴム（Ａ）１００重量部に対して、可塑剤（Ｂ）０.１〜１００重量部を含有してなる、脆化温度が−５０〜−５℃であるニトリル共重合体ゴム架橋物。好ましくは、イソオクタン／トルエン／エタノールの重量比が４０／４０／２０であるガソホールのガソリン透過係数が２００ｇ・ｍｍ／ｍ２・ｄａｙ以下であり、また好ましくは、前記可塑剤（Ｂ）が特定のジカルボン酸化合物とエーテル結合含有アルコールとのエステル化合物である。この発明によると、不飽和ニトリル単量体単位含有量が極めて高いにも拘わらず脆化温度が低く（耐寒性に優れ）、耐ガソリン透過性の低い（耐ガソリン透過性に優れた）ニトリル共重合体ゴム架橋物を提供することができる。It contains 0.1 to 100 parts by weight of a plasticizer (B) with respect to 100 parts by weight of a nitrile copolymer rubber (A) having 55 to 80% by weight of α, β-ethylenically unsaturated nitrile monomer units. A nitrile copolymer rubber cross-linked product having an embrittlement temperature of -50 to -5 ° C. Preferably, the gasoline permeability coefficient of gasohol having a weight ratio of isooctane / toluene / ethanol of 40/40/20 is 200 g · mm / m 2 · day or less, and preferably, the plasticizer (B) is a specific dicarboxylic acid. It is an ester compound of an acid compound and an ether bond-containing alcohol. According to the present invention, although the content of unsaturated nitrile monomer units is extremely high, the nitrile copolymer has a low embrittlement temperature (excellent cold resistance) and low gasoline permeability resistance (excellent gasoline permeability resistance). A polymer rubber cross-linked product can be provided.
Description
本発明は、不飽和ニトリル単量体単位含有量が極めて高いにも拘わらず脆化温度が低く（耐寒性に優れ）、さらには、ガソリン透過性の低い（耐ガソリン透過性に優れた）ニトリル共重合体ゴム架橋物に関する。 The present invention provides a nitrile having a low embrittlement temperature (excellent in cold resistance) despite its extremely high content of unsaturated nitrile monomer units, and further low gasoline permeability (excellent in gasoline permeability resistance). The present invention relates to a crosslinked copolymer rubber.
従来から、α、β−エチレン性不飽和ニトリル単量体単位と、共役ジエン単量体単位又はオレフィン単量体単位と、を含有するゴム（ニトリル共重合体ゴム）は、耐油性に優れるゴムとして知られており、その架橋物は主に燃料用ホース、ガスケット、パッキン、オイルシールなど自動車の各種油類まわりのゴム製品の材料として用いられている。このようなニトリル共重合体ゴムにおいては、一般に、α、β−エチレン性不飽和ニトリル単量体単位の含有量（略して「ニトリル含量」と記す。）を大きくすれば、ガソリン透過性が低くなるが、一方、脆化温度が上昇して、ゴム弾性が低下するという性質を有している。そのため、ニトリル含量が４３〜５０重量％の超高ニトリルのニトリル共重合体ゴムは、しばしば可塑剤を配合して軟化させて使用されている。 Conventionally, a rubber (nitrile copolymer rubber) containing an α, β-ethylenically unsaturated nitrile monomer unit and a conjugated diene monomer unit or an olefin monomer unit is a rubber excellent in oil resistance. The crosslinked product is mainly used as a material for rubber products around various oils of automobiles such as fuel hoses, gaskets, packings, oil seals and the like. In such a nitrile copolymer rubber, generally, if the content of the α, β-ethylenically unsaturated nitrile monomer unit (abbreviated as “nitrile content”) is increased, the gasoline permeability is lowered. However, on the other hand, the embrittlement temperature rises and the rubber elasticity is lowered. Therefore, nitrile copolymer rubbers having an nitrile content of 43 to 50% by weight are often used after being softened with a plasticizer.
最近、世界的な環境保護活動の高まりにより、ガソリンなどの燃料の大気中への蒸散量の削減への取り組みが進んでいる。例えば、日本や欧州ではＮＯＸ排出が規制され、これに伴って燃料蒸散量の低減が求められている。また、わが国では燃料ホース、シール、パッキンなどの用途においてもガソリン透過性が一層低いことが求められるようになってきている。一方、米国ではカリフォルニア州で２００４年から排ガス中の燃料ガス濃度の規制が段階的に強化されている（ＬＥＶＩＩ）。 Recently, due to the increase in global environmental protection activities, efforts are being made to reduce the transpiration of fuels such as gasoline into the atmosphere. For example, NOX emissions are regulated in Japan and Europe, and accordingly, reduction of fuel transpiration is required. In Japan, gasoline permeation is required to be even lower in applications such as fuel hoses, seals, and packing. On the other hand, in the United States, regulations on fuel gas concentration in exhaust gas have been gradually strengthened since 2004 in California (LEVII).
このような状況に対して、特許文献１では、ニトリル含量が４５重量％以上の極高ニトリル（実施例ではニトリル含量が４８重量％）のニトリル共重合体ゴムに対して、耐寒性可塑剤の配合量を増大させて、ガソリン透過性および脆化温度をそれぞれ特定の数値以下とした架橋物層を備えた燃料用ゴムホースが提案されている。しかし、市場からは、さらにニトリル含量の高いゴムの使用を前提としてでも、ガソリン透過性を一層低減させることが望まれている。 For this situation, Patent Document 1 discloses that a cold-resistant plasticizer is used for a nitrile copolymer rubber having a nitrile content of 45% by weight or more (in the examples, the nitrile content is 48% by weight). There has been proposed a fuel hose for a fuel provided with a cross-linked layer in which the blending amount is increased and the gasoline permeability and the embrittlement temperature are respectively set to specific values or less. However, it is desired from the market to further reduce gasoline permeability even on the premise of using rubber having a higher nitrile content.
特許文献２では、ニトリル含量４３〜５０重量％のニトリル共重合体ゴムと、特定の溶解度パラメーター及び分子量を有する塩化ビニル樹脂と、のブレンド物からなる燃料ホース用ゴム組成物が提案されている。しかし、環境問題が厳格になった昨今では、ハロゲンを多く含むゴム架橋物は望まれていない。 Patent Document 2 proposes a rubber composition for a fuel hose comprising a blend of a nitrile copolymer rubber having a nitrile content of 43 to 50% by weight and a vinyl chloride resin having a specific solubility parameter and molecular weight. However, in recent years when environmental problems have become severe, rubber cross-linked products containing a large amount of halogen are not desired.
また、特許文献３では、ガラス転移温度−１５〜３０℃、ガラス転移温度外挿終了温度７０℃以下として用いる超極高ニトリル（超極高ニトリルとは、ニトリル含量５５〜８０重量％の非常に高いニトリル含量であることを意味する。）のニトリル共重合体ゴムが提案されている。しかし、この特許文献３のゴムは脆化温度が−３〜１２℃と高いので使用温度環境が限られており、また可塑剤がブリードし易いものである。 Moreover, in patent document 3, the ultra-high nitrile used as a glass transition temperature -15-30 degreeC and the glass transition temperature extrapolation end temperature 70 degrees C or less (The ultra-high nitrile is a very nitrile content 55-80 weight%. A nitrile copolymer rubber having a high nitrile content has been proposed. However, since the rubber of Patent Document 3 has a high embrittlement temperature of −3 to 12 ° C., the operating temperature environment is limited, and the plasticizer tends to bleed.
そのため、ハロゲン化合物を多量含まず、超極高ニトリルのニトリル共重合体ゴムを用いた、脆化温度が少なくとも−５℃以下である架橋物の開発が望まれている。
本発明の目的は、不飽和ニトリル単量体単位含有量がいわゆる超極高レベルであっても、ガソリン透過性が低く、しかも脆化温度の低いニトリル共重合体ゴム架橋物を提供することにある。 An object of the present invention is to provide a crosslinked nitrile copolymer rubber having a low gasoline permeability and a low embrittlement temperature even when the unsaturated nitrile monomer unit content is a so-called ultra-high level. is there.
本発明者らは、前記課題を解決すべく鋭意研究した結果、例えば、ニトリル含量５５〜８０重量％の超極高ニトリルのニトリル共重合体ゴムのラテックスと、可塑剤のエマルションと、を混合し、その後、凝固、乾燥して得られる固形の混合物を架橋することにより上記の目的が達成されることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above-mentioned problems, the present inventors have mixed, for example, a latex of a very high nitrile nitrile copolymer rubber having a nitrile content of 55 to 80% by weight and an emulsion of a plasticizer. Then, it discovered that said objective was achieved by bridge | crosslinking the solid mixture obtained by coagulation | solidification and drying, and came to complete this invention.
かくして本発明によれば、α、β−エチレン性不飽和ニトリル単量体単位５５〜８０重量％を有するニトリル共重合体ゴム（Ａ）１００重量部に対して、可塑剤（Ｂ）０.１〜１００重量部を含有してなる、脆化温度が−５０〜−５℃であるニトリル共重合体ゴム架橋物が提供される。 Thus, according to the present invention, with respect to 100 parts by weight of the nitrile copolymer rubber (A) having 55 to 80% by weight of the α, β-ethylenically unsaturated nitrile monomer unit, the plasticizer (B) is 0.1. There is provided a crosslinked nitrile copolymer rubber having an embrittlement temperature of -50 to -5 ° C, comprising ~ 100 parts by weight.
該架橋物は、好ましくは、イソオクタン／トルエン／エタノールの重量比が４０／４０／２０であるガソホールに対するガソリン透過係数が、２００ｇ・ｍｍ／ｍ２・ｄａｙ以下である。好ましくは、前記可塑剤（Ｂ）が、下記一般式（１）で表される化学構造を有する化合物（ｂ１）と、エーテル結合含有アルコール（ｂ２）とのエステル化合物（ｂ）である。
ＨＯＯＣＲＣＯＯＨ （１）
（式中のＲは、炭素数２〜１０のアルキレン基を表し、ＣＯＯＨはカルボキシ基を表す。）The crosslinked product preferably has a gasoline permeability coefficient of 200 g · mm / m 2 · day or less with respect to gasohol having a weight ratio of isooctane / toluene / ethanol of 40/40/20. Preferably, the plasticizer (B) is an ester compound (b) of a compound (b1) having a chemical structure represented by the following general formula (1) and an ether bond-containing alcohol (b2).
HOOCRCOOH (1)
(R in the formula represents an alkylene group having 2 to 10 carbon atoms, and COOH represents a carboxy group.)
さらに、該架橋物は、好ましくは、前記α、β−エチレン性不飽和ニトリル単量体単位が、アクリロニトリル単位および／またはメタクリロニトリル単位である。好ましくは、前記ニトリル共重合体ゴム（Ａ）は、ジエン単量体単位および／またはα−オレフィン単量体単位２０〜４５重量％を、さらに有する。好ましくは、前記可塑剤（Ｂ）が、ジブトキシエチルアジペートおよび／またはジ（ブトキシエトキシエチル）アジペートである。 Further, in the cross-linked product, the α, β-ethylenically unsaturated nitrile monomer unit is preferably an acrylonitrile unit and / or a methacrylonitrile unit. Preferably, the nitrile copolymer rubber (A) further has 20 to 45% by weight of a diene monomer unit and / or an α-olefin monomer unit. Preferably, the plasticizer (B) is dibutoxyethyl adipate and / or di (butoxyethoxyethyl) adipate.
別の本発明によれば、α、β−エチレン性不飽和ニトリル単量体単位５５〜８０重量％を有するニトリル共重合体ゴム（Ａ）１００重量部に対して、可塑剤（Ｂ）０.１〜１００重量部を含有してなり、脆化温度が−５０〜−５℃である架橋物を与えるニトリル共重合体ゴム組成物が提供される。 According to another aspect of the present invention, the plasticizer (B) is added to 100 parts by weight of the nitrile copolymer rubber (A) having 55 to 80% by weight of α, β-ethylenically unsaturated nitrile monomer units. A nitrile copolymer rubber composition containing 1 to 100 parts by weight and giving a cross-linked product having an embrittlement temperature of -50 to -5 ° C is provided.
また別の本発明によれば、上記ニトリル共重合体ゴム組成物を製造する方法であって、α、β−エチレン性不飽和ニトリル単量体単位５５〜８０重量％を有するニトリル共重合体ゴム（Ａ）のラテックスと可塑剤（Ｂ）のエマルションとの混合液を調製する工程と、該混合液を凝固させ、その後、乾燥させて固形の混合物とする工程と、該混合物とゴム用配合剤とを混練する工程と、を含むことを特徴とするニトリル共重合体ゴム組成物の製造方法が提供される。該製造方法において、好ましくは、前記可塑剤（Ｂ）が、前記エステル化合物（ｂ）である。 According to another aspect of the present invention, there is provided a method for producing the nitrile copolymer rubber composition, wherein the nitrile copolymer rubber has 55 to 80% by weight of an α, β-ethylenically unsaturated nitrile monomer unit. A step of preparing a mixed solution of the latex of (A) and an emulsion of the plasticizer (B), a step of coagulating the mixed solution and then drying to form a solid mixture, and the mixture and a compounding agent for rubber And a step of kneading the nitrile copolymer rubber composition. In the production method, preferably, the plasticizer (B) is the ester compound (b).
さらにまた別の本発明によれば、上記いずれかのニトリル共重合体ゴム架橋物からなる層（Ｉ）を、少なくとも有する積層体、好ましくは、上記いずれかのニトリル共重合体ゴム架橋物からなり、厚み０.１〜１０ｍｍである層（Ｉ）と、α、β−エチレン性不飽和ニトリル単量体単位５重量％以上、５５重量％未満を有するニトリル共重合体ゴム（Ｌ）１００重量部に対して、可塑剤（Ｍ）０〜１００重量部含有し、脆化温度が−７０〜−１０℃であるニトリル共重合体ゴム架橋物からなり、厚み０.１〜１０ｍｍの層（ＩＩ）と、を積層してなる積層体が提供される。 According to still another aspect of the present invention, a laminate having at least a layer (I) comprising any of the above-mentioned crosslinked nitrile copolymer rubbers, preferably comprising any of the above-mentioned crosslinked nitrile copolymer rubbers. 100 parts by weight of a nitrile copolymer rubber (L) having a layer (I) having a thickness of 0.1 to 10 mm and an α, β-ethylenically unsaturated nitrile monomer unit of 5 wt% or more and less than 55 wt% In contrast, a layer (II) having a thickness of 0.1 to 10 mm, comprising 0 to 100 parts by weight of a plasticizer (M), comprising a crosslinked nitrile copolymer rubber having an embrittlement temperature of −70 to −10 ° C. Are provided.
本発明によれば、不飽和ニトリル単量体単位含有量がいわゆる超極高レベルであっても、ガソリン透過性が低く、しかも脆化温度の低いニトリル共重合体ゴム架橋物が提供される。 According to the present invention, a crosslinked nitrile copolymer rubber having a low gasoline permeability and a low embrittlement temperature is provided even when the unsaturated nitrile monomer unit content is at a so-called ultra-high level.
本発明のニトリル共重合体ゴム架橋物は、α、β−エチレン性不飽和ニトリル単量体単位５５〜８０重量％を有するニトリル共重合体ゴム（Ａ）１００重量部に対して、可塑剤（Ｂ）０.１〜１００重量部を含有してなり、脆化温度が−５０〜−５℃の範囲にある架橋物である。 The crosslinked nitrile copolymer rubber of the present invention comprises a plasticizer (100 parts by weight of a nitrile copolymer rubber (A) having 55 to 80% by weight of an α, β-ethylenically unsaturated nitrile monomer unit. B) A cross-linked product containing 0.1 to 100 parts by weight and having an embrittlement temperature in the range of -50 to -5 ° C.
ニトリル共重合体ゴム（Ａ）は、α，β−エチレン性不飽和ニトリル単量体単位を、全単量体単位１００重量％に対して、５５〜８０重量％、好ましくは５６〜７６重量％、より好ましくは５７〜７２重量％含有する。α，β−エチレン性不飽和ニトリル単量体単位の含有量が少なすぎると、架橋物の耐油性が悪化し、ガソリン透過性が高くなるおそれがある。逆に、α，β−エチレン性不飽和ニトリル単量体単位の含有量が多すぎると、脆化温度が高くなる可能性がある。 The nitrile copolymer rubber (A) is an α, β-ethylenically unsaturated nitrile monomer unit in an amount of 55 to 80% by weight, preferably 56 to 76% by weight, based on 100% by weight of all monomer units. More preferably, it contains 57 to 72% by weight. If the content of the α, β-ethylenically unsaturated nitrile monomer unit is too small, the oil resistance of the crosslinked product is deteriorated and the gasoline permeability may be increased. Conversely, if the content of the α, β-ethylenically unsaturated nitrile monomer unit is too large, the embrittlement temperature may be increased.
α，β−エチレン性不飽和ニトリル単量体単位を形成するα，β−エチレン性不飽和ニトリル単量体は、ニトリル基を有するα，β−エチレン性不飽和化合物であれば限定されない。このような化合物としては、アクリロニトリル；α−クロロアクリロニトリル、α−ブロモアクリロニトリルなどのα−ハロゲノアクリロニトリル；メタクリロニトリルなどのα−アルキルアクリロニトリル；などが挙げられる。これらの中ではアクリロニトリルおよび／またはメタクリロニトリルが好ましい。α，β−エチレン性不飽和ニトリル単量体は、これらの複数種を併用してもよい。 The α, β-ethylenically unsaturated nitrile monomer forming the α, β-ethylenically unsaturated nitrile monomer unit is not limited as long as it is an α, β-ethylenically unsaturated compound having a nitrile group. Examples of such a compound include acrylonitrile; α-halogenoacrylonitrile such as α-chloroacrylonitrile and α-bromoacrylonitrile; α-alkylacrylonitrile such as methacrylonitrile; Of these, acrylonitrile and / or methacrylonitrile are preferred. A plurality of these α, β-ethylenically unsaturated nitrile monomers may be used in combination.
ニトリル共重合体ゴム（Ａ）は、架橋物がゴム弾性を保有するために、通常、ジエン単量体単位またはα−オレフィン単量体単位をも有する。 The nitrile copolymer rubber (A) usually has a diene monomer unit or an α-olefin monomer unit because the crosslinked product has rubber elasticity.
ジエン単量体単位を形成するジエン単量体としては、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエンなどの好ましくは炭素数が４以上の共役ジエン単量体；１，４−ペンタジエン、１，４−ヘキサジエンなどの好ましくは炭素数が５〜１２の非共役ジエン単量体；が挙げられる。これらの中では共役ジエン単量体が好ましく、１，３−ブタジエンがより好ましい。 The diene monomer forming the diene monomer unit is preferably 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene or the like, preferably having 4 or more carbon atoms. Conjugated diene monomers; preferably non-conjugated diene monomers having 5 to 12 carbon atoms such as 1,4-pentadiene and 1,4-hexadiene. Among these, a conjugated diene monomer is preferable, and 1,3-butadiene is more preferable.
α−オレフィン単量体単位を形成するα−オレフィン単量体としては、炭素数が２〜１２のものが好ましく、エチレン、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテンなどが例示される。 As the α-olefin monomer forming the α-olefin monomer unit, those having 2 to 12 carbon atoms are preferable, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, Examples include 1-octene.
ニトリル共重合体ゴム（Ａ）におけるジエン単量体単位またはα−オレフィン単量体単位の含有量は、全単量体単位１００重量％に対して、４５〜２０重量％、好ましくは４４〜２４重量％未満、より好ましくは４３〜２８重量％である。これらの単量体単位が少なすぎると、架橋物のゴム弾性が低下するおそれがある。一方、多すぎると、耐熱老化性や耐化学的安定性が損なわれる可能性がある。 The content of the diene monomer unit or α-olefin monomer unit in the nitrile copolymer rubber (A) is 45 to 20% by weight, preferably 44 to 24%, based on 100% by weight of the total monomer units. Less than wt%, more preferably 43 to 28 wt%. When there are too few these monomer units, there exists a possibility that the rubber elasticity of a crosslinked material may fall. On the other hand, if too much, heat aging resistance and chemical stability may be impaired.
ニトリル共重合体ゴム（Ａ）は、上記α，β−エチレン性不飽和ニトリル単量体単位、ジエン単量体単位またはα−オレフィン単量体単位以外に、これらと共重合可能な他の単量体単位を、全単量体単位１００重量％に対して好ましくは２０重量％以下、より好ましくは１０重量％以下、特に好ましくは５重量％以下有していてもよい。 The nitrile copolymer rubber (A) is not limited to the above α, β-ethylenically unsaturated nitrile monomer unit, diene monomer unit, or α-olefin monomer unit, but other units copolymerizable therewith. The monomer unit may be preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less based on 100% by weight of the total monomer units.
かかる共重合可能な他の単量体としては、例えば、スチレン、α−メチルスチレン、ビニルトルエンなどの芳香族ビニル化合物；アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、無水フマル酸などのα，β−エチレン性不飽和カルボン酸及びその無水物；（メタ）アクリル酸メチル〔アクリル酸メチル及びメタクリル酸メチルの意。以下、（メタ）アクリル酸エチルなど同様。〕、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシルなどのα，β−エチレン性不飽和カルボン酸のアルキルエステル；マレイン酸モノ（ジ）エチル〔マレイン酸モノエチル及びマレイン酸ジエチルの意。以下、マレイン酸モノ（ジ）ブチルなど同様。〕、マレイン酸モノ（ジ）ブチル、フマル酸モノ（ジ）エチル、フマル酸モノ（ジ）ブチル、フマル酸モノ（ジ）シクロヘキシル、イタコン酸モノ（ジ）エチル、イタコン酸モノ（ジ）ブチルなどのα，β−エチレン性不飽和多価カルボン酸のモノ（ジ）エステル；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸メトキシプロピル、（メタ）アクリル酸ブトキシエチルなどのα，β−エチレン性不飽和カルボン酸のアルコキシアルキルエステル；（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピルなどのα，β−エチレン性不飽和カルボン酸のヒドロキシアルキルエステル；ビニルピリジンなどの複素環式芳香族ビニル単量体；Ｎ−（４−アニリノフェニル）アクリルアミド、Ｎ−（４−アニリノフェニル）メタクリルアミド、Ｎ−（４−アニリノフェニル）シンナムアミド、Ｎ−（４−アニリノフェニル）クロトンアミド、 Ｎ−フェニル−４−（３−ビニルベンジルオキシ）アニリン、Ｎ−フェニル−４−（４−ビニルベンジルオキシ）アニリンなどの共重合性老化防止剤；などが挙げられる。 Examples of such other copolymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride , Α, β-ethylenically unsaturated carboxylic acids such as fumaric acid and fumaric anhydride and anhydrides thereof; methyl (meth) acrylate [meaning methyl acrylate and methyl methacrylate. Hereinafter, the same as ethyl (meth) acrylate. ], Alkyl esters of α, β-ethylenically unsaturated carboxylic acids such as ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; mono (di) ethyl maleate [maleic acid] Means monoethyl and diethyl maleate. The same applies to mono (di) butyl maleate. ], Mono (di) butyl maleate, mono (di) ethyl fumarate, mono (di) butyl fumarate, mono (di) cyclohexyl fumarate, mono (di) ethyl itaconate, mono (di) butyl itaconate, etc. [Alpha], [beta] -ethylenically unsaturated polycarboxylic acid mono (di) esters; [alpha], [beta] -ethylene such as methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, butoxyethyl (meth) acrylate Alkoxyalkyl esters of unsaturated carboxylic acids; hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; heterocycles such as vinylpyridine Formula aromatic vinyl monomer; N- (4-anilinophenyl) acrylamide, N- (4-anilinofe ) Methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- ( Copolymerizable anti-aging agents such as 4-vinylbenzyloxy) aniline; and the like.
ニトリル共重合体ゴム（Ａ）のムーニー粘度（以下、「ポリマームーニー粘度」と記すことがある。）（ＭＬ１＋４、１００℃）は、好ましくは１５〜２００、より好ましくは３０〜１２０、特に好ましくは４５〜１００である。ニトリル共重合体ゴム（Ａ）のムーニー粘度が低すぎると、架橋物の強度特性が低下するおそれがある。逆に、高すぎると、ニトリル共重合体ゴム組成物の加工性が低下するおそれがある。The Mooney viscosity of the nitrile copolymer rubber (A) (hereinafter sometimes referred to as “polymer Mooney viscosity”) (ML 1 + 4 , 100 ° C.) is preferably 15 to 200, more preferably 30 to 120, and particularly preferably. Is 45-100. If the Mooney viscosity of the nitrile copolymer rubber (A) is too low, the strength properties of the crosslinked product may be reduced. Conversely, if it is too high, the processability of the nitrile copolymer rubber composition may be reduced.
ニトリル共重合体ゴム（Ａ）の製造方法は特に限定されない。一般的には、α，β−エチレン性不飽和ニトリル単量体、ジエン単量体またはα−オレフィン単量体、および、必要に応じて加えられるこれらと共重合可能なその他の単量体を共重合する方法が便利で好ましい。重合法としては、公知の乳化重合法、懸濁重合法、塊状重合法および溶液重合法のいずれをも用いることができるが、重合反応の制御の容易性、後述する可塑剤（Ｂ）との混合の便などからアニオン界面活性剤を用いて行う乳化重合法が好ましい。 The method for producing the nitrile copolymer rubber (A) is not particularly limited. Generally, α, β-ethylenically unsaturated nitrile monomer, diene monomer or α-olefin monomer, and other monomers copolymerizable with these are added as necessary. A method of copolymerization is convenient and preferred. As the polymerization method, any of the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used, but the ease of control of the polymerization reaction and the plasticizer (B) which will be described later are included. An emulsion polymerization method that uses an anionic surfactant from the convenience of mixing is preferred.
ニトリル共重合体ゴム（Ａ）は、上記のように共重合して得られた共重合体のジエン単量体単位にある不飽和結合部分を水素化（水素添加反応）したものであっても良い。
水素化の方法は特に限定されず、公知の方法を採用すればよい。The nitrile copolymer rubber (A) may be obtained by hydrogenating (hydrogenating reaction) an unsaturated bond portion in a diene monomer unit of a copolymer obtained by copolymerization as described above. good.
The method for hydrogenation is not particularly limited, and a known method may be employed.
ニトリル共重合体ゴム（Ａ）の重合方法は限定されない。たとえば、重合方法の一例として、以下に示す方法などが採用できる。 The polymerization method of the nitrile copolymer rubber (A) is not limited. For example, the following method can be employed as an example of the polymerization method.
すなわち、まず、重合に供されるα，β−エチレン性不飽和ニトリル単量体（ｍ１）と共役ジエン単量体（ｍ２）との合計１００重量％の内、当初（１段目）の重合で６０〜８５重量％の単量体（ｍ１）と、３〜１５重量％の単量体（ｍ２）とを使用する。単量体（ｍ１）の使用量が８５重量％を越えると、又は単量体（ｍ２）の使用量が３重量％未満であると、所定の重合転化率に達する前に単量体（ｍ２）が消失して重合が停止する可能性がある。一方、単量体（ｍ１）の使用量が６０重量％未満であると、又は単量体（ｍ２）の使用量が１５重量％を越えると、生成するニトリル共重合体ゴム中における、全単量体単位１００重量％に対する単量体（ｍ１）単位の含有量が５５重量％未満になるおそれがある。 That is, first, the initial (first stage) polymerization out of a total of 100% by weight of the α, β-ethylenically unsaturated nitrile monomer (m1) and the conjugated diene monomer (m2) used for polymerization. 60 to 85% by weight of monomer (m1) and 3 to 15% by weight of monomer (m2). When the amount of the monomer (m1) used exceeds 85% by weight or the amount of the monomer (m2) used is less than 3% by weight, the monomer (m2) is reached before reaching the predetermined polymerization conversion rate. ) May disappear and polymerization may stop. On the other hand, when the amount of the monomer (m1) used is less than 60% by weight or when the amount of the monomer (m2) used exceeds 15% by weight, There is a possibility that the content of the monomer (m1) unit with respect to 100% by weight of the monomer unit is less than 55% by weight.
１段目の重合を開始した後、単量体の残部を供給する。単量体の残部は連続的に供給しても、また、分割して多段階的に供給してもよい。
単量体の残部を連続的に供給して２段目の重合を行う場合、通常、単量体の残部のすべてを１時間以上かけて供給し、重合転化率が５０〜８０重量％に達した時点で重合を停止する。この２段目の重合においては、２段目の重合で添加する単量体（ｍ１）と単量体（ｍ２）との割合の合計を１００重量％とした場合に、次の通りとすることが好ましい。すなわち、重量比で５０重量％未満の単量体（ｍ１）と５０重量％以上の単量体（ｍ２）、好ましくは２０〜４０重量％の単量体（ｍ１）と６０〜８０重量％の単量体（ｍ２）とすることができ、また、すべてが単量体（ｍ２）であってもよい。単量体（ｍ２）の使用量が５０重量％未満であると、所定の重合転化率に達する前に単量体（ｍ２）が消失して重合が停止する可能性がある。After starting the first stage polymerization, the remainder of the monomer is fed. The remainder of the monomer may be supplied continuously or divided and supplied in multiple stages.
When the second stage polymerization is carried out by continuously supplying the remainder of the monomer, all of the remainder of the monomer is usually supplied over 1 hour, and the polymerization conversion rate reaches 50 to 80% by weight. At this point, the polymerization is stopped. In this second stage polymerization, when the total ratio of the monomer (m1) and the monomer (m2) added in the second stage polymerization is 100% by weight, the following should be done: Is preferred. That is, less than 50% by weight of monomer (m1) and 50% by weight or more of monomer (m2), preferably 20 to 40% by weight of monomer (m1) and 60 to 80% by weight. The monomer (m2) may be used, or all may be the monomer (m2). When the amount of the monomer (m2) used is less than 50% by weight, there is a possibility that the monomer (m2) disappears and the polymerization stops before reaching a predetermined polymerization conversion rate.
あるいは、２段目以降の重合を、単量体の残部を多段階的に供給して行う場合、すなわち、３段階の重合とする場合、例えば、１段目の重合転化率が１０〜３０重量％に達した時点で、単量体の残部のうち一部を一時に供給して２段目の重合を行い、重合転化率が３０〜５０重量％に達した時点で、単量体の残部のすべてを一時に供給して３段目の重合を行い、通常、重合転化率が５０〜８０重量％に達した時点で重合を停止する。また、４段階の重合とする場合、例えば、１段目、２段目、３段目の重合転化率が、それぞれ１０〜３０重量％、３０〜５０重量％、５０〜６５重量％に達した時点で、単量体の残部を順次供給して重合させ、重合転化率が６５〜８５重量％に達した時点で重合を停止する。加えて、更に多段の重合を行うこともでき、各単量体単位の含有量を制御する上では、より多段の重合を行うことが好ましい。 Alternatively, in the case where the second and subsequent stages of polymerization are carried out by supplying the remainder of the monomer in multiple stages, that is, in the case of three-stage polymerization, for example, the first stage polymerization conversion is 10 to 30 wt. %, When a part of the remainder of the monomer is supplied at a time to carry out the second stage polymerization, when the polymerization conversion rate reaches 30 to 50% by weight, the remainder of the monomer All of the above are supplied at a time to carry out the third stage polymerization, and the polymerization is usually stopped when the polymerization conversion rate reaches 50 to 80% by weight. In the case of four-stage polymerization, for example, the first, second, and third stage polymerization conversions reached 10 to 30% by weight, 30 to 50% by weight, and 50 to 65% by weight, respectively. At the time, the remainder of the monomer is sequentially fed and polymerized, and the polymerization is stopped when the polymerization conversion rate reaches 65 to 85% by weight. In addition, multi-stage polymerization can also be performed, and in order to control the content of each monomer unit, it is preferable to perform multi-stage polymerization.
上記多段重合において、２段目以降の各段階で一時に供給される単量体は、各段階で添加する単量体（ｍ１）と単量体（ｍ２）との割合の合計を１００重量％とした場合に、次の通りとすることが好ましい。すなわち、５０重量％未満の単量体（ｍ１）と５０重量％以上の単量体（ｍ２）、好ましくは２０〜４０重量％の単量体（ｍ１）と６０〜８０重量％の単量体（ｍ２）とすることができ、また、すべてが単量体（ｍ２）であってもよい。単量体（ｍ２）が５０重量％未満であると、所定の重合転化率に達する前に単量体（ｍ２）が消失して重合が停止するおそれがある。 In the multi-stage polymerization, the monomer supplied at each stage after the second stage is 100% by weight of the total ratio of the monomer (m1) and the monomer (m2) added at each stage. In this case, the following is preferable. That is, less than 50% by weight of monomer (m1) and 50% by weight or more of monomer (m2), preferably 20-40% by weight of monomer (m1) and 60-80% by weight of monomer. (M2) and all may be monomer (m2). If the monomer (m2) is less than 50% by weight, the monomer (m2) may disappear and polymerization may stop before the predetermined polymerization conversion rate is reached.
本発明のニトリル共重合体ゴム架橋物を得る前段階において、ニトリル共重合体ゴム（Ａ）および可塑剤（Ｂ）を含有するニトリル共重合体ゴム組成物を調製する必要がある。 Prior to obtaining the crosslinked nitrile copolymer rubber of the present invention, it is necessary to prepare a nitrile copolymer rubber composition containing the nitrile copolymer rubber (A) and the plasticizer (B).
可塑剤（Ｂ）としては、従来ゴム配合用の可塑剤として慣用されているものが限定なく使用できる。
このような可塑剤としては、例えば、次のものが挙げられる。
すなわち、ジブトキシエチルアジペート、ジ（ブトキシエトキシエチル）アジペートなどの、下記一般式（１）で表される化学構造を有する化合物（ｂ１）と、エーテル結合含有アルコール（ｂ２）と、のエステル化合物（ｂ）が挙げられる。
ＨＯＯＣＲＣＯＯＨ （１）
（式中のＲは炭素数２〜１０のアルキレン基を表し、ＣＯＯＨはカルボキシ基を表す。）
さらに、上記エステル化合物（ｂ）の他、ジ−（２−エチルヘキシル）アジペート、ジイソデシルアジペート、ジイソノニルアジペートなどのアジピン酸ジアルキルエステル類；ジ−（２−エチルヘキシル）アゼレート、ジイソオクチルアゼレート、ジ−ｎ−ヘキシルアゼレートなどのアゼライン酸エステル類；ジ−ｎ−ブチルセバケート、ジ−（２−エチルヘキシル）セバケートなどのセバシン酸エステル類；ジブチルフタレート、ジ−（２−エチルヘキシル）フタレート、ジ−ｎ−オクチルフタレート、ジイソブチルフタレート、ジヘプチルフタレート、ジフェニルフタレート、ジイソデシルフタレート、ジウンデシルフタレート、ブチルベンジルフタレート、ジノニルフタレート、ジシクロヘキシルフタレートなどのフタル酸エステル類；ジ−（２−エチルヘキシル）イソフタレート、ジイソオクチルイソフタレートなどのイソフタル酸エステル類；ジ−（２−エチルヘキシル）テトラヒドロフタレート、ジ−ｎ−オクチルテトラヒドロフタレート、ジイソデシルテトラヒドロフタレートなどのテトラヒドロフタル酸エステル類；トリ−（２−エチルヘキシル）トリメリテート、トリ−ｎ−オクチルトリメリテート、トリイソデシルトリメリテート、トリイソオクチルトリメリテート、トリ−ｎ−ヘキシルトリメリテート、トリイソノニルトリメリテートなどのトリメリット酸誘導体；などが挙げられる。
なかでも上記エステル化合物（ｂ）が好ましい。As a plasticizer (B), what is conventionally used as a plasticizer for rubber compounding can be used without limitation.
Examples of such plasticizers include the following.
That is, an ester compound of a compound (b1) having a chemical structure represented by the following general formula (1) such as dibutoxyethyl adipate and di (butoxyethoxyethyl) adipate and an ether bond-containing alcohol (b2) ( b).
HOOCRCOOH (1)
(R in the formula represents an alkylene group having 2 to 10 carbon atoms, and COOH represents a carboxy group.)
Furthermore, in addition to the above ester compound (b), adipic acid dialkyl esters such as di- (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate; di- (2-ethylhexyl) azelate, diisooctylazelate, di- azelaic acid esters such as n-hexyl azelate; sebacic acid esters such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate; dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl Phthalic acid esters such as phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, diundecyl phthalate, butyl benzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate Isophthalic acid esters such as di- (2-ethylhexyl) isophthalate and diisooctylisophthalate; tetrahydrophthalic acid esters such as di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate and diisodecyltetrahydrophthalate Tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, triisononyl trimellitate, etc. And trimellitic acid derivatives thereof.
Of these, the ester compound (b) is preferred.
上記エステル化合物（ｂ）の一方の原料成分である上記一般式（１）で表される化合物（ｂ１）〔以下、化合物（ｂ１）という場合がある。〕のアルキレン基Ｒは、直鎖状のものが好ましい。また、炭素数は２〜１０が好ましく、４〜８がより好ましい。化合物（ｂ１）の具体例としては、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸などが挙げられる。 Compound (b1) represented by the above general formula (1), which is one raw material component of the ester compound (b) [hereinafter sometimes referred to as the compound (b1). ] Is preferably a straight chain. Moreover, 2-10 are preferable and, as for carbon number, 4-8 are more preferable. Specific examples of the compound (b1) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like.
また、上記エステル化合物（ｂ）の他方の原料成分であるエーテル結合含有アルコール（ｂ２）〔以下、アルコール（ｂ２）という場合がある。〕は、一価のアルコールが好ましい。また、炭素数は４〜１０が好ましく、６〜８がより好ましい。アルコール（ｂ２）の分子に含有されるエーテル結合の数は好ましくは１〜４、より好ましくは１〜２である。
好ましいアルコール（ｂ２）の具体例としては、メトキシプロピルアルコール、エトキシエチルアルコール、プロポキシメチルアルコールなどの炭素数４でエーテル結合数１のアルコール；ジメトキシエチルアルコール、メトキシエトキシメチルアルコール（ＣＨ３Ｏ−Ｃ２Ｈ４Ｏ−ＣＨ２ＯＨ）などの炭素数４でエーテル結合数２のアルコール；メトキシブチルアルコール、エトキシプロピルアルコール、プロポキシエチルアルコールなどの炭素数５でエーテル結合数が１のアルコール；ジメトキシプロピルアルコール、メトキシエトキシエチルアルコール（ＣＨ３Ｏ−Ｃ２Ｈ４Ｏ−Ｃ２Ｈ４ＯＨ）、ジエトキシメチルアルコールなどの炭素数５でエーテル結合数２のアルコール；ブトキシエチルアルコール、プロポキシプロピルアルコール、エトキシブチルアルコール、メトキシペンチルアルコールなどの炭素数６でエーテル結合数１のアルコール；ジメトキシブチルアルコール、メトキシエトキシプロピルアルコール（ＣＨ３Ｏ−Ｃ２Ｈ４Ｏ−Ｃ３Ｈ６ＯＨ）、ジエトキシエチルアルコールなどの炭素数６でエーテル結合数２のアルコール；ブトキシプロピルアルコール、プロポキシブチルアルコール、エトキシペンチルアルコール、メトキシヘキシルアルコールなどの炭素数７でエーテル結合数１のアルコール；ジメトキシペンチルアルコール、メトキシエトキシブチルアルコール（ＣＨ３Ｏ−Ｃ２Ｈ４Ｏ−Ｃ４Ｈ８ＯＨ）、メトキシプロポキシプロピルアルコール（ＣＨ３Ｏ−Ｃ３Ｈ６Ｏ−Ｃ３Ｈ６ＯＨ）などの炭素数７でエーテル結合数２のアルコール；ペントキシプロピルアルコール、ブトキシブチルアルコール、プロポキシペンチルアルコール、エトキシヘキシルアルコール、メトキシヘプチルアルコールなどの炭素数８でエーテル結合数１のアルコール；ブトキシエトキシエチルアルコール（Ｃ４Ｈ９Ｏ−Ｃ２Ｈ４Ｏ−Ｃ２Ｈ４ＯＨ）、ジプロポキシエチルアルコール、エトキシプロポキシプロピルアルコール（Ｃ２Ｈ５Ｏ−Ｃ３Ｈ６Ｏ−Ｃ３Ｈ６ＯＨ）、プロポキシエトキシプロピルアルコール（Ｃ３Ｈ７Ｏ−Ｃ２Ｈ４Ｏ−Ｃ３Ｈ６ＯＨ）、メトキシブトキシプロピルアルコール（ＣＨ３Ｏ−Ｃ４Ｈ８Ｏ−Ｃ３Ｈ６ＯＨ）、ジエトキシブチルアルコールなどの炭素数８でエーテル結合数２のアルコール；などが挙げられる。Further, the ether bond-containing alcohol (b2) which is the other raw material component of the ester compound (b) [hereinafter sometimes referred to as alcohol (b2). ] Is preferably a monohydric alcohol. Moreover, 4-10 are preferable and, as for carbon number, 6-8 are more preferable. The number of ether bonds contained in the molecule of alcohol (b2) is preferably 1 to 4, more preferably 1 to 2.
Specific examples of the preferred alcohol (b2) include alcohols having 4 carbon atoms and 1 ether bond such as methoxypropyl alcohol, ethoxyethyl alcohol, propoxymethyl alcohol; dimethoxyethyl alcohol, methoxyethoxymethyl alcohol (CH 3 O—C 2 H 4 O—CH 2 OH) and the like having 4 ether bonds, such as methoxybutyl alcohol, ethoxypropyl alcohol, and propoxyethyl alcohol, having 5 carbon atoms and 1 ether bond; dimethoxypropyl alcohol, methoxyethoxyethyl alcohol (CH 3 O-C 2 H 4 O-C 2 H 4 OH), alcohol 5 carbons ether bond number 2, such as diethoxymethyl alcohol; butoxyethyl alcohol, Puropokishipuro Alcohol, ethoxy butyl alcohol, alcohol having 6 carbon atoms in the ether bond number 1, such as methoxy pentyl alcohol; dimethoxy-butyl alcohol, methoxyethoxy propyl alcohol (CH 3 O-C 2 H 4 O-C 3 H 6 OH), di Alcohol having 6 carbon atoms and 2 ether bonds such as ethoxyethyl alcohol; Alcohol having 1 carbon bond and 7 ether bonds such as butoxypropyl alcohol, propoxybutyl alcohol, ethoxypentyl alcohol and methoxyhexyl alcohol; Dimethoxypentyl alcohol and methoxyethoxy butyl alcohol (CH 3 O-C 2 H 4 O-C 4 H 8 OH), ether formation with a carbon number of 7, such as methoxy propoxy-propyl alcohol (CH 3 O-C 3 H 6 O-C 3 H 6 OH) Number 2 alcohol; pentoxy propyl alcohol, butoxy butyl alcohol, propoxy pentyl alcohol, ethoxy hexyl alcohol, alcohol having 8 carbon atoms in the ether bond number 1, such as methoxy heptyl alcohol; butoxyethoxyethyl alcohol (C 4 H 9 O-C 2 H 4 O-C 2 H 4 OH), dipropoxy ethyl alcohol, ethoxy propoxy-propyl alcohol (C 2 H 5 O-C 3 H 6 O-C 3 H 6 OH), propoxy ethoxy propyl alcohol (C 3 H 7 O-C 2 H 4 O- C 3 H 6 OH), methoxy butoxy propyl alcohol (CH 3 O-C 4 H 8 O-C 3 H 6 OH), an ether bond number at 8 carbon atoms, such as diethoxy-butyl alcohol 2 alcohols; and the like.
エステル化合物（ｂ）としては、化合物（ｂ１）とアルコール（ｂ２）とを任意に組み合わせて得られるものを用いることができる。通常、モノエステル化合物及びジエステル化合物が用いられるが、好ましいのはジエステル化合物である。好ましいジエステル化合物の具体例としては、ジブトキシエチルアジペート、ジ（ブトキシエトキシエチル）アジペートなどが挙げられ、特に好ましくはジ（ブトキシエトキシエチル）アジペートである。 As the ester compound (b), a compound obtained by arbitrarily combining the compound (b1) and the alcohol (b2) can be used. Usually, monoester compounds and diester compounds are used, and preferred are diester compounds. Specific examples of preferable diester compounds include dibutoxyethyl adipate and di (butoxyethoxyethyl) adipate, and di (butoxyethoxyethyl) adipate is particularly preferable.
本発明のニトリル共重合体ゴム組成物を調製する方法としては、ニトリル共重合体ゴム（Ａ）のラテックスと可塑剤（Ｂ）のエマルションとの混合液を調製する工程と、該混合液を凝固させ、その後、乾燥させて固形の混合物とする工程と、該固形混合物とゴム用配合剤とを混練する工程と、を含む方法が好ましい。 The method for preparing the nitrile copolymer rubber composition of the present invention includes a step of preparing a mixed solution of a latex of a nitrile copolymer rubber (A) and an emulsion of a plasticizer (B), and coagulating the mixed solution. And a step of drying to obtain a solid mixture and a step of kneading the solid mixture and the compounding agent for rubber are preferable.
ニトリル共重合体ゴム（Ａ）と可塑剤（Ｂ）の混合割合は、ラテックス中のニトリル共重合体ゴム（Ａ）１００重量部に対し、エマルション中の可塑剤（Ｂ）が０.１〜１００重量部、好ましくは３〜５０重量部、より好ましくは５〜２０重量部である。可塑剤（Ｂ）の量が少なすぎると、得られる架橋物の脆化温度が高くなるおそれがある。逆に、多すぎると可塑剤のブリードが生ずる可能性がある。 The mixing ratio of the nitrile copolymer rubber (A) and the plasticizer (B) is such that the plasticizer (B) in the emulsion is 0.1 to 100 parts per 100 parts by weight of the nitrile copolymer rubber (A) in the latex. Parts by weight, preferably 3 to 50 parts by weight, more preferably 5 to 20 parts by weight. When there is too little quantity of a plasticizer (B), there exists a possibility that the brittle temperature of the crosslinked material obtained may become high. Conversely, if the amount is too large, bleeding of the plasticizer may occur.
ニトリル共重合体ゴム（Ａ）ラテックスの濃度は、５〜６０重量％が好ましく、１０〜５０重量％がより好ましい。また、ニトリル共重合体ゴム（Ａ）を乳化重合にて製造し、重合反応の終了の状態で用いると好ましい。 The concentration of the nitrile copolymer rubber (A) latex is preferably 5 to 60% by weight, and more preferably 10 to 50% by weight. Further, it is preferable that the nitrile copolymer rubber (A) is produced by emulsion polymerization and used after completion of the polymerization reaction.
可塑剤（Ｂ）のエマルションは、水を媒体とする濃度１０〜７０重量％のものが好ましく、２０〜６０重量％のものがより好ましい。エマルションの調製法に限定はないが、可塑剤（Ｂ）に対して、好ましくは１〜２０重量％、より好ましくは１．５〜１５重量％の乳化剤を水に溶解し、その後、強撹拌などの剪断力下で可塑剤（Ｂ）を導入する方法が好ましい。
乳化剤の例としては、ロジン酸カリウム、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウムなどのアニオン界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンソルビタンアルキルエステルなどのノニオン界面活性剤；ジデシルジメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライドなどのカチオン界面活性剤などが挙げられ、ニトリル共重合体ゴム（Ａ）の乳化重合に用いられた乳化剤と同一のものを使用することができる。The plasticizer (B) emulsion preferably has a water concentration of 10 to 70% by weight, more preferably 20 to 60% by weight. Although there is no limitation in the preparation method of an emulsion, Preferably 1-20 weight% with respect to a plasticizer (B), More preferably, 1.5-15 weight% of emulsifiers are melt | dissolved in water, Then, strong stirring etc. A method of introducing the plasticizer (B) under the shearing force of is preferable.
Examples of emulsifiers include anionic surfactants such as potassium rosinate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate; nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester A cationic surfactant such as didecyldimethylammonium chloride, stearyltrimethylammonium chloride, and the like, and the same emulsifier used for the emulsion polymerization of the nitrile copolymer rubber (A) can be used.
ニトリル共重合体ゴム（Ａ）のラテックスと、可塑剤（Ｂ）のエマルションと、の混合法としては、これらを十分均一に混合できる方法であれば限定はなく、回分式、連続式のいずれでもよい。 The mixing method of the latex of the nitrile copolymer rubber (A) and the emulsion of the plasticizer (B) is not limited as long as these can be mixed sufficiently uniformly, and either a batch type or a continuous type may be used. Good.
ニトリル共重合体ゴム（Ａ）のラテックスと、可塑剤（Ｂ）のエマルションと、を十分に混合した後、得られた混合液を凝固する。凝固法に限定はないが、通常、塩化カルシウム、硫酸バリウム、硫酸アルミニウムなどの凝固剤を撹拌下の混合液に添加する方法が採られる。凝固物は濾別した後、４０〜１００℃、好ましくは５０〜９０℃にて乾燥して固形物とされる。固形物の含水量は、好ましくは０．０５〜１．５重量％、より好ましくは０．１〜１．０重量％である。 After thoroughly mixing the latex of the nitrile copolymer rubber (A) and the emulsion of the plasticizer (B), the obtained mixed solution is coagulated. The coagulation method is not limited, but usually a method of adding a coagulant such as calcium chloride, barium sulfate, aluminum sulfate or the like to the mixed liquid under stirring is employed. The solidified product is filtered and then dried at 40 to 100 ° C., preferably 50 to 90 ° C., to form a solid. The water content of the solid is preferably 0.05 to 1.5% by weight, more preferably 0.1 to 1.0% by weight.
本発明のニトリル共重合体ゴム組成物は、上記のようにして得られたニトリル共重合体ゴム（Ａ）及び可塑剤（Ｂ）の混合物の他に、通常、ゴム用配合剤を含有し、例えば、架橋物を形成するための架橋剤を含有する。架橋剤としては、ニトリル基含有共重合体ゴムの架橋剤として通常使用されるものであれば限定されない。好ましい架橋剤としては硫黄系架橋剤または有機過酸化物架橋剤が挙げられ、中でも、硫黄系架橋剤がより好ましい。 The nitrile copolymer rubber composition of the present invention usually contains a rubber compounding agent in addition to the mixture of the nitrile copolymer rubber (A) and the plasticizer (B) obtained as described above. For example, it contains a crosslinking agent for forming a crosslinked product. The crosslinking agent is not limited as long as it is usually used as a crosslinking agent for nitrile group-containing copolymer rubber. Preferable crosslinking agents include sulfur-based crosslinking agents or organic peroxide crosslinking agents, among which sulfur-based crosslinking agents are more preferable.
硫黄系架橋剤としては、粉末硫黄、硫黄華、沈降性硫黄、コロイド硫黄、表面処理硫黄及び不溶性硫黄などの硫黄；塩化硫黄、二塩化硫黄、モルホリン・ジスルフィド、アルキルフェノール・ジスルフィド、ジベンゾチアジルジスルフィド、Ｎ，Ｎ’−ジチオ−ビス（ヘキサヒドロ−２Ｈ−アゼノピン−２）、含リンポリスルフィド及び高分子多硫化物などの含硫黄化合物；テトラメチルチウラムジスルフィド、ジメチルジチオカルバミン酸セレン、２−（４’−モルホリノジチオ）ベンゾチアゾールなどの硫黄供与性化合物などが挙げられる。 Sulfur-based crosslinking agents include sulfur such as powdered sulfur, sulfur flower, precipitated sulfur, colloidal sulfur, surface treated sulfur and insoluble sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothiazyl disulfide, Sulfur-containing compounds such as N, N′-dithio-bis (hexahydro-2H-azenopine-2), phosphorus-containing polysulfides and polymer polysulfides; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, 2- (4′-morpholino And sulfur-donating compounds such as dithio) benzothiazole.
硫黄系架橋剤を用いる場合には、亜鉛華、ステアリン酸などの架橋助剤；グアニジン系、アルデヒド−アミン系、アルデヒド−アンモニア系、チアゾール系、スルフェンアミド系、チオ尿素系などの架橋促進剤を使用することができる。これらの架橋助剤及び架橋促進剤の使用量は特に限定されず、ニトリル共重合体ゴム（Ａ）１００重量部に対して、通常、０．１〜５重量部の範囲で使用することができる。 In the case of using a sulfur-based crosslinking agent, a crosslinking assistant such as zinc white and stearic acid; a crosslinking accelerator such as guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based Can be used. The usage-amount of these crosslinking adjuvants and crosslinking accelerators is not specifically limited, Usually, it can be used in 0.1-5 weight part with respect to 100 weight part of nitrile copolymer rubber (A). .
有機過酸化物架橋剤としては、例えば、ジクミルペルオキシド、ｔ−ブチルクミルペルオキシド、ジ−ｔ−ブチルペルオキシド、クメンヒドロペルオキシド、パラメンタンヒドロペルオキシド、１，３−及び１，４−ビス（ｔ−ブチルペルオキシイソプロピル）ベンゼン、１，１−ジ−ｔ−ブチルペルオキシ−３，３−トリメチルシクロヘキサン、４，４−ビス−（ｔ−ブチル−ペルオキシ）−ｎ−ブチルバレレート、２，５−ジメチル−２，５−ジ−ｔ−ブチルペルオキシヘキサン、２，５−ジメチル−２，５−ジ−ｔ−ブチルペルオキシヘキシン−３、１，１−ジ−ｔ−ブチルペルオキシ−３，５，５−トリメチルシクロヘキサン、ｐ−クロロベンゾイルペルオキシド、ｔ−ブチルペルオキシイソプロピルカーボネート、ｔ−ブチルペルオキシベンゾエート等が挙げられる。 Examples of the organic peroxide crosslinking agent include dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, paramentane hydroperoxide, 1,3- and 1,4-bis (t -Butylperoxyisopropyl) benzene, 1,1-di-t-butylperoxy-3,3-trimethylcyclohexane, 4,4-bis- (t-butyl-peroxy) -n-butylvalerate, 2,5-dimethyl -2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, 1,1-di-t-butylperoxy-3,5,5 -Trimethylcyclohexane, p-chlorobenzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxide Carboxymethyl benzoate and the like.
有機過酸化物架橋剤を用いる場合には、架橋助剤としてトリメチロールプロパントリメタクリレート、ジビニルベンゼン、エチレンジメタクリレート、トリアリルイソシアヌレートなどの多官能性単量体などが用いられる。これらの架橋助剤の配合量は特に限定されないが、ニトリル共重合体ゴム（Ａ）１００重量部に対して、通常、０．５〜２０重量部の範囲で使用することができる。 When an organic peroxide crosslinking agent is used, a multifunctional monomer such as trimethylolpropane trimethacrylate, divinylbenzene, ethylene dimethacrylate, triallyl isocyanurate, or the like is used as a crosslinking aid. Although the compounding quantity of these crosslinking adjuvants is not specifically limited, Usually, it can be used in 0.5-20 weight part with respect to 100 weight part of nitrile copolymer rubber (A).
ニトリル共重合体ゴム組成物の架橋剤含有量に限定はないが、ニトリル共重合体ゴム（Ａ）１００重量部に対して、好ましくは０．１〜１０重量部、より好ましくは０．２〜５重量部である。 The content of the crosslinking agent in the nitrile copolymer rubber composition is not limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the nitrile copolymer rubber (A). 5 parts by weight.
ニトリル共重合体ゴム組成物は、その他必要に応じて架橋遅延剤、老化防止剤、充填剤、補強剤、滑剤、粘着剤、潤滑剤、難燃剤、防黴剤、帯電防止剤、着色剤などの添加剤を含有してもよい。 The nitrile copolymer rubber composition is a crosslinking retarder, an anti-aging agent, a filler, a reinforcing agent, a lubricant, an adhesive, a lubricant, a flame retardant, an antifungal agent, an antistatic agent, a colorant, etc. The additive may be contained.
老化防止剤としては、フェノール系、アミン系、ベンズイミダゾール系、リン酸系などの老化防止剤を使用することができる。フェノール系では、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）などが、アミン系では、４，４’−ビス（α、α−ジメチルベンジル）ジフェニルアミンなどが、ベンズイミダゾール系では２−メルカプトベンズイミダゾールなどが挙げられる。これらは１種単独でまたは２種以上併せて使用される。 As the anti-aging agent, an anti-aging agent such as phenol, amine, benzimidazole or phosphoric acid can be used. In the phenol system, 2,2′-methylenebis (4-methyl-6-t-butylphenol) is used, in the amine system, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine is used, and in the benzimidazole system. Examples include 2-mercaptobenzimidazole. These may be used alone or in combination of two or more.
充填剤としては、カーボンブラック、シリカ、炭酸カルシウム、炭酸マグネシウム、タルク、クレー等を使用することができる。これらにはシラン系カップリング剤などを配合することもできる。 As the filler, carbon black, silica, calcium carbonate, magnesium carbonate, talc, clay and the like can be used. These can be blended with a silane coupling agent or the like.
また、ニトリル共重合体ゴム組成物には、本発明の効果を損なわない範囲で、ニトリル共重合体ゴム（Ａ）以外のゴムを配合してもよい。ニトリル共重合体ゴム（Ａ）以外のゴムとしては特に限定されない。その例としては、アクリルゴム、フッ素ゴム、スチレン−ブタジエン共重合体ゴム、エチレン−プロピレン−ジエン三元共重合体ゴム、天然ゴム、ポリイソプレンゴムなどを挙げることができる。これらのゴムを配合する場合には、上記以外の架橋剤として、例えば、金属石けん／硫黄系加硫剤、トリアジン／ジチオカルバミン酸塩系化合物、ポリカルボン酸／オニウム塩系化合物、ポリアミン系化合物（ヘキサメチレンジアミン、トリエチレンジアミン、トリエチレンテトラミン、ヘキサメチレンジアミンカルバメート、エチレンジアミンカルバメートなど）などを必要に応じて併用することができる。 Moreover, you may mix | blend rubbers other than a nitrile copolymer rubber (A) with the nitrile copolymer rubber composition in the range which does not impair the effect of this invention. The rubber other than the nitrile copolymer rubber (A) is not particularly limited. Examples thereof include acrylic rubber, fluorine rubber, styrene-butadiene copolymer rubber, ethylene-propylene-diene terpolymer rubber, natural rubber, and polyisoprene rubber. When these rubbers are blended, as other crosslinking agents, for example, metal soap / sulfur vulcanizing agent, triazine / dithiocarbamate compound, polycarboxylic acid / onium salt compound, polyamine compound (hexa Methylene diamine, triethylene diamine, triethylene tetramine, hexamethylene diamine carbamate, ethylene diamine carbamate, etc.) can be used in combination as required.
ニトリル共重合体ゴム組成物として、可塑剤以外の上記の諸成分を含有するものを調製するには、上記のニトリル共重合体ゴム（Ａ）及び可塑剤（Ｂ）からなる固形の混合物に、通常、架橋剤および熱に不安定な架橋助剤などを除いた老化防止剤、補強剤、などの成分を、バンバリーミキサ、インターミキサ、ニーダなどの混合機で一次混練し、次いでロールなどに移して架橋剤等を加えて二次混練する。 In order to prepare a nitrile copolymer rubber composition containing the above-described components other than the plasticizer, a solid mixture composed of the nitrile copolymer rubber (A) and the plasticizer (B) is used. Usually, components such as anti-aging agents and reinforcing agents, excluding cross-linking agents and heat-labile cross-linking aids, are primarily kneaded with a mixer such as a Banbury mixer, intermixer, or kneader, and then transferred to a roll or the like. Add a cross-linking agent and knead the mixture.
ニトリル共重合体ゴム組成物のムーニー粘度（以下、「コンパウンドムーニー粘度」と記すことがある。）（ＭＬ１＋４，１００℃）は、好ましくは２０〜２００、より好ましくは３０〜１５０である。The Mooney viscosity (hereinafter sometimes referred to as “compound Mooney viscosity”) (ML 1 + 4 , 100 ° C.) of the nitrile copolymer rubber composition is preferably 20 to 200, more preferably 30 to 150.
本発明のニトリル共重合体ゴム架橋物は、上記のようにして調製されたニトリル共重合体ゴム組成物を架橋して得られる。ニトリル共重合体ゴム組成物を架橋するには、得ようとする架橋物の形状に対応した成形機、例えば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、また、架橋反応により架橋物の形状を固定化する。予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、１０〜２００℃、好ましくは２５〜１２０℃である。架橋温度は、通常、１００〜２００℃、好ましくは１３０〜１９０℃であり、架橋時間は、通常、１分〜２４時間、好ましくは２分〜１時間である。 The crosslinked nitrile copolymer rubber of the present invention is obtained by crosslinking the nitrile copolymer rubber composition prepared as described above. In order to crosslink the nitrile copolymer rubber composition, molding is performed by a molding machine corresponding to the shape of the crosslinked product to be obtained, for example, an extruder, an injection molding machine, a compressor, a roll, etc., and a crosslinking reaction is performed. To fix the shape of the cross-linked product. Crosslinking may be performed after molding in advance, or may be performed simultaneously with molding. The molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C. The crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C., and the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 1 hour.
また、上記架橋物は、その形状、大きさなどによっては、表面が架橋していても内部まで十分に架橋していない場合があるので、さらに加熱して二次架橋を行ってもよい。 In addition, depending on the shape, size, and the like of the crosslinked product, even if the surface is crosslinked, it may not be sufficiently crosslinked to the inside. Therefore, secondary crosslinking may be performed by heating.
本発明のニトリル共重合体ゴム架橋物は、ＪＩＳ Ｋ６３０１による脆化温度が−５０〜−５℃、好ましくは−３５〜−５℃、より好ましくは−２５〜−７℃である。脆化温度が低すぎると架橋物のガソリン透過性が高くなるおそれがあり、逆に、高すぎると低温環境下での使用が困難となる。 The crosslinked nitrile copolymer rubber of the present invention has an embrittlement temperature according to JIS K6301 of −50 to −5 ° C., preferably −35 to −5 ° C., more preferably −25 to −7 ° C. If the embrittlement temperature is too low, the gasoline permeability of the cross-linked product may be high. On the other hand, if it is too high, use in a low temperature environment becomes difficult.
また、本発明のニトリル共重合体ゴム架橋物はイソオクタン／トルエン／エタノールの重量比が４０／４０／２０であるガソホール（ガソリンとアルコールの混合物）を用いてアルミカップ法（後述の実施例の試験法参照）によって測定されるガソリン透過性が、２００ｇ・ｍｍ／ｍ２・ｄａｙ以下が好ましく、１８０ｇ・ｍｍ／ｍ２・ｄａｙ以下がより好ましく、１６０ｇ・ｍｍ／ｍ２・ｄａｙ以下が特に好ましい。ガソリン透過性が大きすぎると燃料用ホースなどに求められる低ガソリン透過材料として不適である。Further, the crosslinked nitrile copolymer rubber of the present invention uses an aluminum cup method (test of examples described later) using gasohol (a mixture of gasoline and alcohol) having a weight ratio of isooctane / toluene / ethanol of 40/40/20. gasoline permeability measured by law reference) is preferably not more than 200g · mm / m 2 · day , more preferably at most 180g · mm / m 2 · day , or less 160g · mm / m 2 · day is particularly preferred. If the gasoline permeability is too large, it is not suitable as a low gasoline permeable material required for fuel hoses and the like.
本発明のニトリル共重合体ゴム架橋物はガソリン透過性が低いので、該架橋物からなる層（Ｉ）を少なくとも有する積層体は、燃料用ホースなどとして好適に用いられる。 Since the crosslinked nitrile copolymer rubber of the present invention has low gasoline permeability, the laminate having at least the layer (I) made of the crosslinked product is preferably used as a fuel hose or the like.
該架橋物からなる層（Ｉ）と共に積層され、該積層体を構成する他の層（ＩＩ）としては、次のものが好ましい。
すなわち、層（ＩＩ）としては、α，β−エチレン性不飽和ニトリル単量体単位５重量％以上、５５重量％未満、好ましくは１８重量％以上、４５重量％以下であるニトリル共重合体ゴム（Ｌ）及び該ゴム（Ｌ）１００重量部に対して可塑剤（Ｍ）０〜１００重量部、好ましくは４〜９０重量部含有量してなる、脆化温度が−７０〜−１０℃、好ましくは−６０〜−１４℃、より好ましくは−５０〜−１８℃である層が、ガソリン透過性が低いため好ましい。なお、上記ニトリル共重合体ゴム（Ｌ）は、α，β−エチレン性不飽和ニトリル単量体単位の含有量が異なること以外は、ニトリル共重合体ゴム（Ａ）と同様の単量体単位を有する。また、上記可塑剤（Ｍ）は、前記可塑剤（Ｂ）と同様である。As the other layer (II) which is laminated together with the layer (I) comprising the crosslinked product and constitutes the laminate, the following are preferable.
That is, as the layer (II), the α, β-ethylenically unsaturated nitrile monomer unit is 5% by weight or more and less than 55% by weight, preferably 18% by weight or more and 45% by weight or less. The embrittlement temperature is -70 to -10 ° C, comprising 0 to 100 parts by weight, preferably 4 to 90 parts by weight of the plasticizer (M) with respect to 100 parts by weight of (L) and the rubber (L). A layer having a temperature of preferably −60 to −14 ° C., more preferably −50 to −18 ° C. is preferable because of low gasoline permeability. The nitrile copolymer rubber (L) is a monomer unit similar to the nitrile copolymer rubber (A) except that the content of the α, β-ethylenically unsaturated nitrile monomer unit is different. Have The plasticizer (M) is the same as the plasticizer (B).
ここで、各層の厚みは、層（Ｉ）が好ましくは０.１〜１０ｍｍ、より好ましくは０.２〜５ｍｍであり、層（ＩＩ）が好ましくは０.１〜１０ｍｍ、より好ましくは０.２〜５ｍｍである。
層（Ｉ）の材料のみからなる厚いゴム材料の代わりに、全体の厚みがこれと同様の上記の層（Ｉ）及び層（ＩＩ）からなる積層体とすることにより、層（Ｉ）の有する低ガソリン透過性と、層（ＩＩ）の有する低脆化温度特性を高度にバランスさせることができる。このような積層体からなる、少なくとも層（Ｉ）を内層とする二層以上の多層ホースは、燃料用ホースとして使用できる。Here, the thickness of each layer is preferably 0.1 to 10 mm, more preferably 0.2 to 5 mm for the layer (I), and preferably 0.1 to 10 mm, more preferably 0.1 to the layer (II). 2-5 mm.
Instead of the thick rubber material consisting only of the material of the layer (I), the layer (I) has a layered body consisting of the above-mentioned layer (I) and layer (II) having the same overall thickness. The low gasoline permeability and the low embrittlement temperature characteristic of the layer (II) can be highly balanced. A multilayer hose composed of such a laminate and having two or more layers having at least the layer (I) as an inner layer can be used as a fuel hose.
本発明のニトリル共重合体ゴム架橋物は、不飽和ニトリル単量体単位含有量が５５〜８０重量％のいわゆる超極高レベルであっても、ガソリン透過性が低く、しかも脆化温度が低いという利点を有する。そのため、例えば、該架橋物単層の燃料用ホースとして、また、該架橋物を内層に有する多層構造の燃料用ホースとして有用である。
さらに、本発明のニトリル共重合体ゴム架橋物は、シール用途（パッキン、ガスケット、ダイヤフラム等）にも好適に使用することができる。The crosslinked nitrile copolymer rubber of the present invention has a low gasoline permeability and a low embrittlement temperature even at a so-called ultra-high level where the unsaturated nitrile monomer unit content is 55 to 80% by weight. Has the advantage. Therefore, it is useful, for example, as a fuel hose having a single layer of the cross-linked product and as a fuel hose having a multilayer structure having the cross-linked product as an inner layer.
Furthermore, the crosslinked nitrile copolymer rubber of the present invention can also be suitably used for sealing applications (packing, gasket, diaphragm, etc.).
以下に実施例および比較例を挙げて本発明を具体的に説明する。以下において、特記しない限り「部」は重量基準である。なお、試験、評価は以下によった。 The present invention will be specifically described below with reference to examples and comparative examples. In the following, “parts” are based on weight unless otherwise specified. The test and evaluation were as follows.
（１）アクリロニトリル単量体単位の含有量
ＪＩＳ Ｋ６３８４に従い、ケルダール法によって測定したニトリル共重合体ゴム中の窒素含量から計算により、アクリロニトリル単量体単位の含有量（重量％）を求めた。(1) Content of acrylonitrile monomer unit The content (% by weight) of the acrylonitrile monomer unit was determined by calculation from the nitrogen content in the nitrile copolymer rubber measured by the Kjeldahl method according to JIS K6384.
（２）ムーニー粘度（ＭＬ１＋４ ，１００℃）
「ニトリル共重合体ゴム」のムーニー粘度（ポリマームーニー）、及び、「ニトリル共重合体ゴム組成物」のムーニー粘度（コンパウンドムーニー）をＪＩＳ Ｋ６３００に従って測定した。(2) Mooney viscosity (ML 1 + 4 , 100 ° C.)
The Mooney viscosity (polymer Mooney) of the “nitrile copolymer rubber” and the Mooney viscosity (compound Mooney) of the “nitrile copolymer rubber composition” were measured according to JIS K6300.
（３）常態物性（引張強さ、伸び、１００％引張応力）
ニトリル共重合体ゴム組成物を縦１５ｃｍ、横１５ｃｍ、深さ０．２ｃｍの金型に入れ、加圧しながら１６０℃で２０分間プレス成形してシート状架橋物を得た。得られたシート状架橋物をＪＩＳ３号形ダンベルで打ち抜き、試験片を作製した。得られた試験片を用いて、ＪＩＳ Ｋ６２５１に従い、架橋物の引張強さ、伸び及び１００％引張応力を測定した。(3) Normal physical properties (tensile strength, elongation, 100% tensile stress)
The nitrile copolymer rubber composition was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and press-molded at 160 ° C. for 20 minutes while applying pressure to obtain a sheet-like crosslinked product. The obtained sheet-like crosslinked product was punched with a JIS No. 3 dumbbell to prepare a test piece. Using the obtained test piece, the tensile strength, elongation and 100% tensile stress of the cross-linked product were measured according to JIS K6251.
（４）常態物性（硬さ）
上記（３）と同様にして得たシート状ゴム架橋物につき、ＪＩＳ Ｋ６２５３に従い、デュロメータ硬さ試験機タイプＡを用いて架橋物の硬さを測定した。(4) Normal physical properties (hardness)
About the sheet-like rubber cross-linked product obtained in the same manner as (3) above, the hardness of the cross-linked product was measured using a durometer hardness tester type A according to JIS K6253.
（５）耐熱老化性（空気加熱老化試験）
上記（３）と同様にして得た試験片をＪＩＳ Ｋ６２５７のノーマルオーブン法に従って１００℃に７０時間置き、その後取り出して、上記（３）と同様にして引張強さおよび伸びを測定し、得られた引張強さおよび伸びにつき、上記（３）の常態物性のそれぞれの値からの変化率（％）を求めた。また、硬さを上記（４）と同様にして測定し、得られた硬さにつき、上記（４）の常態物性の値からの変化（ポイント）を求めた。(5) Heat aging resistance (air heat aging test)
A test piece obtained in the same manner as in the above (3) was placed at 100 ° C. for 70 hours in accordance with the normal oven method of JIS K6257, then taken out and measured for tensile strength and elongation in the same manner as in (3) above. For the tensile strength and elongation, the rate of change (%) from each value of the normal physical properties of (3) above was determined. Further, the hardness was measured in the same manner as in the above (4), and the change (point) from the value of the normal physical properties in the above (4) was determined for the obtained hardness.
（６）耐油性（浸漬試験）
ＪＩＳ Ｋ６２５８に従い、それぞれ、燃料油Ｃ（イソオクタンとトルエンとを容積比１：１で混合したもの）中、燃料油ＣＥ−２０（イソオクタン／トルエン／エタノールの重量比が４０／４０／２０であるガソホール）中に、４０℃で４８時間浸漬し、浸漬前後の体積の変化率（単位：％）を測定した。(6) Oil resistance (immersion test)
Gasohol with fuel oil CE-20 (isooctane / toluene / ethanol weight ratio of 40/40/20) in fuel oil C (mixture of isooctane and toluene in a volume ratio of 1: 1) according to JIS K6258, respectively. ) For 48 hours at 40 ° C., and the volume change rate (unit:%) before and after immersion was measured.
（７）ガソリン透過性
燃料油Ｃおよび燃料油ＣＥ−２０について、アルミカップ法によりそれぞれガソリン透過性を測定した。アルミカップ法とは、まず、１００ｍｌ容量のアルミニウム製のカップに５０ｍｌの燃料油Ｃまたは燃料油ＣＥ−２０を入れ、これに上記試験片で蓋をし、締め具で該試験片によりアルミカップ内外を隔てる部分の面積が２５．５０ｃｍ２になるように調整し、該アルミカップを２３℃の恒温槽内に放置し、その後、２４時間毎に重量測定することにより２４時間毎の油の透過量を測定し、その最大量を透過量とするものである（単位：ｇ・ｍｍ／ｍ２・ｄａｙ）。
なお、ガソリン透過量が少ない程、ガソリン透過性が低いと評価でき、耐ガソリン性に優れる。(7) Gasoline permeability About the fuel oil C and the fuel oil CE-20, the gasoline permeability was measured by the aluminum cup method, respectively. In the aluminum cup method, first, 50 ml of fuel oil C or fuel oil CE-20 is put into a 100 ml capacity aluminum cup, and the test piece is covered with the above test piece. The amount of oil permeation every 24 hours is adjusted by adjusting the area of the part separating 25.50 cm 2 , leaving the aluminum cup in a thermostat at 23 ° C., and then measuring the weight every 24 hours. And the maximum amount is defined as the transmission amount (unit: g · mm / m 2 · day).
In addition, it can be evaluated that gasoline permeability is so low that there is little gasoline permeability, and it is excellent in gasoline resistance.
（８）脆化温度
ＪＩＳ Ｋ６３０１に従い、脆化温度（℃）を測定した。(8) Brittle temperature The brittle temperature (° C.) was measured according to JIS K6301.
（製造例１）ニトリル共重合体ゴム（Ａ１）のラテックスの製造
反応容器に、水２４０部、アクリロニトリル６８．２部、１，３−ブタジエン８．４部及びドデシルベンゼンスルホン酸ナトリウム（乳化剤）２．５部を仕込み、温度を５℃に調整した。次いで、気相を減圧して十分に脱気してからラジカル開始剤としてパラメンタンヒドロペルオキシド０．０６部、エチレンジアミン四酢酸ナトリウム０．０２部、硫酸第一鉄（７水塩）０．００６部及びホルムアルデヒドスルホキシル酸ナトリウム０．０６部並びにドデシルメルカプタン（連鎖移動剤）１部を添加して乳化重合の１段目の反応を開始した。
そして、重合転化率が２８重量％、４７重量％、６１重量％及び７２重量％に達した時点で、反応容器に１，３−ブタジエンをそれぞれ６．９部、６．３部、５．５部及び４．７部追加して２段目、３段目、４段目及び５段目の重合反応を行った。その後、重合転化率が８０重量％に達した時点でヒドロキシルアミン硫酸塩０．３部と水酸化カリウム０．２部を添加して重合を停止させた。次いで、反応容器の内容物を７０℃に加温し、減圧下に水蒸気蒸留により未反応の単量体を回収してニトリル共重合体ゴム（Ａ１）のラテックス（固形分２６重量％）を得た。ニトリル共重合体ゴム（Ａ１）のアクリロニトリル単量体単位の含有量は、全単量体全体１００重量％に対して、５８．６重量％であり、ポリマームーニー粘度は９７．７であった。 (Production Example 1) Production of latex of nitrile copolymer rubber (A1) In a reaction vessel, 240 parts of water, 68.2 parts of acrylonitrile, 8.4 parts of 1,3-butadiene and sodium dodecylbenzenesulfonate (emulsifier) 2 .5 parts was charged and the temperature was adjusted to 5 ° C. Next, after depressurizing and sufficiently degassing the gas phase, 0.06 part of paramentane hydroperoxide, 0.02 part of sodium ethylenediaminetetraacetate, 0.006 part of ferrous sulfate (7 water salt) are used as radical initiators. Then, 0.06 part of sodium formaldehyde sulfoxylate and 1 part of dodecyl mercaptan (chain transfer agent) were added to initiate the first stage reaction of the emulsion polymerization.
When the polymerization conversion rate reached 28% by weight, 47% by weight, 61% by weight and 72% by weight, 6.9 parts, 6.3 parts and 5.5 parts of 1,3-butadiene were added to the reaction vessel, respectively. Part and 4.7 parts were added and the second, third, fourth and fifth polymerization reactions were carried out. Thereafter, when the polymerization conversion reached 80% by weight, 0.3 part of hydroxylamine sulfate and 0.2 part of potassium hydroxide were added to terminate the polymerization. Next, the contents of the reaction vessel were heated to 70 ° C., and unreacted monomers were recovered by steam distillation under reduced pressure to obtain a latex of nitrile copolymer rubber (A1) (solid content 26 wt%). It was. The content of acrylonitrile monomer units in the nitrile copolymer rubber (A1) was 58.6% by weight with respect to 100% by weight of the whole monomers, and the polymer Mooney viscosity was 97.7.
（製造例２）ニトリル共重合体ゴム（Ａ２）のラテックスの製造
製造例１の１段目の反応において、アクリロニトリル及び１，３−ブタジエンの量をそれぞれ７１．６部及び６．２部とした他は、製造例１と同様にして乳化重合１段目の反応を開始した。
そして、重合転化率が１９重量％、３８重量％、５１重量％及び６２重量％に達した時点で、反応容器に１，３−ブタジエンをそれぞれ７．０部、５．５部、５．１部及び４．７部追加して２段目、３段目、４段目及び５段目の重合反応を行った。その後、重合転化率が７０重量％に達した時点でヒドロキシルアミン硫酸塩０．３部と水酸化カリウム０．２部を添加して重合を停止させ、製造例１と同様に水蒸気蒸留を行ってニトリル共重合体ゴム（Ａ２）のラテックス（固形分２４重量％）を得た。ニトリル共重合体ゴム（Ａ２）のアクリロニトリル単量体単位の含有量は６０．０重量％であり、ポリマームーニー粘度は７７．６であった。 (Production Example 2) Production of latex of nitrile copolymer rubber (A2) In the first stage reaction of Production Example 1, the amounts of acrylonitrile and 1,3-butadiene were 71.6 parts and 6.2 parts, respectively. Otherwise, the reaction in the first stage of emulsion polymerization was started in the same manner as in Production Example 1.
When the polymerization conversion rate reaches 19% by weight, 38% by weight, 51% by weight and 62% by weight, 7.0 parts, 5.5 parts and 5.1 parts of 1,3-butadiene are added to the reaction vessel, respectively. Part and 4.7 parts were added and the second, third, fourth and fifth polymerization reactions were carried out. Thereafter, when the polymerization conversion rate reached 70% by weight, 0.3 part of hydroxylamine sulfate and 0.2 part of potassium hydroxide were added to stop the polymerization, and steam distillation was performed in the same manner as in Production Example 1. A latex of nitrile copolymer rubber (A2) (solid content: 24% by weight) was obtained. The content of the acrylonitrile monomer unit in the nitrile copolymer rubber (A2) was 60.0% by weight, and the polymer Mooney viscosity was 77.6.
（比較製造例１）ニトリル共重合体ゴム（Ａ３）のラテックスの製造
反応容器に、水２５０部、アクリロニトリル６０部、１，３−ブタジエン２０部、ドデシルベンゼンスルホン酸ナトリウム２．５部、ｔ−ドデシルメルカプタン１部および硫酸第一鉄０．００８部を仕込み、気相を減圧して十分に脱気した後、パラメンタンヒドロペルオキシド０．０３部を仕込み、１０℃で乳化重合を開始した。仕込み単量体に対する重合転化率が４２および６０重量％に達した時点で、１，３−ブタジエンをそれぞれ１０部添加し、仕込み全単量体に対する重合転化率が７４重量％に達した時点で、反応容器に０.３部のヒドロキシルアミン硫酸塩と０．２部の水酸化カリウムとを添加して重合を停止させた。その後、製造例１と同様にして水蒸気蒸留を行って、ニトリル共重合体ゴム（Ａ３）のラテックスを得た。ニトリル共重合体ゴム（Ａ３）のアクリロニトリル単量体単位含有量は４９重量％、ポリマームーニー粘度は９０．０であった。 (Comparative Production Example 1) Production of latex of nitrile copolymer rubber (A3) In a reaction vessel, 250 parts of water, 60 parts of acrylonitrile, 20 parts of 1,3-butadiene, 2.5 parts of sodium dodecylbenzenesulfonate, t- After charging 1 part of dodecyl mercaptan and 0.008 part of ferrous sulfate and sufficiently degassing the gas phase, 0.03 part of paramentane hydroperoxide was charged and emulsion polymerization was started at 10 ° C. When the polymerization conversion ratio with respect to the charged monomer reaches 42 and 60% by weight, 10 parts of 1,3-butadiene is added respectively, and when the polymerization conversion ratio with respect to the charged monomer reaches 74% by weight. The polymerization was stopped by adding 0.3 parts of hydroxylamine sulfate and 0.2 parts of potassium hydroxide to the reaction vessel. Thereafter, steam distillation was performed in the same manner as in Production Example 1 to obtain a latex of nitrile copolymer rubber (A3). The nitrile copolymer rubber (A3) had an acrylonitrile monomer unit content of 49% by weight and a polymer Mooney viscosity of 90.0.
（調製例１）可塑剤のエマルションの調製
ジ（ブトキシエトキシエチル）アジペート（可塑剤）５０重量％の水性エマルションを、乳化剤としてオレイン酸カリウムを、同可塑剤に対して２．０重量％使用して強撹拌下で混合することにより調製した。 (Preparation Example 1) Preparation of emulsion of plasticizer An aqueous emulsion of 50% by weight of di (butoxyethoxyethyl) adipate (plasticizer) was used, and potassium oleate as an emulsifier was used in an amount of 2.0% by weight based on the plasticizer. And mixing under strong stirring.
実施例１
ニトリル共重合体ゴム（Ａ１）のラテックスを容器内で撹拌しつつ、該ラテックスの固形分（重合体）１００重量部に対して、上記にて調製したジ（ブトキシエトキシエチル）アジペートを含有するエマルション３０重量部を加えて混合液を得た。その後、この混合液を、該ラテックスの固形分に対して４重量％となる量の塩化カルシウム（凝固剤）を含有する水溶液に、撹拌下で注ぎ入れて重合体を凝固させた。これを濾別してクラムを回収し、水洗した後、６０℃で減圧乾燥して、ニトリル共重合体ゴム（Ａ１）及び可塑剤の固形の混合物を得た。 Example 1
An emulsion containing di (butoxyethoxyethyl) adipate prepared above with respect to 100 parts by weight of the solid content (polymer) of the latex while stirring the latex of the nitrile copolymer rubber (A1) in a container. 30 parts by weight was added to obtain a mixed solution. Thereafter, the mixed solution was poured into an aqueous solution containing calcium chloride (coagulant) in an amount of 4% by weight based on the solid content of the latex with stirring to coagulate the polymer. The crumb was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain a solid mixture of the nitrile copolymer rubber (A1) and the plasticizer.
次いで、バンバリーミキサを用いて、該混合物中のニトリル共重合体ゴム（Ａ１）１００部に対して、ＦＥＦカーボンブラック（製品名「シーストＳＯ」、東海カーボン社製、充填剤）２０部、ステアリン酸１部、酸化亜鉛５部を添加して５０℃にて混合した後、この混合物をロールに移してテトラメチルチウラムジスルフィド（製品名「ノクセラーＴＴ」、大内新興社製、架橋促進剤）１．５部、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（製品名「ノクセラーＣＺ」、大内新興社製、架橋促進剤）１．５部、および、３２５メッシュ硫黄０．５部を添加して５０℃で混練し、ニトリル共重合体ゴム組成物を調製した。
得られたニトリル共重合体ゴム組成物のコンパウンドムーニー粘度と、該組成物を架橋して得た架橋物について常態物性、空気加熱老化試験（耐熱老化性）、浸漬試験、ガソリン透過性および脆化温度について試験、評価した結果を表１に記す。Then, using a Banbury mixer, 20 parts of FEF carbon black (product name “Seast SO”, manufactured by Tokai Carbon Co., Ltd., filler) with respect to 100 parts of nitrile copolymer rubber (A1) in the mixture, stearic acid After 1 part and 5 parts of zinc oxide were added and mixed at 50 ° C., this mixture was transferred to a roll and tetramethylthiuram disulfide (product name “Noxeller TT”, manufactured by Ouchi Shinsei Co., Ltd., crosslinking accelerator). 5 parts, 1.5 parts of N-cyclohexyl-2-benzothiazolylsulfenamide (product name “Noxeller CZ”, manufactured by Ouchi Shinsei Co., Ltd., crosslinking accelerator), and 0.5 part of 325 mesh sulfur are added. And kneaded at 50 ° C. to prepare a nitrile copolymer rubber composition.
Compound Mooney viscosity of the resulting nitrile copolymer rubber composition, and normal properties, air heat aging test (heat aging resistance), immersion test, gasoline permeability and embrittlement of the crosslinked product obtained by crosslinking the composition Table 1 shows the results of the test and evaluation for temperature.
実施例２
実施例１において、ニトリル共重合体ゴム（Ａ１）のラテックスに代えてニトリル共重合体ゴム（Ａ２）のラテックスを用いた他は、実施例１と同様に行ってニトリル共重合体ゴム組成物を調製した。実施例１と同様の項目につき試験、評価を行った結果を表１に記す。 Example 2
A nitrile copolymer rubber composition was prepared in the same manner as in Example 1 except that the latex of the nitrile copolymer rubber (A2) was used instead of the latex of the nitrile copolymer rubber (A1). Prepared. Table 1 shows the results of tests and evaluations for the same items as in Example 1.
比較例１
ニトリル共重合体ゴム（Ａ１）のラテックスを、該ラテックスの固形分に対して４重量％となる量の塩化カルシウム（凝固剤）を含有する水溶液に、撹拌下で注ぎ入れて重合体を凝固させた。凝固物を濾別してクラムを回収し、水洗した後、６０℃で減圧乾燥してニトリル共重合体ゴム（Ａ１）を得た。 Comparative Example 1
The latex of the nitrile copolymer rubber (A1) is poured under stirring into an aqueous solution containing calcium chloride (coagulant) in an amount of 4% by weight based on the solid content of the latex to coagulate the polymer. It was. The coagulated product was separated by filtration, and crumbs were collected, washed with water, and dried under reduced pressure at 60 ° C. to obtain a nitrile copolymer rubber (A1).
バンバリーミキサを用いて、ニトリル共重合体ゴム（Ａ１）１００部に、ＦＥＦカーボンブラック２０部、ステアリン酸１部及び酸化亜鉛５部を添加して５０℃にて混合した。次いで、この混合物をロールに移して、ジ（ブトキシエトキシエチル）アジペート１５部を添加して混練したが、表面へのブリードが多くて十分に混合することができなかった。ロール表面に未混合の可塑剤が多量に付着していたため、この混練物を他のロールに移し、テトラメチルチウラムジスルフィド１．５部、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド１．５部、及び、３２５メッシュ硫黄０．５部を添加して５０℃で混練し、ニトリル共重合体ゴム組成物を調製した。実施例１と同様の項目につき試験、評価を行った結果を表１に記す。 Using a Banbury mixer, 20 parts of FEF carbon black, 1 part of stearic acid and 5 parts of zinc oxide were added to 100 parts of nitrile copolymer rubber (A1) and mixed at 50 ° C. Next, this mixture was transferred to a roll, and 15 parts of di (butoxyethoxyethyl) adipate was added and kneaded. However, there were many bleeds on the surface, and sufficient mixing was not possible. Since a large amount of unmixed plasticizer was adhered to the roll surface, this kneaded product was transferred to another roll, and 1.5 parts of tetramethylthiuram disulfide and 1.5 parts of N-cyclohexyl-2-benzothiazolylsulfenamide were added. Part and 0.5 part of 325 mesh sulfur were added and kneaded at 50 ° C. to prepare a nitrile copolymer rubber composition. Table 1 shows the results of tests and evaluations for the same items as in Example 1.
比較例２、３
比較例２においては、比較例１で得られたニトリル共重合体ゴム（Ａ１）を、また、比較例３においては、比較例１と同様にして凝固及び乾燥して得たニトリル共重合体ゴム（Ａ３）を、それぞれ用いて、ロールでの混練においてジ（ブトキシエトキシエチル）アジペートを添加しなかった他は、比較例１と同様に行い、それぞれニトリル共重合体ゴム組成物を調製した。実施例１と同様の項目につき試験、評価を行った結果を表１に記す。 Comparative Examples 2 and 3
In Comparative Example 2, the nitrile copolymer rubber (A1) obtained in Comparative Example 1 was used. In Comparative Example 3, the nitrile copolymer rubber obtained by coagulation and drying in the same manner as Comparative Example 1. A nitrile copolymer rubber composition was prepared in the same manner as in Comparative Example 1 except that (A3) was used and di (butoxyethoxyethyl) adipate was not added in kneading with a roll. Table 1 shows the results of tests and evaluations for the same items as in Example 1.
表１に示すように、本発明のニトリル共重合体ゴム架橋物は、十分な常態物性及び耐熱老化性を有し、さらには、油類への浸漬試験で油類の浸透が少なく、ガソリン透過性が低く、脆化温度も十分低かった（実施例１、２）。 As shown in Table 1, the nitrile copolymer rubber cross-linked product of the present invention has sufficient normal physical properties and heat aging resistance. The embrittlement temperature was low enough (Examples 1 and 2).
これに対して、可塑剤をロールで配合して架橋して得た架橋物は、ロール混練時の可塑剤のブリードが甚大で作業性が悪く、脆化温度も高かった（比較例１）。
また、可塑剤を添加しないと、架橋物のガソリン透過性は、本発明の実施例よりも低かったが、浸漬試験の膨潤が大きく、脆化温度が高かった（比較例２）。
さらに、可塑剤を添加せず、さらには、本発明所定のニトリル含量を有しないニトリル共重合体ゴムの場合、脆化温度が高いことに加えて、浸漬試験での膨潤が大きく、ガソリン透過性が大きくなった（比較例３）。On the other hand, the crosslinked product obtained by blending a plasticizer with a roll had a large plasticizer bleed during roll kneading, poor workability, and a high embrittlement temperature (Comparative Example 1).
When the plasticizer was not added, the gasoline permeability of the crosslinked product was lower than that of the examples of the present invention, but the swelling in the immersion test was large and the embrittlement temperature was high (Comparative Example 2).
Furthermore, in the case of a nitrile copolymer rubber not having a plasticizer added and further having a predetermined nitrile content of the present invention, in addition to a high embrittlement temperature, the swelling in the immersion test is large and the gasoline permeability is high. Increased (Comparative Example 3).
実施例３
バンバリーミキサにて、高ニトリルゴム（ＤＮ４０５０、日本ゼオン社製、アクリロニトリル単量体単位含有量４０重量％、ポリマームーニー粘度５０.０、脆化温度−２０．２℃）１００部に、ＦＥＦカーボンブラック６０部、ステアリン酸１部、酸化亜鉛５部及びジ（ブトキシエトキシエチル）アジペート５部を添加し、５０℃で混合した。次いで、混合物をロールに移してテトラメチルチウラムジスルフィド１．５部、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド１．５部、および、３２５メッシュ硫黄０．５部を添加して５０℃で混練し、高ニトリルゴム組成物を調製した。 Example 3
In a Banbury mixer, 100 parts of high nitrile rubber (DN4050, manufactured by Nippon Zeon Co., Ltd., acrylonitrile monomer unit content 40 wt%, polymer Mooney viscosity 50.0, embrittlement temperature -20.2 ° C), FEF carbon black 60 parts, 1 part of stearic acid, 5 parts of zinc oxide and 5 parts of di (butoxyethoxyethyl) adipate were added and mixed at 50 ° C. The mixture was then transferred to a roll and 1.5 parts of tetramethylthiuram disulfide, 1.5 parts of N-cyclohexyl-2-benzothiazolylsulfenamide, and 0.5 parts of 325 mesh sulfur were added at 50 ° C. A high nitrile rubber composition was prepared by kneading.
実施例１と同様にして得たニトリル共重合体ゴム組成物と、上記で得た高ニトリルゴム組成物と、を用いてロールにてそれぞれ別々に一次混練し、別々にシート化することにより、それぞれ厚み１.２ｍｍのシート状物を作製した。次いで、両シート状物を積層して、１６０℃、２０分、プレス圧１０ＭＰａでプレス架橋を行い、合計の厚みが２ｍｍの積層体を得た。得られた積層体につき実施例１と同様の項目について試験、評価した結果を表２に記す。 By using the nitrile copolymer rubber composition obtained in the same manner as in Example 1 and the high nitrile rubber composition obtained above, respectively, primary kneading separately with a roll, and separately forming a sheet, Sheet-like materials each having a thickness of 1.2 mm were produced. Subsequently, both sheet-like materials were laminated and subjected to press crosslinking at 160 ° C. for 20 minutes at a press pressure of 10 MPa to obtain a laminate having a total thickness of 2 mm. Table 2 shows the results of testing and evaluating the same items as in Example 1 for the obtained laminate.
比較例４
比較例３と同様にして得たニトリル共重合体ゴム組成物と、実施例３と同様にして得た高ニトリルゴム組成物を用い、実施例３と同様な工程でプレス架橋を行い、合計の厚みが厚み２ｍｍの積層体を得た。得られた積層体につき実施例１と同様の項目について試験、評価した結果を表２に記す。 Comparative Example 4
Using the nitrile copolymer rubber composition obtained in the same manner as in Comparative Example 3 and the high nitrile rubber composition obtained in the same manner as in Example 3, press crosslinking was performed in the same process as in Example 3, and the total A laminate having a thickness of 2 mm was obtained. Table 2 shows the results of testing and evaluating the same items as in Example 1 for the obtained laminate.
表２に示すように、本発明のニトリル共重合体ゴム架橋物を用いてなる層（Ｉ）と、ニトリル含量が４０重量％であるニトリル共重合体ゴムを用いてなる層（ＩＩ）とで構成される積層体は、ガソリン透過性が低く（層（Ｉ）の影響によると考えられる。）、また、脆化温度も十分低かった（実施例３）。
これに対し、本発明所定のニトリル含量を有しないニトリル共重合体ゴムを用いた積層体は、ガソリン透過性が高い架橋物を与えた（比較例４）。
As shown in Table 2, the layer (I) using the crosslinked nitrile copolymer rubber of the present invention and the layer (II) using a nitrile copolymer rubber having a nitrile content of 40% by weight. The constructed laminate had low gasoline permeability (considered by the influence of layer (I)), and the brittle temperature was sufficiently low (Example 3).
On the other hand, the laminated body using the nitrile copolymer rubber having no predetermined nitrile content of the present invention gave a crosslinked product having high gasoline permeability (Comparative Example 4).
Claims (11)
ＨＯＯＣＲＣＯＯＨ （１）
（式中のＲは、炭素数２〜１０のアルキレン基を表し、ＣＯＯＨはカルボキシ基を表す。）The plasticizer (B) is an ester compound (b) of a compound (b1) having a chemical structure represented by the following general formula (1) and an ether bond-containing alcohol (b2). The nitrile copolymer rubber crosslinked product described.
HOOCRCOOH (1)
(R in the formula represents an alkylene group having 2 to 10 carbon atoms, and COOH represents a carboxy group.)
α、β−エチレン性不飽和ニトリル単量体単位５５〜８０重量％を有するニトリル共重合体ゴム（Ａ）のラテックスと、可塑剤（Ｂ）のエマルションと、の混合液を調製する工程と、
該混合液を凝固させ、その後、乾燥させて固形の混合物とする工程と、
該混合物とゴム用配合剤とを混練する工程と、
を含むことを特徴とするニトリル共重合体ゴム組成物の製造方法。A method for producing a nitrile copolymer rubber composition according to claim 7,
a step of preparing a mixture of a latex of a nitrile copolymer rubber (A) having 55 to 80% by weight of an α, β-ethylenically unsaturated nitrile monomer unit and an emulsion of a plasticizer (B);
Solidifying the mixture and then drying to form a solid mixture;
Kneading the mixture and a rubber compounding agent;
The manufacturing method of the nitrile copolymer rubber composition characterized by including.
ＨＯＯＣＲＣＯＯＨ （１）
（式中のＲは、炭素数２〜１０のアルキレン基を表し、ＣＯＯＨはカルボキシ基を表す。）The plasticizer (B) is an ester compound (b) of a compound (b1) having a chemical structure represented by the following general formula (1) and an ether bond-containing alcohol (b2). A process for producing a nitrile copolymer rubber composition.
HOOCRCOOH (1)
(R in the formula represents an alkylene group having 2 to 10 carbon atoms, and COOH represents a carboxy group.)
α、β−エチレン性不飽和ニトリル単量体単位５重量％以上、５５重量％未満を有するニトリル共重合体ゴム（Ｌ）１００重量部に対して、可塑剤（Ｍ）０〜１００重量部含有し、脆化温度が−７０〜−１０℃であるニトリル共重合体ゴム架橋物からなり、厚み０.１〜１０ｍｍの層（ＩＩ）と、
を積層してなる積層体。A layer (I) comprising the crosslinked nitrile copolymer rubber according to any one of claims 1 to 6 and having a thickness of 0.1 to 10 mm;
Containing 0-100 parts by weight of plasticizer (M) for 100 parts by weight of nitrile copolymer rubber (L) having 5% by weight or more and less than 55% by weight of α, β-ethylenically unsaturated nitrile monomer unit And a nitrile copolymer rubber cross-linked product having an embrittlement temperature of −70 to −10 ° C., and a layer (II) having a thickness of 0.1 to 10 mm,
A laminate formed by laminating layers.
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| CN101932649B (en) | 2008-01-30 | 2013-04-24 | 日本瑞翁株式会社 | Nitrile copolymer latex composition and nitrile copolymer rubber composition |
| CN105330913B (en) * | 2015-11-24 | 2018-04-13 | 中国航空工业集团公司沈阳飞机设计研究所 | A kind of rubber compound |
| JP7200569B2 (en) * | 2018-09-26 | 2023-01-10 | 日本ゼオン株式会社 | Rubber mixture, nitrile group-containing copolymer rubber composition, crosslinkable rubber composition and crosslinked rubber |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2223233A (en) * | 1988-08-18 | 1990-04-04 | Lexington Precision Corp | Fuel resistant elastomeric composition |
| EP0430349A3 (en) * | 1989-11-27 | 1991-10-16 | Stamicarbon B.V. | Process for the polymerization and recovery of nitrile rubber containing high bound acrylonitrile |
| EP1152029A4 (en) * | 1998-11-04 | 2002-11-20 | Nippon Zeon Co | Polyblend composition, crosslinked object, and hose for fuel |
| JP2001072804A (en) * | 1999-06-28 | 2001-03-21 | Tokai Rubber Ind Ltd | Rubber composition and fuel delivery hose for automobile |
| JP2001131347A (en) * | 1999-11-08 | 2001-05-15 | Tokai Rubber Ind Ltd | Rubber composition for fuel transportation hose for automobile |
| JP4899262B2 (en) * | 2000-11-13 | 2012-03-21 | Ｊｓｒ株式会社 | Unsaturated nitrile-conjugated diene rubber, rubber composition and production method thereof |
| JP2004059695A (en) * | 2002-07-26 | 2004-02-26 | Nippon Zeon Co Ltd | Polymer alloy, crosslinked material and fuel hose |
-
2006
- 2006-08-29 JP JP2007533262A patent/JPWO2007026707A1/en active Pending
- 2006-08-29 WO PCT/JP2006/316999 patent/WO2007026707A1/en active Application Filing
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| Publication number | Publication date |
|---|---|
| WO2007026707A1 (en) | 2007-03-08 |
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