JP2007154095A - Rubber composition and tire by using the same - Google Patents
Rubber composition and tire by using the same Download PDFInfo
- Publication number
- JP2007154095A JP2007154095A JP2005353428A JP2005353428A JP2007154095A JP 2007154095 A JP2007154095 A JP 2007154095A JP 2005353428 A JP2005353428 A JP 2005353428A JP 2005353428 A JP2005353428 A JP 2005353428A JP 2007154095 A JP2007154095 A JP 2007154095A
- Authority
- JP
- Japan
- Prior art keywords
- group
- natural rubber
- meth
- rubber composition
- tire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- 239000005060 rubber Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 55
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 55
- 229920001194 natural rubber Polymers 0.000 claims abstract description 55
- 239000006229 carbon black Substances 0.000 claims abstract description 37
- 229920006173 natural rubber latex Polymers 0.000 claims abstract description 31
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 230000001112 coagulating effect Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003990 inverse gas chromatography Methods 0.000 claims abstract description 4
- -1 hydrazo group Chemical group 0.000 claims description 49
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 7
- 238000004040 coloring Methods 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000002560 nitrile group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 3
- 125000002228 disulfide group Chemical group 0.000 claims description 3
- 125000005462 imide group Chemical group 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 3
- 125000000101 thioether group Chemical group 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 30
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000005299 abrasion Methods 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 2
- 238000002845 discoloration Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 33
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 26
- 239000000945 filler Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920000126 latex Polymers 0.000 description 8
- 239000004816 latex Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000004103 aminoalkyl group Chemical group 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010559 graft polymerization reaction Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VNSCVITYYHPXKX-UHFFFAOYSA-N 2-(4-anilinophenyl)-3-phenylbut-2-enedioic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)=C(C(O)=O)C(C=C1)=CC=C1NC1=CC=CC=C1 VNSCVITYYHPXKX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007717 redox polymerization reaction Methods 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- UUZJJNBYJDFQHL-UHFFFAOYSA-N 1,2,3-triazolidine Chemical compound C1CNNN1 UUZJJNBYJDFQHL-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KDELZSILBPDHCV-UHFFFAOYSA-N 1-trimethylsilyloxypropyl prop-2-enoate Chemical compound C[Si](C)(C)OC(CC)OC(=O)C=C KDELZSILBPDHCV-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- AOCFPNHJAUWWQS-UHFFFAOYSA-N 2-(3-methylbuta-1,3-dienyl)-n-phenylaniline Chemical compound CC(=C)C=CC1=CC=CC=C1NC1=CC=CC=C1 AOCFPNHJAUWWQS-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
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- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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- XKRDOHUZWLIZFI-UHFFFAOYSA-N 3-(4-anilinophenyl)-2-methylprop-2-enal Chemical compound C1=CC(C=C(C=O)C)=CC=C1NC1=CC=CC=C1 XKRDOHUZWLIZFI-UHFFFAOYSA-N 0.000 description 1
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- NDIUUUZOUAQYFI-UHFFFAOYSA-N 3-(4-anilinophenyl)prop-2-enenitrile Chemical compound C1=CC(C=CC#N)=CC=C1NC1=CC=CC=C1 NDIUUUZOUAQYFI-UHFFFAOYSA-N 0.000 description 1
- IUAIGUGUXHPCNN-UHFFFAOYSA-N 3-(4-anilinophenyl)prop-2-enoic acid Chemical compound C1=CC(C=CC(=O)O)=CC=C1NC1=CC=CC=C1 IUAIGUGUXHPCNN-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- XIWKWGKHZFFEEA-UHFFFAOYSA-N 3-[dimethyl(phenoxy)silyl]propyl prop-2-enoate Chemical compound C=CC(=O)OCCC[Si](C)(C)OC1=CC=CC=C1 XIWKWGKHZFFEEA-UHFFFAOYSA-N 0.000 description 1
- NFRMMOZYKVAQBB-UHFFFAOYSA-N 3-[dimethyl(phenylmethoxy)silyl]propyl prop-2-enoate Chemical compound C=CC(=O)OCCC[Si](C)(C)OCC1=CC=CC=C1 NFRMMOZYKVAQBB-UHFFFAOYSA-N 0.000 description 1
- JUINTNKGYWNEDR-UHFFFAOYSA-N 3-[dimethyl(propoxy)silyl]propyl prop-2-enoate Chemical compound CCCO[Si](C)(C)CCCOC(=O)C=C JUINTNKGYWNEDR-UHFFFAOYSA-N 0.000 description 1
- DGBFOBNYTYHFPN-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C=C DGBFOBNYTYHFPN-UHFFFAOYSA-N 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物及び該ゴム組成物を用いたタイヤに関し、特にタイヤのトレッドに用いることで、低ロス性に加え、タイヤに十分な耐摩耗性及び耐破壊性を付与することが可能なゴム組成物に関するものである。 The present invention relates to a rubber composition and a tire using the rubber composition, and in particular, by using it for a tread of a tire, it is possible to impart sufficient wear resistance and fracture resistance to the tire in addition to low loss. The present invention relates to a rubber composition.
昨今、自動車の低燃費化に対する要求が強くなりつつあり、転がり抵抗の小さいタイヤが求められている。そのため、タイヤのトレッド等に使用するゴム組成物として、低ロス性（低発熱性）に優れたゴム組成物が求められている。また、トレッド用のゴム組成物においては、低ロス性に加え、耐摩耗性及び破壊特性に優れることが求められる。これらの要求に対して、ゴム成分にカーボンブラック等の充填剤を配合したゴム組成物の低ロス性、耐摩耗性及び破壊特性を改良するには、ゴム組成物中の充填剤とゴム成分との親和性を向上させることが有効である。 In recent years, there is an increasing demand for lower fuel consumption of automobiles, and tires with low rolling resistance are required. Therefore, a rubber composition excellent in low loss (low heat generation) is required as a rubber composition used for tire treads and the like. In addition, a rubber composition for a tread is required to have excellent wear resistance and fracture characteristics in addition to low loss. In response to these requirements, in order to improve the low loss property, wear resistance and fracture characteristics of a rubber composition containing a filler such as carbon black in the rubber component, the filler and rubber component in the rubber composition It is effective to improve the affinity.
例えば、ゴム組成物中の充填剤とゴム成分との親和性を向上させ、充填剤による補強効果を向上させるために、末端変性により充填剤との親和性を向上させた合成ゴムや、官能基含有単量体を共重合させて充填剤との親和性を向上させた合成ゴム等が開発されている。 For example, in order to improve the affinity between the filler and the rubber component in the rubber composition and to improve the reinforcing effect by the filler, synthetic rubber or functional group having improved affinity with the filler by terminal modification Synthetic rubbers and the like have been developed in which the monomers are copolymerized to improve the affinity with the filler.
一方、天然ゴムは、その優れた物理特性を生かして多量に使用されているものの、天然ゴム自体を改良して充填剤との親和性を向上させ、充填剤による補強効果を大幅に向上させる技術はない。 On the other hand, although natural rubber is used in large quantities by taking advantage of its excellent physical properties, it is a technology that improves the natural rubber itself to improve the affinity with the filler and greatly enhance the reinforcing effect of the filler. There is no.
例えば、天然ゴムをエポキシ化する技術が提案されているが、該技術では天然ゴムと充填剤との親和性を十分に向上させることができないため、充填剤による補強効果を十分に向上させることができない。また、天然ゴムラテックスにビニル系単量体を添加してグラフト重合する技術が知られており、該技術で得られたグラフト化天然ゴムは、接着剤用途等で実用化されている。しかし、該グラフト化天然ゴムは、天然ゴム自身の特性を変えるために単量体として多量（20〜50質量％）のビニル化合物をグラフト化しているため、カーボンブラックと配合すると、大幅な粘度上昇を招き、加工性が低下する。また、多量のビニル化合物が天然ゴム分子鎖に導入されているため、天然ゴム本来の優れた物理特性（粘弾性、引張試験等における応力−歪曲線）が損なわれてしまう。 For example, a technology for epoxidizing natural rubber has been proposed. However, since this technology cannot sufficiently improve the affinity between the natural rubber and the filler, the reinforcing effect of the filler can be sufficiently improved. Can not. Further, a technique of graft polymerization by adding a vinyl monomer to natural rubber latex is known, and the grafted natural rubber obtained by the technique has been put into practical use for adhesives and the like. However, the grafted natural rubber is grafted with a large amount (20 to 50% by mass) of a vinyl compound as a monomer to change the properties of the natural rubber itself. And processability is reduced. In addition, since a large amount of vinyl compound is introduced into the natural rubber molecular chain, the excellent physical properties of natural rubber (stress-strain curve in viscoelasticity, tensile test, etc.) are impaired.
また、特許公開公報２００４−３５９７１３号（特許文献４）には、天然ゴムラテックス中の天然ゴム分子に極性基含有単量体をグラフト重合してなる変性天然ゴムにより、耐摩耗性及び低発熱性を改良したゴム組成物が得られることが開示されている。 Patent Publication No. 2004-359713 (Patent Document 4) discloses a modified natural rubber obtained by graft-polymerizing a polar group-containing monomer to a natural rubber molecule in natural rubber latex, thereby providing wear resistance and low heat generation. It is disclosed that a rubber composition improved in the above can be obtained.
しかし、特許公開公報２００４−３５９７１３号に開示の技術をもってしても、ゴム組成物の低ロス性及び耐摩耗性には改善の余地がある。 However, even with the technique disclosed in Japanese Patent Publication No. 2004-359713, there is room for improvement in the low loss and wear resistance of the rubber composition.
そこで、本発明の目的は、上記従来技術の問題を解決し、低ロス性に加え、タイヤに十分な耐摩耗性及び耐破壊性を付与することが可能なゴム組成物と、該ゴム組成物を用いたタイヤを提供することにある。 Accordingly, an object of the present invention is to solve the above-described problems of the prior art and to provide a rubber composition capable of imparting sufficient wear resistance and fracture resistance to a tire in addition to low loss characteristics, and the rubber composition It is to provide a tire using the tire.
本発明者は、上記目的を達成するために鋭意検討した結果、特定の変性天然ゴムに対して分散性の高いカーボンブラックを配合してなるゴム組成物をタイヤ、特にタイヤのトレッドに適用することで、低ロス性、耐摩耗性及び破壊特性を改善するタイヤが得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventor applied a rubber composition comprising carbon black having high dispersibility to a specific modified natural rubber to a tire, particularly a tire tread. Thus, the present inventors have found that a tire that improves low loss, wear resistance, and fracture characteristics can be obtained, thereby completing the present invention.
即ち、本発明のゴム組成物は、天然ゴムラテックスに極性基含有単量体を添加し、該極性基含有単量体を天然ゴムラテックス中の天然ゴム分子にグラフト重合させ、更に凝固及び乾燥してなる変性天然ゴムに対して、トルエン着色透過度が90％以上であって表面自由エネルギーとセチルトリメチルアンモニウムブロミド吸着比表面積(ＣＴＡＢ)（m2/g）が下記式（I）：
γd s＜２８７×ｌｎ(ＣＴＡＢ)−９８９ ・・・ (I）
[式中、γd sはインバースガスクロマトグラフィーを使用して算出した表面自由エネルギー（mJ/m2）である]の関係を満たすカーボンブラックを配合してなることを特徴とする。
That is, the rubber composition of the present invention is obtained by adding a polar group-containing monomer to natural rubber latex, graft polymerizing the polar group-containing monomer to natural rubber molecules in the natural rubber latex, and further coagulating and drying. For the modified natural rubber, the toluene coloring permeability is 90% or more, and the surface free energy and the cetyltrimethylammonium bromide adsorption specific surface area (CTAB) (m 2 / g) are represented by the following formula (I):
γ d s <287 × ln (CTAB) −989 (I)
Carbon black satisfying the relationship of [wherein γ d s is the surface free energy (mJ / m 2 ) calculated by using inverse gas chromatography] is characterized.
本発明のゴム組成物の好適例においては、前記極性基含有単量体の極性基がアミノ基、イミノ基、ニトリル基、アンモニウム基、イミド基、アミド基、ヒドラゾ基、アゾ基、ジアゾ基、ヒドロキシル基、カルボキシル基、カルボニル基、エポキシ基、オキシカルボニル基、スルフィド基、ジスルフィド基、スルホニル基、スルフィニル基、チオカルボニル基、含窒素複素環基、含酸素複素環基及びアルコキシシリル基からなる群から選ばれる少なくとも一つである。 In a preferred example of the rubber composition of the present invention, the polar group of the polar group-containing monomer is an amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, Group consisting of hydroxyl group, carboxyl group, carbonyl group, epoxy group, oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group and alkoxysilyl group Is at least one selected from
本発明のゴム組成物の他の好適例においては、前記極性基含有単量体のグラフト量が天然ゴムラテックスのゴム成分に対して0.01〜5.0質量％である。 In another preferred embodiment of the rubber composition of the present invention, the graft amount of the polar group-containing monomer is 0.01 to 5.0 mass% with respect to the rubber component of the natural rubber latex.
さらに本発明のゴム組成物の好適例においては、前記天然ゴムラテックスに界面活性剤を添加する。 Furthermore, in a preferred example of the rubber composition of the present invention, a surfactant is added to the natural rubber latex.
また、本発明のタイヤは、上記ゴム組成物をタイヤ部材のいずれかに用いたことを特徴とする。ここで、前記タイヤ部材がトレッドであることが好ましい。 The tire of the present invention is characterized in that the rubber composition is used for any of tire members. Here, the tire member is preferably a tread.
本発明によれば、特定の変性天然ゴムに対して分散性の高いカーボンブラックを配合することで、低ロス性に加え、タイヤに十分な耐摩耗性及び耐破壊性を付与することが可能なゴム組成物、並びに該ゴム組成物を用いたタイヤを提供することができる。 According to the present invention, by adding carbon black having high dispersibility to a specific modified natural rubber, it is possible to impart sufficient wear resistance and fracture resistance to a tire in addition to low loss. A rubber composition and a tire using the rubber composition can be provided.
以下に、本発明を詳細に説明する。本発明のゴム組成物は、天然ゴムラテックスに極性基含有単量体を添加し、該極性基含有単量体を天然ゴムラテックス中の天然ゴム分子にグラフト重合させ、更に凝固及び乾燥してなる変性天然ゴムに対して、トルエン着色透過度が90％以上であって表面自由エネルギー(γd s)とセチルトリメチルアンモニウムブロミド吸着比表面積(ＣＴＢＡ)が上記式（I）の関係を満たすカーボンブラックを配合してなることを特徴とする。上記極性基含有単量体をグラフト重合により天然ゴム分子に導入した変性天然ゴムは、未変性の天然ゴムに比べてカーボンブラックに対する親和性が高い。さらに上記式（I）の関係を満たすカーボンブラックは、通常のカーボンブラックよりもゴム成分に対する分散性が高い。そのため、該変性天然ゴムと上記カーボンブラックとを用いた本発明のゴム組成物は、ゴム成分に対するカーボンブラックの分散性が非常に高く、カーボンブラックの補強効果が十分に発揮されて、耐破壊性及び耐摩耗性に優れる上、低ロス性も大幅に向上している。 The present invention is described in detail below. The rubber composition of the present invention is obtained by adding a polar group-containing monomer to natural rubber latex, graft-polymerizing the polar group-containing monomer to natural rubber molecules in the natural rubber latex, and further coagulating and drying. Compared to the modified natural rubber, carbon black having a toluene coloring permeability of 90% or more and a surface free energy (γ d s ) and a cetyltrimethylammonium bromide adsorption specific surface area (CTBA) satisfying the relationship of the above formula (I). It is characterized by blending. The modified natural rubber in which the polar group-containing monomer is introduced into the natural rubber molecule by graft polymerization has higher affinity for carbon black than unmodified natural rubber. Furthermore, carbon black satisfying the relationship of the above formula (I) has higher dispersibility with respect to rubber components than ordinary carbon black. Therefore, the rubber composition of the present invention using the modified natural rubber and the carbon black has a very high dispersibility of the carbon black with respect to the rubber component, and the reinforcing effect of the carbon black is sufficiently exerted, so that the fracture resistance In addition to being excellent in wear resistance, low loss is also greatly improved.
上記変性天然ゴムの製造に用いる天然ゴムラテックスとしては、特に限定されず、例えば、フィールドラテックス、アンモニア処理ラテックス、遠心分離濃縮ラテックス、界面活性剤や酵素で処理した脱タンパク質ラテックス、及びこれらを組み合せたもの等を用いることができる。 The natural rubber latex used for the production of the modified natural rubber is not particularly limited. For example, field latex, ammonia-treated latex, centrifugal concentrated latex, deproteinized latex treated with a surfactant or an enzyme, and a combination thereof. A thing etc. can be used.
上記天然ゴムラテックスに添加される極性基含有単量体は、分子内に少なくとも一つの極性基を有し、天然ゴム分子とグラフト重合できる限り特に制限されるものでない。ここで、該極性基含有単量体は、天然ゴム分子とグラフト重合するために、分子内に炭素−炭素二重結合を有することが好ましく、極性基含有ビニル系単量体であることが好ましい。上記極性基の具体例としては、アミノ基、イミノ基、ニトリル基、アンモニウム基、イミド基、アミド基、ヒドラゾ基、アゾ基、ジアゾ基、ヒドロキシル基、カルボキシル基、カルボニル基、エポキシ基、オキシカルボニル基、スルフィド基、ジスルフィド基、スルホニル基、スルフィニル基、チオカルボニル基、含窒素複素環基、含酸素複素環基及びアルコキシシリル基等を好適に挙げることができる。これら極性基を含有する単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 The polar group-containing monomer added to the natural rubber latex is not particularly limited as long as it has at least one polar group in the molecule and can be graft-polymerized with the natural rubber molecule. Here, the polar group-containing monomer preferably has a carbon-carbon double bond in the molecule for graft polymerization with a natural rubber molecule, and is preferably a polar group-containing vinyl monomer. . Specific examples of the polar group include amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl group, epoxy group, oxycarbonyl Preferred examples include a group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group and alkoxysilyl group. These monomers containing polar groups may be used alone or in combination of two or more.
上記アミノ基を含有する単量体としては、１分子中に第１級、第２級及び第３級アミノ基から選ばれる少なくとも１つのアミノ基を含有する重合性単量体が挙げられる。該アミノ基を有する重合性単量体の中でも、ジアルキルアミノアルキル(メタ)アクリレート等の第３級アミノ基含有単量体が特に好ましい。これらアミノ基含有単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 Examples of the monomer containing an amino group include polymerizable monomers containing at least one amino group selected from primary, secondary and tertiary amino groups in one molecule. Among the polymerizable monomers having an amino group, a tertiary amino group-containing monomer such as dialkylaminoalkyl (meth) acrylate is particularly preferable. These amino group-containing monomers may be used alone or in a combination of two or more.
ここで、第１級アミノ基含有単量体としては、アクリルアミド、メタクリルアミド、４-ビニルアニリン、アミノメチル(メタ)アクリレート、アミノエチル(メタ)アクリレート、アミノプロピル(メタ)アクリレート、アミノブチル(メタ)アクリレート等が挙げられる。 Here, as the primary amino group-containing monomer, acrylamide, methacrylamide, 4-vinylaniline, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) ) Acrylate and the like.
また、第２級アミノ基含有単量体としては、（１）アニリノスチレン、β-フェニル-ｐ-アニリノスチレン、β-シアノ-ｐ-アニリノスチレン、β-シアノ-β-メチル-ｐ-アニリノスチレン、β-クロロ-ｐ-アニリノスチレン、β-カルボキシ-ｐ-アニリノスチレン、β-メトキシカルボニル-ｐ-アニリノスチレン、β-(２-ヒドロキシエトキシ)カルボニル-ｐ-アニリノスチレン、β-ホルミル-ｐ-アニリノスチレン、β-ホルミル-β-メチル-ｐ-アニリノスチレン、α-カルボキシ-β-カルボキシ-β-フェニル-ｐ-アニリノスチレン等のアニリノスチレン類、（２）１-アニリノフェニル-１,３-ブタジエン、１-アニリノフェニル-３-メチル-１,３-ブタジエン、１-アニリノフェニル-３-クロロ-１,３-ブタジエン、３-アニリノフェニル-２-メチル-１,３-ブタジエン、１-アニリノフェニル-２-クロロ-１,３-ブタジエン、２-アニリノフェニル-１,３-ブタジエン、２-アニリノフェニル-３-メチル-１,３-ブタジエン、２-アニリノフェニル-３-クロロ-１,３-ブタジエン等のアニリノフェニルブタジエン類、（３）Ｎ-メチル(メタ)アクリルアミド、Ｎ-エチル(メタ)アクリルアミド、Ｎ-メチロールアクリルアミド、Ｎ-(４-アニリノフェニル)メタクリルアミド等のＮ-モノ置換(メタ)アクリルアミド類等が挙げられる。 The secondary amino group-containing monomer includes (1) anilinostyrene, β-phenyl-p-anilinostyrene, β-cyano-p-anilinostyrene, β-cyano-β-methyl-p. -Anilinostyrene, β-chloro-p-anilinostyrene, β-carboxy-p-anilinostyrene, β-methoxycarbonyl-p-anilinostyrene, β- (2-hydroxyethoxy) carbonyl-p-anilino Anilinostyrenes such as styrene, β-formyl-p-anilinostyrene, β-formyl-β-methyl-p-anilinostyrene, α-carboxy-β-carboxy-β-phenyl-p-anilinostyrene, (2) 1-anilinophenyl-1,3-butadiene, 1-anilinophenyl-3-methyl-1,3-butadiene, 1-anilinophenyl-3-chloro-1,3-butadiene, 3-aniline Linophenyl-2-methyl-1,3-butadiene, 1-anilinov Nyl-2-chloro-1,3-butadiene, 2-anilinophenyl-1,3-butadiene, 2-anilinophenyl-3-methyl-1,3-butadiene, 2-anilinophenyl-3-chloro- Anilinophenylbutadienes such as 1,3-butadiene, (3) N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide, N- (4-anilinophenyl) methacrylamide, etc. N-mono substituted (meth) acrylamides and the like can be mentioned.
更に、第３級アミノ基含有単量体としては、Ｎ,Ｎ-ジ置換アミノアルキル(メタ)アクリレート及びＮ,Ｎ-ジ置換アミノアルキル(メタ)アクリルアミド等が挙げられる。 Furthermore, examples of the tertiary amino group-containing monomer include N, N-disubstituted aminoalkyl (meth) acrylate and N, N-disubstituted aminoalkyl (meth) acrylamide.
上記Ｎ,Ｎ-ジ置換アミノアルキル(メタ)アクリレートとしては、Ｎ,Ｎ-ジメチルアミノメチル(メタ)アクリレート、Ｎ,Ｎ-ジメチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジメチルアミノプロピル(メタ)アクリレート、Ｎ,Ｎ-ジメチルアミノブチル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノプロピル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノブチル(メタ)アクリレート、Ｎ-メチル-Ｎ-エチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジプロピルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジブチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジブチルアミノプロピル(メタ)アクリレート、Ｎ,Ｎ-ジブチルアミノブチル(メタ)アクリレート、Ｎ,Ｎ-ジヘキシルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジオクチルアミノエチル(メタ)アクリレート、アクリロイルモルフォリン等のアクリル酸又はメタクリル酸のエステル等が挙げられる。これらの中でも、Ｎ,Ｎ-ジメチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジエチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジプロピルアミノエチル(メタ)アクリレート、Ｎ,Ｎ-ジオクチルアミノエチル(メタ)アクリレート、Ｎ-メチル-Ｎ-エチルアミノエチル(メタ)アクリレート等が特に好ましい。 Examples of the N, N-disubstituted aminoalkyl (meth) acrylate include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N-methyl -N-ethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate, N, N-dibutylaminobutyl (meth) acrylate, N, N-dihexylaminoethyl (meth) acrylate, N, N-dioctyl Aminoethyl (meth) acrylate, esters of acrylic acid or methacrylic acid such as acryloyl morpholine and the like. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) Particularly preferred are acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate, and the like.
また、上記Ｎ,Ｎ-ジ置換アミノアルキル(メタ)アクリルアミドとしては、Ｎ,Ｎ-ジメチルアミノメチル(メタ)アクリルアミド、Ｎ,Ｎ-ジメチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジメチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジメチルアミノブチル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノブチル(メタ)アクリルアミド、Ｎ-メチル-Ｎ-エチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジプロピルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジブチルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジブチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジブチルアミノブチル(メタ)アクリルアミド、Ｎ,Ｎ-ジヘキシルアミノエチル(メタ)アクリルアミド、Ｎ,Ｎ-ジヘキシルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジオクチルアミノプロピル(メタ)アクリルアミド等のアクリルアミド化合物又はメタクリルアミド化合物等が挙げられる。これらの中でも、Ｎ,Ｎ-ジメチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジエチルアミノプロピル(メタ)アクリルアミド、Ｎ,Ｎ-ジオクチルアミノプロピル(メタ)アクリルアミド等が特に好ましい。 Examples of the N, N-disubstituted aminoalkyl (meth) acrylamide include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( (Meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N -Methyl-N-ethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dibutylaminobutyl (meth) acrylamide, N, N-dihexylaminoethyl ( Data) acrylamide, N, N-dihexyl-aminopropyl (meth) acrylamide, N, N-acrylamide compounds such as dioctyl aminopropyl (meth) acrylamide or methacrylamide compounds and the like. Among these, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide and the like are particularly preferable.
上記ニトリル基を含有する単量体としては、(メタ)アクリロニトリル、シアン化ビニリデン等が挙げられる。これらニトリル基含有単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 Examples of the nitrile group-containing monomer include (meth) acrylonitrile, vinylidene cyanide, and the like. These nitrile group-containing monomers may be used alone or in a combination of two or more.
上記ヒドロキシル基を含有する単量体としては、１分子中に少なくとも１つの第１級、第２級及び第３級ヒドロキシル基を有する重合性単量体が挙げられる。かかる単量体としては、ヒドロキシル基含有不飽和カルボン酸系単量体、ヒドロキシル基含有ビニルエーテル系単量体、ヒドロキシル基含有ビニルケトン系単量体等が挙げられる。ここで、ヒドロキシル基含有単量体の具体例としては、２-ヒドロキシエチル(メタ)アクリレート、２-ヒドロキシプロピル(メタ)アクリレート、３-ヒドロキシプロピル(メタ)アクリレート、２-ヒドロキシブチル(メタ)アクリレート、３-ヒドロキシブチル(メタ)アクリレート、４-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類；ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール（アルキレングリコール単位数は、例えば、２〜２３である）のモノ(メタ)アクリレート類；Ｎ-ヒドロキシメチル(メタ)アクリルアミド、Ｎ-(２-ヒドロキシエチル)(メタ)アクリルアミド、Ｎ,Ｎ-ビス(２-ヒドロキシエチル)(メタ)アクリルアミド等のヒドロキシル基含有不飽和アミド類；ｏ-ヒドロキシスチレン、ｍ-ヒドロキシスチレン、ｐ-ヒドロキシスチレン、ｏ-ヒドロキシ-α-メチルスチレン、ｍ-ヒドロキシ-α-メチルスチレン、ｐ-ヒドロキシ-α-メチルスチレン、ｐ-ビニルベンジルアルコール等のヒドロキシル基含有ビニル芳香族化合物類等が挙げられる。これらの中でも、ヒドロキシル基含有不飽和カルボン酸系単量体、ヒドロキシアルキル(メタ)アクリレート類、ヒドロキシル基含有ビニル芳香族化合物が好ましく、ヒドロキシル基含有不飽和カルボン酸系単量体が特に好ましい。ここで、ヒドロキシル基含有不飽和カルボン酸系単量体としては、アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸等のエステル、アミド、無水物等の誘導体が挙げられ、これらの中でも、アクリル酸、メタクリル酸等のエステルが特に好ましい。これらヒドロキシル基含有単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 Examples of the monomer containing a hydroxyl group include polymerizable monomers having at least one primary, secondary, and tertiary hydroxyl group in one molecule. Examples of such monomers include hydroxyl group-containing unsaturated carboxylic acid monomers, hydroxyl group-containing vinyl ether monomers, hydroxyl group-containing vinyl ketone monomers, and the like. Here, specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 23 Mono (meth) acrylates; N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, etc. Hydroxyl group-containing unsaturated amides; o-hydroxy Hydroxyl group-containing vinyl such as tylene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl alcohol Aromatic compounds etc. are mentioned. Among these, hydroxyl group-containing unsaturated carboxylic acid monomers, hydroxyalkyl (meth) acrylates, and hydroxyl group-containing vinyl aromatic compounds are preferable, and hydroxyl group-containing unsaturated carboxylic acid monomers are particularly preferable. Here, examples of the hydroxyl group-containing unsaturated carboxylic acid-based monomer include esters such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, amides, and anhydrides. Among these, Particularly preferred are esters such as acrylic acid and methacrylic acid. These hydroxyl group-containing monomers may be used alone or in a combination of two or more.
上記カルボキシル基を含有する単量体としては、(メタ)アクリル酸、マレイン酸、フマル酸、イタコン酸、テトラコン酸、桂皮酸等の不飽和カルボン酸類；フタル酸、コハク酸、アジピン酸等の非重合性多価カルボン酸と、(メタ)アリルアルコール、２-ヒドロキシエチル(メタ)アクリレート等の水酸基含有不飽和化合物とのモノエステルのような遊離カルボキシル基含有エステル類及びその塩等が挙げられる。これらの中でも、不飽和カルボン酸類が特に好ましい。これらカルボキシル基含有単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 Examples of the monomer containing a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid and cinnamic acid; non-phthalic acids such as phthalic acid, succinic acid and adipic acid. Examples thereof include free carboxyl group-containing esters such as monoesters of a polymerizable polycarboxylic acid and a hydroxyl group-containing unsaturated compound such as (meth) allyl alcohol and 2-hydroxyethyl (meth) acrylate, and salts thereof. Of these, unsaturated carboxylic acids are particularly preferred. These carboxyl group-containing monomers may be used alone or in a combination of two or more.
上記エポキシ基を含有する単量体としては、(メタ)アリルグリシジルエーテル、グリシジル(メタ)アクリレート、３,４-オキシシクロヘキシル(メタ)アクリレート等が挙げられる。これらエポキシ基含有単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 Examples of the monomer containing an epoxy group include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, and 3,4-oxycyclohexyl (meth) acrylate. These epoxy group-containing monomers may be used alone or in combination of two or more.
上記含窒素複素環基を含有する単量体において、該含窒素複素環としては、ピロール、ヒスチジン、イミダゾール、トリアゾリジン、トリアゾール、トリアジン、ピリジン、ピリミジン、ピラジン、インドール、キノリン、プリン、フェナジン、プテリジン、メラミン等が挙げられる。なお、該含窒素複素環は、他のヘテロ原子を環中に含んでいてもよい。ここで、含窒素複素環基としてピリジル基を含有する単量体としては、２-ビニルピリジン、３-ビニルピリジン、４-ビニルピリジン、５-メチル-２-ビニルピリジン、５-エチル-２-ビニルピリジン等のピリジル基含有ビニル化合物等が挙げられ、これらの中でも、２-ビニルピリジン、４-ビニルピリジン等が特に好ましい。これら含窒素複素環基含有単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 In the monomer containing the nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic ring includes pyrrole, histidine, imidazole, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indole, quinoline, purine, phenazine, pteridine, Examples include melamine. The nitrogen-containing heterocycle may contain other heteroatoms in the ring. Here, as a monomer containing a pyridyl group as a nitrogen-containing heterocyclic group, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2- Examples include vinyl compounds containing a pyridyl group such as vinyl pyridine, among which 2-vinyl pyridine, 4-vinyl pyridine and the like are particularly preferable. These nitrogen-containing heterocyclic group-containing monomers may be used alone or in a combination of two or more.
上記アルコキシシリル基を含有する単量体としては、(メタ)アクリロキシメチルトリメトキシシラン、(メタ)アクリロキシメチルメチルジメトキシシラン、(メタ)アクリロキシメチルジメチルメトキシシラン、(メタ)アクリロキシメチルトリエトキシシラン、(メタ)アクリロキシメチルメチルジエトキシシラン、(メタ)アクリロキシメチルジメチルエトキシシラン、(メタ)アクリロキシメチルトリプロポキシシラン、(メタ)アクリロキシメチルメチルジプロポキシシラン、(メタ)アクリロキシメチルジメチルプロポキシシラン、γ-(メタ)アクリロキシプロピルトリメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジメトキシシラン、γ-(メタ)アクリロキシプロピルジメチルメトキシシラン、γ-(メタ)アクリロキシプロピルトリエトキシシラン、γ-(メタ)アクリロキシプロピルメチルジエトキシシラン、γ-(メタ)アクリロキシプロピルジメチルエトキシシラン、γ-(メタ)アクリロキシプロピルトリプロポキシシラン、γ-(メタ)アクリロキシプロピルメチルジプロポキシシラン、γ-(メタ)アクリロキシプロピルジメチルプロポキシシラン、γ-(メタ)アクリロキシプロピルメチルジフェノキシシラン、γ-(メタ)アクリロキシプロピルジメチルフェノキシシラン、γ-(メタ)アクリロキシプロピルメチルジベンジロキシシラン、γ-(メタ)アクリロキシプロピルジメチルベンジロキシシラン、トリメトキシビニルシラン、トリエトキシビニルシラン、６-トリメトキシシリル-１,２-ヘキセン、ｐ-トリメトキシシリルスチレン等が挙げられる。これらアルコキシシリル基含有単量体は、一種単独で用いてもよく、二種以上を組み合せて用いてもよい。 Examples of the monomer containing the alkoxysilyl group include (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethylmethyldimethoxysilane, (meth) acryloxymethyldimethylmethoxysilane, (meth) acryloxymethyltrimethoxysilane. Ethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethyldimethylethoxysilane, (meth) acryloxymethyltripropoxysilane, (meth) acryloxymethylmethyldipropoxysilane, (meth) acryloxy Methyldimethylpropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyltri Ethoxysilane, γ -(Meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ -(Meth) acryloxypropyldimethylpropoxysilane, γ- (meth) acryloxypropylmethyldiphenoxysilane, γ- (meth) acryloxypropyldimethylphenoxysilane, γ- (meth) acryloxypropylmethyldibenzyloxysilane, γ- (meth) acryloxypropyldimethylbenzyloxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 6-trimethoxysilyl-1,2-hexene, p-trimethoxysilylstyrene and the like can be mentioned. These alkoxysilyl group-containing monomers may be used alone or in a combination of two or more.
本発明においては、上記極性基含有単量体の天然ゴム分子へのグラフト重合を、乳化重合で行う。ここで、該乳化重合においては、一般的に、天然ゴムラテックスに水及び必要に応じて乳化剤を加えた溶液中に、上記極性基含有単量体を加え、更に重合開始剤を加えて、所定の温度で撹拌して極性基含有単量体を重合させることが好ましい。なお、上記極性基含有単量体の天然ゴムラテックスへの添加においては、予め天然ゴムラテックス中に乳化剤を加えてもよいし、極性基含有単量体を乳化剤で乳化した後に天然ゴムラテックス中に加えてもよい。なお、天然ゴムラテックス及び／又は極性基含有単量体の乳化に使用できる乳化剤としては、特に限定されず、ポリオキシエチレンラウリルエーテル等のノニオン系の界面活性剤が挙げられる。 In the present invention, the graft polymerization of the polar group-containing monomer to the natural rubber molecule is carried out by emulsion polymerization. Here, in the emulsion polymerization, generally, the polar group-containing monomer is added to a solution obtained by adding water and, if necessary, an emulsifier to a natural rubber latex, and a polymerization initiator is further added. It is preferable to polymerize the polar group-containing monomer by stirring at the temperature. In addition, in the addition of the polar group-containing monomer to the natural rubber latex, an emulsifier may be added to the natural rubber latex in advance, or after emulsifying the polar group-containing monomer with the emulsifier, May be added. In addition, it does not specifically limit as an emulsifier which can be used for emulsification of a natural rubber latex and / or a polar group containing monomer, Nonionic surfactants, such as polyoxyethylene lauryl ether, are mentioned.
上記重合開始剤としては、特に制限はなく、種々の乳化重合用の重合開始剤を用いることができ、その添加方法についても特に制限はない。一般に用いられる重合開始剤の例としては、過酸化ベンゾイル、過酸化水素、クメンハイドロパーオキサイド、tert-ブチルハイドロパーオキサイド、ジ-tert-ブチルパーオキサイド、２,２-アゾビスイソブチロニトリル、２,２-アゾビス(２-ジアミノプロパン)ヒドロクロライド、２,２-アゾビス(２-ジアミノプロパン)ジヒドロクロライド、２,２-アゾビス(２,４-ジメチルバレロニトリル)、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等が挙げられる。なお、重合温度を低下させるためには、レドックス系の重合開始剤を用いることが好ましい。かかるレドックス系重合開始剤において、過酸化物と組み合せる還元剤としては、例えば、テトラエチレンペンタミン、メルカプタン類、酸性亜硫酸ナトリウム、還元性金属イオン、アスコルビン酸等が挙げられる。レドックス系重合開始剤における過酸化物と還元剤との好ましい組み合せとしては、tert-ブチルハイドロパーオキサイドとテトラエチレンペンタミンとの組み合せ等が挙げられる。 There is no restriction | limiting in particular as said polymerization initiator, The polymerization initiator for various emulsion polymerization can be used, and there is no restriction | limiting in particular also about the addition method. Examples of commonly used polymerization initiators include benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2-diaminopropane) dihydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), potassium persulfate, sodium persulfate And ammonium persulfate. In order to lower the polymerization temperature, it is preferable to use a redox polymerization initiator. Examples of the reducing agent to be combined with the peroxide in the redox polymerization initiator include tetraethylenepentamine, mercaptans, acidic sodium sulfite, reducing metal ions, ascorbic acid and the like. A preferred combination of a peroxide and a reducing agent in the redox polymerization initiator includes a combination of tert-butyl hydroperoxide and tetraethylenepentamine.
上記変性天然ゴムに上記カーボンブラックを配合して、ゴム組成物の加工性を低下させることなく低ロス性及び耐摩耗性を向上させるには、各天然ゴム分子に上記極性基含有単量体が少量且つ均一に導入されることが重要であるため、上記重合開始剤の添加量は、上記極性基含有単量体に対し1〜100mol％の範囲が好ましく、10〜100mol％の範囲が更に好ましい。 In order to improve the low loss and wear resistance without reducing the processability of the rubber composition by blending the carbon black with the modified natural rubber, the polar group-containing monomer is added to each natural rubber molecule. Since it is important that the polymerization initiator is introduced in a small amount and uniformly, the addition amount of the polymerization initiator is preferably in the range of 1 to 100 mol%, more preferably in the range of 10 to 100 mol% with respect to the polar group-containing monomer. .
上述した各成分を反応容器に仕込み、30〜80℃で10分〜7時間反応させることで、天然ゴム分子に上記極性基含有単量体がグラフト共重合した変性天然ゴムラテックスが得られる。また、該変性天然ゴムラテックスを凝固させ、洗浄後、真空乾燥機、エアドライヤー、ドラムドライヤー等の乾燥機を用いて乾燥することで変性天然ゴムが得られる。ここで、変性天然ゴムラテックスを凝固するのに用いる凝固剤としては、特に限定されるものではないが、ギ酸、硫酸等の酸や、塩化ナトリウム等の塩が挙げられる。 Each component described above is charged into a reaction vessel and reacted at 30 to 80 ° C. for 10 minutes to 7 hours, whereby a modified natural rubber latex in which the polar group-containing monomer is graft copolymerized with a natural rubber molecule is obtained. The modified natural rubber latex is coagulated, washed, and then dried using a dryer such as a vacuum dryer, an air dryer, a drum dryer or the like to obtain a modified natural rubber. Here, the coagulant used for coagulating the modified natural rubber latex is not particularly limited, and examples thereof include acids such as formic acid and sulfuric acid, and salts such as sodium chloride.
上記変性天然ゴムラテックス及び変性天然ゴムにおいて、上記極性基含有単量体のグラフト量は、天然ゴムラテックス中のゴム成分に対して0.01〜5.0質量％の範囲が好ましく、0.01〜1.0質量％の範囲が更に好ましい。極性基含有単量体のグラフト量が0.01質量％未満では、ゴム組成物の低ロス性及び耐摩耗性を十分に改良できないことがある。また、極性基含有単量体のグラフト量が5.0質量％を超えると、粘弾性、Ｓ−Ｓ特性（引張試験機における応力−歪曲線）等の天然ゴム本来の物理特性を大きく変えてしまい、天然ゴム本来の優れた物理特性が損なわれると共に、ゴム組成物の加工性が大幅に悪化するおそれがある。 In the modified natural rubber latex and the modified natural rubber, the graft amount of the polar group-containing monomer is preferably in the range of 0.01 to 5.0% by mass, and in the range of 0.01 to 1.0% by mass with respect to the rubber component in the natural rubber latex. Is more preferable. If the graft amount of the polar group-containing monomer is less than 0.01% by mass, the low loss and wear resistance of the rubber composition may not be sufficiently improved. Moreover, when the graft amount of the polar group-containing monomer exceeds 5.0% by mass, the natural physical properties of natural rubber such as viscoelasticity and SS characteristics (stress-strain curve in a tensile tester) are greatly changed. The inherent physical properties of natural rubber are impaired, and the processability of the rubber composition may be greatly deteriorated.
本発明のゴム組成物に用いるカーボンブラックは、トルエン着色透過度が90％以上であって、表面自由エネルギーとセチルトリメチルアンモニウムブロミド吸着比表面積(ＣＴＢＡ)（m2/g）が下記式（I）：
γd s＜２８７×ｌｎ(ＣＴＡＢ)−９８９ ・・・ （I）
[式中、γd sはインバースガスクロマトグラフィーを使用して算出した表面自由エネルギー（mJ/m2）である]の関係を満たす。
The carbon black used in the rubber composition of the present invention has a toluene coloring permeability of 90% or more, and the surface free energy and the cetyltrimethylammonium bromide adsorption specific surface area (CTBA) (m 2 / g) are represented by the following formula (I) :
γ d s <287 × ln (CTAB) −989 (I)
Where γ d s is the surface free energy (mJ / m 2 ) calculated using inverse gas chromatography.
上記式（I）に示すように、表面自由エネルギーを少なくすることにより、分散性を改善することができる。ＣＴＡＢの増加とともに一般的には分散性の低下が見られ、ゴム組成物の加工性が悪化する。これは微粒径化（ＣＴＡＢの増加）とともに表面自由エネルギー（γd s）が増加するためである。ここで、表面自由エネルギー（γd s）は分子間力の大きさを示す。即ち、この値が大きいと自己凝集する。しかし、表面自由エネルギー（γd s）とＣＴＡＢが上記式（I）の関係を満たすことにより、カーボンブラック粒子間の自己凝集力を低下させることができ、分散性を改善することができる。従って、変性天然ゴムに対して上記カーボンブラックを配合する際に、カーボンブラックが自己凝集を起こすことなく分散し、低ロス性及び耐摩耗性に優れたゴム組成物を提供することができる。 As shown in the above formula (I), the dispersibility can be improved by reducing the surface free energy. A decrease in dispersibility is generally observed with an increase in CTAB, and the processability of the rubber composition deteriorates. This is because the surface free energy (γ d s ) increases as the particle size is reduced (increase in CTAB). Here, the surface free energy (γ d s ) indicates the magnitude of the intermolecular force. That is, when this value is large, self-aggregation occurs. However, when the surface free energy (γ d s ) and CTAB satisfy the relationship of the above formula (I), the self-aggregation force between the carbon black particles can be reduced, and the dispersibility can be improved. Therefore, when the carbon black is blended with the modified natural rubber, the carbon black is dispersed without causing self-aggregation, and a rubber composition excellent in low loss and wear resistance can be provided.
表面自由エネルギー(γd s)（mJ/m2）は以下のように算出する。まず、内径3mmのステンレス製カラムに、篩を用いて造粒径0.25〜0.75mmに選別したカーボンブラックを充填し、該カーボンブラックを吸着層としてガスクロマトグラフィーで測定を行う。測定は、180℃に保持したカラムにキャリアーガスとしてヘリウムを30ml/minの流量で流通させて行う。プローブには、メタン、Ｃ４（ｎ-ブタン）、Ｃ５（ｎ-ペンタン）、Ｃ６（ｎ-ヘキサン）を用いる。上記プローブを0.1μl注入し、それぞれのリテンションタイムを求める。 The surface free energy (γ d s ) (mJ / m 2 ) is calculated as follows. First, carbon black selected to have a particle size of 0.25 to 0.75 mm using a sieve is packed in a stainless steel column having an inner diameter of 3 mm, and measurement is performed by gas chromatography using the carbon black as an adsorption layer. The measurement is performed by flowing helium as a carrier gas at a flow rate of 30 ml / min through a column maintained at 180 ° C. As the probe, methane, C4 (n-butane), C5 (n-pentane), or C6 (n-hexane) is used. Inject 0.1 μl of the probe and determine the retention time for each.
各プローブのリテンションタイムより、無限希釈保持容積（Ｖn）を下記式（II）：
Ｖn＝Ｄｊ（ｔr−ｔm）×（１−Ｐw／Ｐp）×Ｔc／Ｔf ・・・ （II）
により算出する。ここで、Ｄはセッケン膜流量計で測定された未補正流量（m3）、ｔrは各プローブのリテンションタイム（分）、ｔmはメタンのリテンションタイム（分）、Ｐwはキャリアーガス温度の飽和蒸気圧（Pa）、Ｐpはキャリアーガスの流れの圧力（Pa）、Ｔcはカラム温度（K）、Ｔfはキャリアーガス温度（K）である。また、ｊはJames-Martin因子であり、下記式（III）：
ｊ＝［３（Ｐi／Ｐou）2−１］／［２（Ｐi／Ｐou）3−１］ ・・・ （III）
によって算出される。ここで、Ｐiはカラム入り口での圧力（kgf/cm3）、Ｐouはカラム出口での圧力（kgf/cm3）である。
From the retention time of each probe, the infinite dilution holding volume (V n ) is expressed by the following formula (II):
V n = Dj (t r -t m) × (1-P w / P p) × T c / T f ··· (II)
Calculated by Here, D is uncorrected flow rate is measured with soap film flow meter (m 3), t r is in each probe retention time (min), t m methane retention time (min), P w is the carrier gas temperature saturated vapor pressure of (Pa), a P p is the carrier gases flow pressure (Pa), T c is the column temperature (K), T f is the carrier gas temperature (K). J is a James-Martin factor, and the following formula (III):
j = [3 (P i / P ou ) 2 −1] / [2 (P i / P ou ) 3 −1] (III)
Is calculated by Here, P i is the pressure at the column inlet (kgf / cm 3 ), and P ou is the pressure at the column outlet (kgf / cm 3 ).
次いで、ＣＨ2基１モルあたりの吸着自由エネルギーの変化量（ΔＧCH2）を下記式（IV）：
ΔＧCH2＝−ＲＴｌｎ(ＶN(n)／ＶN(n+1)) ・・・ （IV）
により算出する。ここで、Ｖ(n+1)はＶ(n)より炭素数が１つ多い直鎖のアルカンの無限希釈保持容積である。
Next, the amount of change in adsorption free energy per mole of CH 2 group (ΔG CH2 ) is expressed by the following formula (IV):
ΔG CH2 = -RTln (V N ( n) / V N (n + 1)) ··· (IV)
Calculated by Here, V (n + 1) is an infinite dilution holding volume of a linear alkane having one carbon number larger than V (n) .
そして表面自由エネルギー（γd s）を下記式（V）：
γd s＝ΔＧCH2 2／（４ＮA 2×ａCH2 2×γCH2） ・・・ （V）
により算出する。ここで、ＮAはアボガドロ数［6.022×1023］（mol-1）、ａCH2はＣＨ2基１個あたりの接触面積［0.06×10-18］（m2）、γCH2はＣＨ2基の表面自由エネルギーの分散相互作用［35.6+0.058(293-Ｔ)］（J/m2）（Ｔは温度K）である。
And the surface free energy (γ d s ) is expressed by the following formula (V):
γ d s = ΔG CH2 2 / (4N A 2 × a CH2 2 × γ CH2) ··· (V)
Calculated by Here, N A is Avogadro's number [6.022 × 10 23 ] (mol −1 ), a CH2 is the contact area per CH 2 group [0.06 × 10 −18 ] (m 2 ), and γ CH2 is the CH 2 group. The surface free energy dispersion interaction [35.6 + 0.058 (293-T)] (J / m 2 ) (T is temperature K).
また、上記トルエン着色透過度が低い場合は、補強性の阻害因子となるタール分が増加し、補強性の低下を招く。特に、トルエン着色透過度が90％未満の場合は、補強性の阻害となるタール分が多く存在するため補強性の維持が困難となる。 Moreover, when the said toluene coloring permeability | transmittance is low, the tar content used as the obstruction factor of reinforcement increases, and the reinforcement is fallen. In particular, when the toluene coloring permeability is less than 90%, it is difficult to maintain the reinforcing property because there is a large amount of tar which inhibits the reinforcing property.
上記カーボンブラックは、例えば、カーボンブラック製造炉における空気導入条件、原料油導入条件、並びに反応停止のために導入する水の導入位置、導入量及びその後の温度等を調整することで製造できる。 The carbon black can be produced, for example, by adjusting the air introduction conditions, the feedstock introduction conditions, the introduction position of the water to be introduced for stopping the reaction, the introduction amount, the subsequent temperature, and the like in the carbon black production furnace.
上記カーボンブラックの配合量は、特に限定されるものではないが、上記変性天然ゴム100質量部に対して30〜150質量部の範囲が好ましい。カーボンブラックの配合量が30質量部未満では、ゴム組成物の補強性を十分に確保することができず、150質量部を超えると、カーボンブラックの分散性が低下して、ゴム組成物の耐摩耗性が低下する。 The compounding amount of the carbon black is not particularly limited, but is preferably in the range of 30 to 150 parts by mass with respect to 100 parts by mass of the modified natural rubber. If the blending amount of the carbon black is less than 30 parts by mass, the rubber composition cannot be sufficiently strengthened. If it exceeds 150 parts by mass, the dispersibility of the carbon black is lowered, and the rubber composition has a resistance to resistance. Abrasion is reduced.
本発明のゴム組成物には、上記変性天然ゴム及びカーボンブラックの他に、ゴム業界で通常使用される配合剤、例えば、他の補強性充填剤、軟化剤、老化防止剤、加硫剤、加硫促進剤、スコーチ防止剤、亜鉛華、ステアリン酸、シランカップリング剤等を目的に応じて適宜配合することができる。これら配合剤としては、市販品を好適に使用することができる。本発明のゴム組成物は、上記変性天然ゴムに、上記カーボンブラックと、必要に応じて適宜選択した各種配合剤とを配合して、混練り、熱入れ、押出等することにより製造することができる。 In addition to the modified natural rubber and carbon black, the rubber composition of the present invention includes compounding agents usually used in the rubber industry, such as other reinforcing fillers, softeners, anti-aging agents, vulcanizing agents, Vulcanization accelerators, scorch inhibitors, zinc white, stearic acid, silane coupling agents and the like can be appropriately blended depending on the purpose. As these compounding agents, commercially available products can be suitably used. The rubber composition of the present invention can be produced by blending the above-described modified natural rubber with the carbon black and various compounding agents appropriately selected as necessary, kneading, heating, extruding, and the like. it can.
本発明のタイヤは、上記ゴム組成物をタイヤ部材のいずれかに用いたことを特徴とする。ここで、本発明のタイヤにおいては、上記ゴム組成物をトレッドゴムに用いることが特に好ましく、上記ゴム組成物をトレッドに用いたタイヤは、破壊特性及び耐摩耗性が高い。なお、本発明のタイヤに充填する気体としては、通常の或いは酸素分圧を変えた空気、又は窒素等の不活性ガスが挙げられる。 The tire according to the present invention is characterized in that the rubber composition is used in any of tire members. Here, in the tire of the present invention, it is particularly preferable to use the rubber composition as a tread rubber, and a tire using the rubber composition as a tread has high fracture characteristics and wear resistance. In addition, as gas with which the tire of the present invention is filled, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen is exemplified.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
＜変性天然ゴムの製造例＞
（天然ゴムラテックスの変性反応工程）
フィールドラテックスをラテックスセパレーター［斎藤遠心工業製］を用いて回転数7500rpmで遠心分離して、乾燥ゴム濃度60％の濃縮ラテックスを得た。この濃縮ラテックス1000gを、撹拌機及び温調ジャケットを備えたステンレス製反応容器に投入し、予め10mLの水と90mgの乳化剤［エマルゲン１１０８，花王株式会社製］をＮ,Ｎ-ジエチルアミノエチルメタクリレート3.0gに加えて乳化したものを990mLの水と共に添加し、これらを窒素置換しながら常温で30分間撹拌した。次に、重合開始剤としてtert-ブチルハイドロパーオキサイド1.2gとテトラエチレンペンタミン1.2gとを加え、40℃で30分間反応させることにより、変性天然ゴムラテックスを得た。
<Example of production of modified natural rubber>
(Natural rubber latex modification reaction process)
The field latex was centrifuged using a latex separator (manufactured by Saito Centrifugal Industries Co., Ltd.) at a rotational speed of 7500 rpm to obtain a concentrated latex having a dry rubber concentration of 60%. 1000 g of this concentrated latex is put into a stainless steel reaction vessel equipped with a stirrer and a temperature control jacket, and 10 mL of water and 90 mg of emulsifier [Emulgen 1108, manufactured by Kao Corporation] are added in advance to 3.0 g of N, N-diethylaminoethyl methacrylate. The emulsified product was added with 990 mL of water, and the mixture was stirred at room temperature for 30 minutes while purging with nitrogen. Next, 1.2 g of tert-butyl hydroperoxide and 1.2 g of tetraethylenepentamine were added as polymerization initiators and reacted at 40 ° C. for 30 minutes to obtain a modified natural rubber latex.
（凝固及び乾燥工程）
上記変性天然ゴムラテックスにギ酸を加えｐＨを4.7に調整し、変性天然ゴムラテックスを凝固させた。このようにして得られた固形物をクレーパーで５回処理し、シュレッダーに通してクラム化した後、熱風式乾燥機により110℃で210分間乾燥して変性天然ゴムを得た。このようにして得られた変性天然ゴムの質量から、単量体として加えたＮ,Ｎ-ジエチルアミノエチルメタクリレートの転化率が100％であることが確認された。また、該変性天然ゴムを石油エーテルで抽出し、更にアセトンとメタノールの２：１混合溶媒で抽出することによりホモポリマーの分離を試みたが、抽出物を分析したところホモポリマーは検出されず、添加した単量体の100％が天然ゴム分子に導入されていることが確認された。従って、得られた変性天然ゴムにおける単量体のグラフト量は、天然ゴムラテックス中のゴム成分に対して0.5質量％である。
(Coagulation and drying process)
Formic acid was added to the modified natural rubber latex to adjust the pH to 4.7 to coagulate the modified natural rubber latex. The solid thus obtained was treated five times with a creper, passed through a shredder and crushed, and then dried at 110 ° C. for 210 minutes with a hot air dryer to obtain a modified natural rubber. From the mass of the modified natural rubber thus obtained, it was confirmed that the conversion rate of N, N-diethylaminoethyl methacrylate added as a monomer was 100%. In addition, the modified natural rubber was extracted with petroleum ether and further extracted with a 2: 1 mixed solvent of acetone and methanol, but when the extract was analyzed, the homopolymer was not detected. It was confirmed that 100% of the added monomer was introduced into the natural rubber molecule. Therefore, the graft amount of the monomer in the resulting modified natural rubber is 0.5% by mass with respect to the rubber component in the natural rubber latex.
＜天然ゴムの製造例＞
上記天然ゴムラテックスを変性反応工程を経ずに、直接、凝固及び乾燥させて天然ゴムを調製した。
<Examples of natural rubber production>
Natural rubber was prepared by directly coagulating and drying the natural rubber latex without undergoing a modification reaction step.
＜カーボンブラックの製造例＞
表１に示す条件でカーボンブラックをそれぞれ製造した。また、カーボンブラックの物性に関して、表面自由エネルギーについては上述した方法により算出し、トルエン着色透過度及びセチルトリメチルアンモニウムブロミド吸着比表面積を下記の方法で測定した。
<Production example of carbon black>
Carbon black was produced under the conditions shown in Table 1. Regarding the physical properties of carbon black, the surface free energy was calculated by the method described above, and the toluene color permeability and the cetyltrimethylammonium bromide adsorption specific surface area were measured by the following methods.
（１）セチルトリメチルアンモニウムブロミド吸着比表面積
ＡＳＴＭ Ｄ３７６５−９２に準拠して、カーボンブラックの単位質量当りの比表面積（m2/g）を測定した。
(1) Cetyltrimethylammonium bromide adsorption specific surface area Based on ASTM D3765-92, the specific surface area (m 2 / g) per unit mass of carbon black was measured.
（２）トルエン着色透過度
ＪＩＳ Ｋ６２１８(１９９７)の第８項Ｂ法に準拠して、カーボンブラックとトルエン混合物の濾液の透過率パーセントを測定し、純粋なトルエンとの百分率で表示した。
(2) Permeability of Toluene Coloring Permeability of the filtrate of the carbon black and toluene mixture was measured according to JIS K6218 (1997), Item 8 Method B, and expressed as a percentage of pure toluene.
＜ゴム組成物の実施例１＞
上記変性天然ゴム100質量部に対して、上記製造例１で得たカーボンブラックを50質量部、ステアリン酸を2質量部、老化防止剤６Ｃ（Ｎ-(１,３-ジメチルブチル)-Ｎ’-フェニル-ｐ-フェニレンジアミン）を1質量部、亜鉛華を3質量部、加硫促進剤ＤＺ（Ｎ,Ｎ’-ジシクロヘキシル-２-ベンゾチアゾリルスルフェンアミド）を0.8質量部、及び硫黄を1質量部配合してなるゴム組成物を混練りして調製した。
<Example 1 of rubber composition>
50 parts by mass of carbon black obtained in Production Example 1 above, 2 parts by mass of stearic acid, and anti-aging agent 6C (N- (1,3-dimethylbutyl) -N ′ with respect to 100 parts by mass of the modified natural rubber -Phenyl-p-phenylenediamine) 1 part by weight, zinc white 3 parts by weight, vulcanization accelerator DZ (N, N'-dicyclohexyl-2-benzothiazolylsulfenamide) 0.8 parts by weight, and sulfur A rubber composition containing 1 part by mass was prepared by kneading.
＜ゴム組成物の比較例１〜３＞
比較のため、変性天然ゴムの代わりに天然ゴムを用いて上記実施例１と同様の配合処方によりゴム組成物を調製した（比較例１）。また、上記変性天然ゴム又は天然ゴムと上記製造例２で得たカーボンブラックを用いて上記実施例１と同様の配合処方によりゴム組成物を調製した（比較例２及び３）。
<Comparative Examples 1-3 of Rubber Composition>
For comparison, a rubber composition was prepared by the same formulation as in Example 1 above using natural rubber instead of modified natural rubber (Comparative Example 1). Moreover, the rubber composition was prepared by the same mixing | blending prescription as the said Example 1 using the said modified natural rubber or natural rubber, and the carbon black obtained by the said manufacture example 2 (comparative examples 2 and 3).
実施例１及び比較例１〜３で得たゴム組成物をそれぞれ通常の条件で加硫して得た加硫ゴムに対し、下記の方法で、tanδ及び耐摩耗性を測定・評価した。結果を表２に示す。 With respect to the vulcanized rubber obtained by vulcanizing the rubber compositions obtained in Example 1 and Comparative Examples 1 to 3 under normal conditions, tan δ and abrasion resistance were measured and evaluated by the following methods. The results are shown in Table 2.
（１）tanδ
レオメトリックス社製の粘弾性測定装置を用いて、温度50℃、周波数15Hz、歪5％でtanδを測定し、表２における比較例３のtanδを100として指数表示した。指数値が小さい程、低ロス性に優れることを示す。
(1) tanδ
Using a viscoelasticity measuring device manufactured by Rheometrics, tan δ was measured at a temperature of 50 ° C., a frequency of 15 Hz, and a strain of 5%. It shows that it is excellent in low-loss property, so that an index value is small.
（２）耐摩耗性
ランボーン型摩耗試験機を用い、室温におけるスリップ率60％での摩耗量を測定し、表２における比較例３の摩耗量の逆数を100として指数表示した。指数値が大きい程、摩耗量が少なく、耐摩耗性に優れることを示す。
(2) Abrasion resistance Using a Ramborn-type abrasion tester, the amount of wear at a slip rate of 60% at room temperature was measured, and the reciprocal of the amount of wear in Comparative Example 3 in Table 2 was taken as an index. The larger the index value, the smaller the wear amount and the better the wear resistance.
実施例１及び比較例１で用いた上記式（I）の関係を満たす分散性に優れたカーボンブラックを、それぞれ比較例２及び３で用いたカーボンブラックと比べると、ゴム組成物の低ロス性が向上していることが分かる。 When the carbon black excellent in dispersibility satisfying the relationship of the above formula (I) used in Example 1 and Comparative Example 1 is compared with the carbon black used in Comparative Examples 2 and 3, respectively, the low loss property of the rubber composition It can be seen that is improved.
また、実施例１及び比較例１と比較例２及び３の比較から、上記変性天然ゴムの使用により耐摩耗性が高いことが分かる。 Moreover, it turns out that abrasion resistance is high by use of the said modified natural rubber from the comparison of Example 1, Comparative Example 1, and Comparative Examples 2 and 3.
さらに、表２から明らかなように、天然ゴムに代えて極性基含有単量体で変性した変性天然ゴムと、上記式（I）の関係を満たすカーボンブラックとを用いることで、両者の相乗効果によってゴム組成物の低ロス性を大幅に改善できることが分かる。 Furthermore, as is clear from Table 2, the synergistic effect of both is obtained by using a modified natural rubber modified with a polar group-containing monomer instead of natural rubber and carbon black satisfying the relationship of the above formula (I). It can be seen that the low loss property of the rubber composition can be greatly improved.
Claims (6)
γd s＜２８７×ｌｎ(ＣＴＡＢ)−９８９ ・・・ （I）
[式中、γd sはインバースガスクロマトグラフィーを使用して算出した表面自由エネルギー（mJ/m2）である]の関係を満たすカーボンブラックを配合してなるゴム組成物。 To a modified natural rubber obtained by adding a polar group-containing monomer to natural rubber latex, graft-polymerizing the polar group-containing monomer to a natural rubber molecule in the natural rubber latex, and further coagulating and drying. The coloring permeability is 90% or more, and the surface free energy and the cetyltrimethylammonium bromide adsorption specific surface area (CTAB) (m 2 / g) are represented by the following formula (I):
γ d s <287 × ln (CTAB) −989 (I)
A rubber composition comprising carbon black satisfying the relationship [wherein γ d s is a surface free energy (mJ / m 2 ) calculated using inverse gas chromatography].
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| JP2007238816A (en) * | 2006-03-09 | 2007-09-20 | Bridgestone Corp | Rubber composition and tire using it |
| WO2014189826A1 (en) | 2013-05-20 | 2014-11-27 | Cabot Corporation | Elastomer composites, blends and methods for preparing same |
| US9156955B2 (en) | 2009-09-17 | 2015-10-13 | Cabot Corporation | Formation of latex coagulum composite |
| WO2017011561A1 (en) | 2015-07-15 | 2017-01-19 | Cabot Corporation | Methods of making an elastomer composite reinforced with silica and products containing same |
| WO2017011548A1 (en) | 2015-07-15 | 2017-01-19 | Cabot Corporation | Methods of making an elastomer composite reinforced with silica and products containing same |
| US10030128B2 (en) | 2009-09-17 | 2018-07-24 | Cabot Corporation | Elastomer composite blends, method and apparatus for producing same |
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Cited By (10)
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| JP2007238816A (en) * | 2006-03-09 | 2007-09-20 | Bridgestone Corp | Rubber composition and tire using it |
| US9156955B2 (en) | 2009-09-17 | 2015-10-13 | Cabot Corporation | Formation of latex coagulum composite |
| US10030128B2 (en) | 2009-09-17 | 2018-07-24 | Cabot Corporation | Elastomer composite blends, method and apparatus for producing same |
| WO2014189826A1 (en) | 2013-05-20 | 2014-11-27 | Cabot Corporation | Elastomer composites, blends and methods for preparing same |
| WO2017011561A1 (en) | 2015-07-15 | 2017-01-19 | Cabot Corporation | Methods of making an elastomer composite reinforced with silica and products containing same |
| WO2017011548A1 (en) | 2015-07-15 | 2017-01-19 | Cabot Corporation | Methods of making an elastomer composite reinforced with silica and products containing same |
| DE112016003162T5 (en) | 2015-07-15 | 2018-04-19 | Cabot Corporation | Silica reinforced elastomer composites and these comprehensive products |
| DE112016003169B4 (en) | 2015-07-15 | 2024-05-16 | Cabot Corporation | METHOD FOR PRODUCING AN ELASTOMER COMPOSITE, SOLID SILICA-CONTAINING CONTINUOUS RUBBER PHASE ARTICLE OBTAINABLE BY SAID METHOD, AND METHOD FOR PRODUCING A RUBBER MIXTURE AND A RUBBER ARTICLE |
| DE112016003168B4 (en) | 2015-07-15 | 2024-08-08 | Cabot Corporation | METHOD FOR PRODUCING A SILICA ELASTOMER COMPOSITE AND PRODUCTS CONTAINING SAME |
| WO2019094551A1 (en) | 2017-11-10 | 2019-05-16 | Cabot Corporation | Methods of producing an elastomer compound and elastomer compounds |
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